WO2015146226A1 - 光電変換素子、電気モジュール及び光電変換素子の製造方法 - Google Patents

光電変換素子、電気モジュール及び光電変換素子の製造方法 Download PDF

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Publication number
WO2015146226A1
WO2015146226A1 PCT/JP2015/050850 JP2015050850W WO2015146226A1 WO 2015146226 A1 WO2015146226 A1 WO 2015146226A1 JP 2015050850 W JP2015050850 W JP 2015050850W WO 2015146226 A1 WO2015146226 A1 WO 2015146226A1
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Prior art keywords
substrate
photoelectric conversion
electrode
conversion element
wall portion
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PCT/JP2015/050850
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English (en)
French (fr)
Japanese (ja)
Inventor
智弘 大塚
中嶋　節男
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積水化学工業株式会社
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Priority to CN201580015418.2A priority Critical patent/CN106104729B/zh
Priority to KR1020167026103A priority patent/KR20160138032A/ko
Publication of WO2015146226A1 publication Critical patent/WO2015146226A1/ja

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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 a photoelectric conversion element, an electric module, and a method for manufacturing a photoelectric conversion element.
  • the semiconductor layer 103 Surrounding the semiconductor layer 103 is the first electrode 104 on which the semiconductor layer 103 is formed, the second electrode 107 on which the counter conductive film 106 provided on the counter substrate 105 so as to face the transparent conductive film 102 is formed. At the same time, the outer peripheral wall portion of the first electrode 104 and the outer peripheral wall portion of the second electrode 107 are bonded together to form an internal space S, and a sealing material 108 that seals the internal space S is injected into the internal space S.
  • the electrolyte solution 109 is provided.
  • the transparent substrate 101 and the counter substrate 105 are formed in the internal space. In the vicinity of the center of S, it bends and swells, resulting in a curved shape in which the thickness of the layer of electrolyte 109 is larger than the portion where the sealing material 108 is disposed.
  • this invention makes it a subject to provide the photoelectric conversion element which suppressed the reduction
  • a transparent conductive film is formed on a plate surface of one substrate, a semiconductor layer is formed on the surface of the transparent conductive film, and the first substrate is spaced from the first electrode.
  • a second electrode in which a counter conductive film is formed on a plate surface of another substrate disposed opposite to the transparent conductive film, and an electrolyte sealed between the first electrode and the second electrode And at least one of the one substrate and the other substrate is bent or curved inside the outer peripheral wall portion that seals the electrolyte, and the other substrate or the one substrate disposed opposite to each other It is characterized by projecting toward it.
  • At least one of the one substrate and the other substrate is bent or curved inside the outer peripheral wall portion that seals the electrolyte, so that the inner side of the outer peripheral wall portion protrudes. It is possible to provide strength against bending in a direction opposite to the direction in which the head is located. Therefore, it can be prevented that one substrate and another substrate swell in a direction away from each other. Then, one substrate can be curved and approached to the other substrate that faces the substrate. Therefore, it is possible to prevent a decrease in incident light due to a decrease in the distance between one substrate and another substrate and increase the thickness of the electrolyte layer, and to improve the efficiency of the oxidation-reduction reaction by shortening the electron movement distance.
  • At least one of the one substrate and the other substrate of the present invention is bent toward the other substrate or the one substrate arranged to face each other inside the outer peripheral wall portion that seals the electrolyte. It is good also as a structure provided with the side wall part formed along the outer peripheral wall part, and the inner side wall part formed inside the front-end
  • the one substrate of the present invention may be configured to be curved inside an outer peripheral wall portion that seals the electrolyte. According to this configuration, it is possible to prevent the one substrate from being bent so as to swell in a direction away from the other substrate facing the substrate. In addition, since one substrate is curved and approached to another opposing substrate, the distance between the one substrate and the other substrate can be reduced to efficiently perform the oxidation-reduction reaction.
  • At least one of the one substrate or the other substrate protruding toward the other substrate or the one substrate of the present invention is formed of a resin film. According to this structure, the said photoelectric conversion element can be manufactured simply and efficiently.
  • the outer peripheral wall portion of the one substrate and the outer peripheral wall portion of the other substrate are bonded by a sealing material, and the sealing material is bent or curved. It is preferable that the corner
  • the sealing material may be chamfered along a bent or curved shape inside the outer peripheral wall portion. According to this configuration, the one substrate and / or the other substrate can be bent or curved along the chamfered sealing material.
  • the electric module of the present invention includes a plurality of the photoelectric conversion elements described above. According to the present invention, it is possible to obtain an electrical module that exhibits any one of the actions and functions described above.
  • At least one of the one substrate and the other substrate protruding toward the other substrate or the one substrate is formed by pressing.
  • the said photoelectric conversion element can be manufactured simply.
  • any one of the above-described methods for manufacturing a photoelectric conversion element it is preferable that a semiconductor layer is formed, compressive internal stress is applied to the one substrate, and the one substrate is curved. According to this configuration, the one substrate can be easily bent.
  • the semiconductor layer of the present invention is preferably formed by an aerosol deposition method. According to this method, one substrate can be easily bent.
  • the present invention it is possible to suppress a decrease in incident light and a reduction in the efficiency of the oxidation-reduction reaction, and thus it is possible to improve the power generation efficiency of the photoelectric conversion element and the electric module. Moreover, according to the manufacturing method of the photoelectric conversion element of this invention, there exists an effect that the photoelectric conversion element of this invention can be manufactured easily.
  • a dye-sensitized solar cell (photoelectric conversion element) (hereinafter referred to as “solar cell”) 1A includes a transparent conductive film 3 formed on a plate surface 2a of a single substrate 2 and a transparent conductive film.
  • the transparent conductive film 3 is formed on the first electrode 5 provided with the semiconductor layer 4 formed on the surface 3a of the film 3 and the plate surface 6a of the other substrate 6 disposed opposite to the substrate 2 with a space.
  • the sealing material is provided between the outer peripheral wall 2p of one substrate 2 and the outer peripheral wall 6p of another substrate 6 with the separator 9 interposed between the first electrode 5 and the second electrode 8. 10 is sealed in a frame shape so as to go around the outer periphery of the first electrode 5 and the second electrode 8, and the sealed internal space S is filled with the electrolytic solution 11.
  • one substrate 2 is bent toward another substrate 6 disposed opposite to the inside of the outer peripheral wall portion 2 p that seals the electrolyte solution 11.
  • Wall portions 15 and 16 inside the outer peripheral wall portion 2p protrude toward the other substrate 6.
  • one substrate 2 has an outer peripheral wall portion 2p formed with a predetermined width dimension d entering the predetermined dimension inside from the outer edge e, and toward the other substrate 6 inside the outer peripheral wall portion 2p.
  • the side wall 15 that is bent and rises up (hangs down) along the outer peripheral wall 2p, and is bent again at the tip of the side wall 15, and is formed so as to close the region surrounded by the tip of the side wall 15.
  • a convex portion 17 that protrudes toward the other substrate 6.
  • One substrate 2 and another substrate 6 are members that serve as bases for the transparent conductive film 3 and the counter conductive film 7, respectively.
  • transparent thermoplastic such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET). It is made of a resin material.
  • substrate 6 may be formed in the film form.
  • the transparent conductive film 3 is formed on substantially the entire plate surface 2 a of one substrate 2.
  • indium tin oxide or zinc oxide is used as the material of the transparent conductive film 3.
  • the semiconductor layer 4 has a function of receiving and transporting electrons from a sensitizing dye described later, and is formed on the surface 3 a of the transparent conductive film 3 by a semiconductor made of a metal oxide.
  • a metal oxide for example, titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ) or the like is used.
  • the semiconductor layer 4 carries a sensitizing dye.
  • the sensitizing dye is composed of an organic dye or a metal complex dye.
  • the organic dye for example, various organic dyes such as coumarin, polyene, cyanine, hemicyanine, and thiophene can be used.
  • the metal complex dye for example, a ruthenium complex is preferably used.
  • the first electrode 5 is configured by forming the transparent conductive film 3 on one plate surface 2 a of one substrate 2 and providing the semiconductor layer 4 formed on the surface 3 a of the transparent conductive film 3. .
  • the counter conductive film 7 is formed on substantially the entire plate surface 6 a of the other substrate 6.
  • indium tin oxide (ITO), zinc oxide, or the like is used as the material of the counter conductive film 7.
  • a catalyst layer 18 made of carbon paste, platinum, or the like, which is arbitrarily provided, is formed on the surface of the counter conductive film 7.
  • the opposing conductive film 7 is formed on one plate surface 6 a of the other substrate 6, and the catalyst layer 18 is formed on the surface of the opposing conductive film 7 to form the second electrode 8.
  • the second electrode 8 is disposed opposite to the first electrode 5 with the opposing conductive film 7 facing the transparent conductive film 3. Then, the first electrode 5 and the second electrode 8 are bonded to each other in one direction so that the end 3h of the transparent conductive film 3 and the end 7h of the counter conductive film 7 protrude from both ends of the solar cell 1A, respectively. Has been. These end portions 3 h and end portions 7 h constitute the terminals of the first electrode 5 and the second electrode 8. In addition, how to take an electric current is not limited to the structure of this embodiment.
  • the sealing material 10 hot melt resin or the like is used.
  • the sealing material 10 is arranged in a frame shape on the surface 3a of the transparent conductive film 3 positioned on the outer peripheral wall 2p or the surface of the opposing conductive film 7 positioned on the outer peripheral wall 6p, and is heated and pressed to form the first electrode 5. And the second electrode 8 are bonded.
  • a sheet material such as a nonwoven fabric having a large number of holes (not shown) through which the sealing material 10 and the electrolyte solution (electrolyte) 11 pass.
  • the electrolytic solution 11 examples include non-aqueous solvents such as acetonitrile and propionitrile; liquid components such as ionic liquids such as dimethylpropylimidazolium iodide and butylmethylimidazolium iodide; and a supporting electrolytic solution such as lithium iodide.
  • a solution or the like in which iodine and iodine are mixed is used.
  • the electrolytic solution 11 may contain t-butylpyridine in order to prevent a reverse electron transfer reaction.
  • An electric module is obtained by connecting solar cells 1A having the above configuration in series or in parallel.
  • Electrode plate forming step As shown in FIG. 3, a transparent conductive film 3 is formed on one plate surface 2a of one substrate 2, and a semiconductor layer 4 is formed on the surface 3a of the transparent conductive film 3. As shown in FIG. 4, the first electrode 5 and the second electrode 8 on which the opposing conductive film 7 is formed on one plate surface 6 a of the other substrate 6 and the catalyst layer 18 is further formed are formed. Specifically, the first electrode 5 and the second electrode 8 are formed as follows.
  • PET or the like is used as one substrate 2, and a plate-like member is formed in which convex portions 17 that protrude toward one plate surface are formed inside the substrate.
  • a manufacturing method of the plate-shaped member provided with the convex part 17 It can shape
  • the transparent conductive film 3 is formed by sputtering indium tin oxide (ITO) or the like over the entire plate surface 2a of the single substrate 2.
  • the semiconductor layer 4 is formed to be porous by, for example, applying a bakable titanium oxide-containing paste to the surface 3a of the transparent conductive film 3 by a mask, a printing method, or the like, and then baking at about 120 ° C.
  • the transparent conductive film 3 is made porous by a low-temperature film forming method that does not require firing, such as an aerosol deposition method or a cold spray method. It may be formed on the surface 3a.
  • the semiconductor layer 4 is immersed in a sensitizing dye solution in which a sensitizing dye is dissolved in a solvent, and the sensitizing dye is supported on the semiconductor layer 4.
  • the method for supporting the sensitizing dye on the semiconductor layer 4 is not limited to the above, and a method of continuously charging, dipping and pulling up while moving the semiconductor layer 4 in the sensitizing dye solution is also employed. .
  • the first electrode 5 shown in FIG. 3 is obtained.
  • the second electrode 8 is formed by forming a counter conductive film 7 by sputtering ITO, zinc oxide, platinum or the like on one plate surface 6a of another substrate 6 made of polyethylene terephthalate (PET) or the like.
  • the counter conductive film 7 may be formed by a printing method, a spray method, or the like.
  • a catalyst layer 18 is formed on the surface of the opposing conductive film 7 by forming a carbon paste or the like.
  • the injection hole forming member 19 is disposed so as to protrude from the outer peripheral wall portion 6 p of the other substrate 6 across the sealing material 10.
  • a releasable resin sheet formed in a strip shape is used as the injection hole forming member 19.
  • the releasable resin sheet for example, polyester, polyethylene terephthalate, polybutylene terephthalate, or the like can be used.
  • the second electrode 8 is brought into contact with the first electrode 5 so that the transparent conductive film 3 and the counter conductive film 7 are opposed to each other with the separator 9 interposed therebetween.
  • the first electrode 5 and the second electrode 8 are attached while being shifted in one direction (arrow Y direction), and the first electrode 5 and the second electrode 8 attached together as shown in FIG.
  • the transparent conductive film 3 and the counter conductive film 7 are projected from both ends of the two electrodes 8 to form terminals 5t and 8t.
  • the one substrate 2 resists the force that causes the electrolyte solution 11 to expand outward in the thickness direction.
  • the inner wall portion 16 can be kept flat. As described above, the solar cell 1A shown in FIG. 1 in which the inner wall 16 of one substrate 2 is kept flat is obtained.
  • one substrate 2 is bent and the inner wall portion 16 faces the other substrate 6. It is formed to protrude. Accordingly, the thickness dimension of the inner space S into which the electrolyte solution 11 is injected is made as small as possible, and the inner wall portion 16 is given strength against bending outward in the thickness direction by bending the one substrate 2. can do.
  • the inner space S in which the layer of the electrolyte solution 11 is formed is avoided by preventing the one substrate 2 from expanding outward in the central portion of the internal space S. It is possible to maintain a constant thickness with the thickness of as small as possible. And by this structure of this invention, while the thickness dimension of the layer of the electrolyte solution 11 becomes large in the center part of the internal space S, it is suppressed that the loss of incident light arises, and the moving distance of an electron becomes long. Thus, the effect of preventing the efficiency of the oxidation-reduction reaction from being lowered can be obtained.
  • the one substrate 2 is bent at an obtuse angle between the side wall 15 and the outer peripheral wall 2p and between the side wall 15 and the inner wall 16. Therefore, the convex portion can be easily formed by pressing as compared with the case where the convex portion 17 is formed by bending one substrate 2 vertically or at an acute angle. Further, by bending one substrate 2 at an obtuse angle, it is possible to prevent the thickness of the one substrate 2 from being reduced at the bent portion and to bend while maintaining the strength due to the thickness as much as possible. An effect is obtained.
  • one substrate 2 and / or another substrate 6 is preferably formed of a resin film (for example, a film thickness of 25 ⁇ m to 200 ⁇ m).
  • the production efficiency can be improved by conveying the resin film by roll-to-roll and bending or bending the substrate in the process. Even if one substrate 2 and / or another substrate 6 is formed of such a resin film, the one substrate 2 and / or another substrate 6 is bent or curved so that By reducing the rigidity, it is possible to effectively prevent a decrease in photoelectric conversion efficiency due to one substrate 2 and another substrate 6 being bent and swollen.
  • the transparent conductive film which faces the internal space S by being bent at an obtuse angle between the side wall 15 and the outer peripheral wall 2p and between the side wall 15 and the inner side wall 16. 3 can be easily formed on the entire surface. Therefore, according to the electric module in which the solar cells 1A or the solar cells 1A are connected in series or in parallel, the effect that the redox reaction can be performed in a wider area is obtained.
  • the curved surfaces 2 a and 2 b are formed so that one substrate 2 slightly protrudes toward the other substrate 6, that is, warps against the other substrate 6. Therefore, even if the inner space S is filled with a large amount of the electrolytic solution 11 and the pressure that causes the one substrate 2 to swell outward is applied by the electrolytic solution 11, this pressure can be countered by the curvature of the one substrate 2. It is possible to prevent the substrate 2 from bulging outward at the center.
  • the one substrate 2 having a slightly curved shape is coated with a film on one plate surface of the one substrate 2 by a powder spraying method (for example, aerosol deposition method). It can be formed easily and efficiently by forming.
  • a powder spraying method for example, aerosol deposition method
  • fine particles made of an oxide semiconductor are dispersed in N 2 gas, and fine particles made of an oxide semiconductor are sprayed at high speed from a nozzle toward one substrate 2, so that a semiconductor layer is formed on the transparent conductive film 3 of the one substrate 2. 4 is formed.
  • fine particles made of an oxide semiconductor are formed in a state where heat is applied to one substrate 2 and then cooled, or oxide semiconductor particles are formed in a state where the single substrate 2 is stretched under tension. After that, by releasing the tension, the plate surface 2b opposite to the side on which the fine particles of oxide semiconductor of the one substrate 2 are formed shrinks, and the one substrate 2 protrudes toward the plate surface 2a side. Can be curved (compressive internal stress).
  • the size of a particle such as an oxide semiconductor particle may be in the range of 5 nm to 1000 nm, preferably in the range of 10 nm to 500 nm, and more preferably in the range of 15 nm to 50 nm.
  • the curvature of the curved surfaces 2a and 2b of one substrate 2 may be in the range of 0.01 to 0.1, and is preferably in the range of 0.03 to 0.06.
  • the thickness dimension of the internal space S forming the layer of the electrolyte solution 11 is made as small as possible, and one substrate 2 swells outward.
  • the slightly curved one substrate 2 to the first electrode 5 can be easily manufactured, the loss of incident light and the oxidation-reduction can be suppressed while suppressing the manufacturing cost of the solar cell 1B. It is possible to obtain a solar cell 1B with high reaction efficiency or an electric module in which the solar cells 1B are connected in series or in parallel.
  • one substrate 2 is bent to form the convex portion 17 or curved, but the other substrate 6 is bent or curved. It may be a configuration. Furthermore, both the one substrate 2 and the other substrate 6 are bent or curved and bonded so as to protrude from each other with respect to the other substrate 6 or the one substrate 2 (see FIG. 10B). ). When both the one substrate 2 and the other substrate 6 are bent or curved and bonded to each other so as to protrude from the other substrate 6 or the one substrate 2, the thickness of the internal space S can be made as large as possible. Therefore, it is possible to prevent the bending of both the one substrate 2 and the other substrate 6 while preventing the bending.
  • the sealing material 10 for bonding between the outer peripheral wall portion 2p of one substrate 2 and the outer peripheral wall portion 6p of another substrate 6 is provided inside the outer peripheral wall portion 2p. It is comprised and manufactured similarly to 1st Embodiment except the point chamfered by the corner
  • the inside of the sealing material 10 that surrounds the internal space S is an inclined surface 51 that is chamfered at the corner 50 indicated by an imaginary line of the sealing material 10 and descends toward the internal space S. Yes.
  • the inclination angle of the side wall portion 15 of one substrate 2 can be made gentle. Therefore, by bending one substrate 2 at a steep angle, it is possible to prevent the transparent conductive film 3 from being scratched or cracked, and there is an effect that a high-quality photoelectric conversion element 1D can be obtained. can get.
  • angular part 50 of the sealing material 10 prevents reducing the electric power generation area by crushing the transparent conductive film 3, the both ends of the oxide semiconductor 4, and the catalyst layer 18 depending on the case at the time of press work. The effect of being able to be obtained.
  • the side wall 15 of the one substrate 2 can be arranged along the chamfered inclined surface 51 of the sealing material 10, sealing is performed when an external force is applied to the side wall 15 of the one substrate 2.
  • the side wall 15 can be supported by the inclined surface 51 of the material 10. Therefore, the photoelectric conversion element 1D has an effect that the transparent conductive film 3 can be prevented from being damaged by the inclined surface 51 when an external force is applied to one substrate 2.
  • the photoelectric conversion element 1D can press the one substrate 2 on the inclined surface 51 of the sealing material 10 at the time of manufacture.
  • the photoelectric conversion element 1D can be pressed using the chamfered sealing material 10 as a support base, excessive bending of one substrate 2 is prevented and damage to the transparent conductive film 3 is prevented. The effect that it can be obtained.
  • the electric module 80 when the electric module 80 is continuously produced by so-called roll-to-roll by connecting a plurality of photoelectric conversion elements 1D, one substrate using the chamfered sealing material 10 as a support base.
  • the photoelectric conversion elements 1 ⁇ / b> D and 1 ⁇ / b> D are connected to each other through the conductive material 70 by forming the grooves 75 in the transparent conductive film 3 and the opposing conductive film 7 to alternately insulate them. The case where it connects in series is shown.
  • the sealing material 10 of the present invention may be chamfered so as to be smoothly curved as long as the inclination angle of the side wall portion 15 can be set gently. Moreover, the corner
  • the case where only one substrate 2 is bent has been described as an example.
  • the other substrate 6 is bent so as to protrude toward the internal space S, the sealing is performed.
  • the corners on the other substrate 6 side of the material 10 and on the inner space S side may be chamfered.
  • the one substrate 2 side of the sealing material 10 and Both of the other substrate 6 sides may be chamfered.
  • Example 1 A solar cell similar to the solar cell 1A was manufactured according to the following specifications schematically illustrated in FIG.
  • a PEN film having a thickness of 125 ⁇ m was embossed to form a convex portion 17 having a height L1 of 30 ⁇ m shown in FIG.
  • ITO indium tin oxide
  • a TiO 2 paste was applied onto ITO so as to be 10 ⁇ 50 mm square with an applicator, and heated at 120 ° C. to be cured. Thereafter, the organic dye was dissolved in a solvent so that the dye concentration was 0.02 to 0.5 mM, and the substrate was immersed in the solution for 10 minutes. The substrate taken out from the solution was washed with ethanol and dried.
  • ITO Indium tin oxide
  • the separator 9 (manufactured by Hirose Paper Co., Ltd.) had a size larger than that covering the ITO except for the current extraction wiring portion, and had a thickness of 20 ⁇ m and 15 ⁇ 55 mm.
  • the first electrode 5 and the second electrode 8 obtained as described above are arranged so that the TiO 2 layer 4 and the carbon layer 18 face each other, and the first electrode 5-hot melt resin 10-separator 9-hot
  • the melt resin 10 -the releasable resin sheet (Naflon sheet) -the second electrode 8 were laminated in this order, and were bonded by hot pressing while applying pressure at 120.degree.
  • a releasable resin sheet disposed between the first electrode 5 and the second electrode 8 is pulled out to form a liquid injection hole 21 (see FIG. 7), and the bonded first electrode 5 and second electrode 8 are foldered.
  • the desiccator is evacuated by immersing the injection hole 21 in the electrolyte 11, and the vacuum is released to 100 Pa. After that, the atmosphere is opened and the electrolyte 11 is placed between the first electrode 5 and the second electrode 8. Injected. Since the electrolyte solution 11 adhered to the periphery of the injection hole 21, it was cleaned by wiping with a solvent (ethanol). Thereafter, the liquid injection hole 21 was sealed by hot pressing. Thus, solar cell 1A was produced.
  • the thickness dimension of the convex portion 17 shown in FIG. 10A with a micrometer that is, the dimension between the outer plate surfaces of the PEN films facing each other in the region where the convex portion 17 is formed.
  • Table 1 shows the results of measuring the thickness dimension N1 of M1 and the sealing material 10 (that is, the dimension between the outer plate surfaces of the PEN films facing each other at the place where the sealing material 10 is disposed).
  • the results of confirming the power generation performance of the solar cell 1A with a solar simulator are shown in Table 2.
  • Example 2 A solar cell 1 ⁇ / b> C was manufactured according to the following specifications schematically illustrated in FIG. ⁇ First electrode 5> A first electrode 5 similar to that of Example 1 was formed.
  • ⁇ Second electrode 8> The PEN film is formed with a convex portion 17 projecting at the same height as the first electrode 5, and indium tin oxide (ITO) is sputtered as a counter conductive film on the plate surface on the side where the convex portion 17 is formed.
  • ITO indium tin oxide
  • a second electrode 8 similar to that of Example 1 was formed except that the film was formed.
  • ⁇ Encapsulant 10> A sealing material 10 similar to that of Example 1 was prepared.
  • ⁇ Separator 9> A separator 9 similar to that in Example 1 was prepared.
  • the first electrode 5 and the second electrode 8 obtained as described above are arranged so that the TiO 2 layer 4 and the carbon layer 18 face each other, and the first electrode 5-hot melt resin 10-separator 9-hot
  • the melt resin 10—the releasable resin sheet (Naflon sheet) —the second electrode 8 were laminated in this order and hot pressed while applying pressure at 120 ° C.
  • a solar cell 1B was produced according to the following specifications schematically illustrated in FIG. ⁇ First electrode 5> Fine particles made of an oxide semiconductor were dispersed in N 2 gas, and fine particles made of an oxide semiconductor were sprayed from a nozzle toward the plate surface of the PEN film at a high speed to form a film. At this time, the PEN film is stretched under tension, and after the oxide semiconductor particles are formed, the tension is released to shrink the plate surface opposite to the side on which the oxide semiconductor particles are formed. The PEN film was bent so as to protrude toward the plate surface on which fine particles made of an oxide semiconductor were formed. Then, it cut
  • PEDOT was formed as a counter electrode on ITO with a film thickness of 35 nm.
  • the formed ITO-PEN film was cut to 16 ⁇ 54 mm to obtain the second electrode 8.
  • ⁇ Encapsulant 10> The thermosetting resin was cut into strips to obtain two types having a thickness of 100 ⁇ m and 3 ⁇ 14 mm and a thickness of 100 ⁇ m and 3 ⁇ 54 mm.
  • the two types of thermosetting resins were arranged in a rectangular shape on the outer periphery of the first electrode 5, and the thermosetting resins were arranged so that the distance between the semiconductor layer 4 and the sealing material 10 was 1 mm or less. In this example, the separator was not used. However, even if the PEDOT layer and the TiO 2 layer are in contact with each other, the catalyst layer 18 and the transparent conductive film 3 are difficult to contact with each other, so that no short circuit occurs.
  • the first electrode 5 and the second electrode 8 are arranged so that the TiO 2 layer and the PEDOT layer face each other. Then, thermal lamination was performed while laminating the first electrode 5 and the second electrode 8. Thus, the solar cell 1B was created.
  • Table 1 shows the results of measuring the thickness dimension M3 of the convex portion 17 and the thickness dimension N3 of the sealing material 10 shown in FIG. The results of confirming the power generation performance of the solar cell 1B with a solar simulator are shown in Table 2.
  • a solar cell 100 was manufactured according to the following specifications schematically illustrated in FIG. ⁇ First electrode> A first electrode similar to that of Example 1 was formed except that a PEN film cut to a size of 16 ⁇ 54 mm was not flat and formed a flat surface. ⁇ Second electrode> A second electrode similar to that in Example 1 was formed. ⁇ Encapsulant> A sealing material similar to that in Example 1 was prepared. ⁇ Separator 9> A separator similar to that in Example 1 was prepared.
  • the first electrode 5 and the second electrode 8 obtained as described above are arranged so that the TiO 2 layer 4 and the carbon layer 18 face each other, and the first electrode 5-hot melt resin 10-separator 9-hot
  • the melt resin 10—the releasable resin sheet (Naflon sheet) —the second electrode 8 were laminated in this order and hot pressed while applying pressure at 120 ° C.
  • the releasable resin sheet disposed between the first electrode 5 and the second electrode 8 is pulled out, the bonded first electrode 5 and second electrode 8 are attached and fixed to a folder, and the injection hole is formed in the electrolyte solution 11.
  • the atmosphere was opened and the electrolyte solution 11 was injected between the first electrode 5 and the second electrode 8. Thereafter, the injection hole was sealed by hot pressing.
  • Table 1 shows the results of measuring the thickness dimension M4 inside the sealing material 10 and the thickness dimension N4 of the sealing material 10 with respect to the solar cell 100 using a micrometer. The results of confirming the power generation performance of the solar cell with a solar simulator are shown in Table 2.
  • the thickness dimensions M1 to M3 and the power generation performance of Examples 1, 2, 3 are both ⁇ 5%.
  • the thickness dimension M4 and power generation performance of Comparative Example 1 both varied by ⁇ 10% or more. From this, it can be seen that the thicknesses M1 to M3 after filling the electrolytic solution 11 are more uniform in the structures of Examples 1, 2, and 3 than in the structure of Comparative Example 1. It was.
  • the distance between the second electrode 8 and the first electrode 5 which was a problem in the production of the solar cell 100 can be made as constant as possible. It was also found that the power generation performance of the solar cells 1A to 1C can be stabilized by making the distance between the second electrode 8 and the first electrode 5 as constant as possible.

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PCT/JP2015/050850 2014-03-27 2015-01-14 光電変換素子、電気モジュール及び光電変換素子の製造方法 WO2015146226A1 (ja)

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