JP2012182040A - Dye-sensitized solar cell module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell module having sufficiently high connection reliability while having a large aperture ratio, and sufficiently preventing a malfunction.SOLUTION: A dye-sensitized solar cell module 100 comprises a plurality of dye-sensitized solar cells 50 connected in series and electrically. A transparent conductive film 12 of one of the dye-sensitized solar cells 50 adjacent to each other comprises a projecting portion 12c projecting from a main body 12a beyond a sealing portion 30A laterally to the arrangement direction of the plurality of dye-sensitized solar cells 50A to 50D, and an extending portion 12d extending from the projecting portion 12c to a position being outside the sealing portion 30A of the other dye-sensitized solar cell 50 and toward the side of the main body 12a of the other dye-sensitized solar cell 50. The extending portion 12d, and a metal substrate 21 of a second electrode 20 of the other dye-sensitized solar cell 50 are connected via a conductive material 60.

Description

  The present invention relates to a dye-sensitized solar cell module.

  As a photoelectric conversion element module, a dye-sensitized solar cell module has attracted attention because it is inexpensive and has high photoelectric conversion efficiency, and various developments have been made on the dye-sensitized solar cell module.

  A dye-sensitized solar cell module generally includes a plurality of dye-sensitized solar cells connected in series, and each dye-sensitized solar cell connects a working electrode, a counter electrode, and a working electrode and a counter electrode. And an annular sealing portion. The working electrode includes a transparent substrate, a transparent conductive film formed thereon, and an oxide semiconductor layer provided on the transparent conductive film. As such a dye-sensitized solar cell module, the thing of the following patent document 1 is known, for example. In Patent Document 1 below, in two adjacent dye-sensitized solar cells, a conductive member extending from the counter electrode of one dye-sensitized solar cell and a transparent conductive film of the other dye-sensitized solar cell are adjacent to each other. A dye-sensitized solar cell module connected between stops is disclosed.

International Publication No. 2009/133689

  By the way, the dye-sensitized solar cell module is usually housed in a case having an opening. In this case, the dye-sensitized solar cell module is disposed so that the light-receiving surfaces of all the dye-sensitized solar cells are accommodated inside the outer frame member provided along the edge of the opening. Accordingly, the larger the total area of the light receiving surface in the area inside the outer frame member, the higher the aperture ratio.

  In recent years, a dye-sensitized solar cell module having a small size such that the power generation current of one dye-sensitized solar cell is less than 500 mA, and a dye-sensitized solar cell module used in a place with relatively low illuminance such as indoors are sensors. It is used for such purposes. A dye-sensitized solar cell module used for such applications usually has a smaller light receiving area and a smaller amount of light received than a dye-sensitized solar cell module used outdoors. For this reason, in a dye-sensitized solar cell module, it is calculated | required to have especially high aperture ratio so that electric power generation may be performed efficiently.

  However, in the dye-sensitized solar cell module described in Patent Document 1, a conductive member extending from the counter electrode of one dye-sensitized solar cell in two adjacent dye-sensitized solar cells and the other dye-sensitized solar cell. The transparent conductive film is connected between the adjacent sealing portions. That is, the connection location where the edge of the counter electrode and the transparent conductive film are connected exists in the light receiving area such as the inner region of the outer frame member described above. For this reason, it does not contribute to power generation by the area of the connection location, and the aperture ratio becomes low. In particular, the area required for the connection site is usually almost the same for a dye-sensitized solar cell module having a large light receiving area and a small dye-sensitized solar cell module. For this reason, when the connection location between two adjacent dye-sensitized solar cells is within the light receiving area, the dye-sensitized solar cell module having a smaller light receiving area has a lower aperture ratio. Here, in order to obtain a high aperture ratio, it is conceivable to reduce the area of the connection portion. However, in this case, the bonding strength at the connection location is lowered, and the connection reliability is lowered. Therefore, in the dye-sensitized solar cell module described in Patent Document 1, it is difficult to obtain a higher aperture ratio.

  Thus, the dye-sensitized solar cell module described in Patent Document 1 has room for improvement in terms of improving the aperture ratio.

  Here, when using a metal substrate for the counter electrode of the dye-sensitized solar cell, one end of the jumper wire is connected to the surface opposite to the working electrode with respect to the counter electrode, and from the transparent conductive film of the adjacent dye-sensitized solar cell By providing an overhanging portion that protrudes to the outside of the sealing portion and to the side of the sealing portion, and by connecting the other end of the jumper wire to this overhanging portion, the adjacent dye-sensitized solar cells are outside the light receiving area. It is also conceivable to improve the aperture ratio by electrically connecting the two.

  However, in this case, the jumper wire tends to be long because it connects the counter electrode of one dye-sensitized solar cell and the overhanging portion of the transparent conductive film of the other dye-sensitized solar cell. For this reason, for example, when an operator's hand gets caught in a jumper wire when handling a dye-sensitized solar cell module, the connection location between the jumper wire and the counter electrode or the connection location between the jumper wire and the overhanging portion of the transparent conductive film is excessive. Easy to be stressed. As a result, connection reliability may be impaired.

  Here, it is conceivable to use a metal film instead of the jumper wire. When a metal film is used, the operator's hand is less likely to get caught on the jumper wire. However, when the counter electrode of one dye-sensitized solar cell and the overhanging portion of the transparent conductive film of the other dye-sensitized solar cell are connected using a metal film, the metal film becomes the counter electrode of the other dye-sensitized solar cell. There is a risk of contact. As a result, a malfunction occurs in the dye-sensitized solar cell module.

  The present invention has been made in view of the above-described matters, and provides a dye-sensitized solar cell module that can sufficiently improve connection reliability while improving an aperture ratio and can sufficiently prevent malfunction. Objective.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following invention, and have completed the present invention.

  That is, the present invention provides a dye-sensitized solar cell module having a plurality of dye-sensitized solar cells connected in series and electrically, wherein the dye-sensitized solar cell is provided on the transparent substrate and the transparent substrate. A first electrode having a transparent conductive film having a main body, a second electrode having a metal substrate facing the first electrode, and an oxide semiconductor layer provided on the first electrode or the second electrode, And an annular sealing portion for joining the first electrode and the second electrode, and the transparent substrate is composed of a common transparent substrate of the plurality of dye-sensitized solar cells, and two adjacent dyes In the sensitized solar cell, the transparent conductive film in one dye-sensitized solar cell protrudes beyond the sealing portion laterally with respect to the arrangement direction of the plurality of dye-sensitized solar cells from the main body portion. Overhang portion and the overhang portion An extension portion extending to a position outside the sealing portion of the other dye-sensitized solar cell and to the side of the main body portion of the other dye-sensitized solar cell, In the dye-sensitized solar cell module, the projecting portion and the metal substrate of the second electrode in the other dye-sensitized solar cell are connected via a conductive material.

  According to this dye-sensitized solar cell module, the transparent conductive film in one of the dye-sensitized solar cells extends from the main body side to the side of the arrangement direction of the plurality of dye-sensitized solar cells beyond the sealing portion. An overhang portion that extends, and an extension portion that extends from the overhang portion to the outside of the sealing portion of the other dye-sensitized solar cell and to the side of the main body portion of the other dye-sensitized solar cell, The extension part and the metal substrate of the second electrode in the other dye-sensitized solar cell are connected via a conductive material. That is, in the dye-sensitized solar cell module of the present invention, in two adjacent dye-sensitized solar cells, the transparent conductive film of one dye-sensitized solar cell and the second electrode of the other dye-sensitized solar cell are And connected outside the light receiving area including the sealing portion of all the dye-sensitized solar cells. In other words, a connection location that does not contribute to power generation in the dye-sensitized solar cell module is provided outside the light receiving area. Therefore, the aperture ratio can be improved. Moreover, since the transparent conductive film of one dye-sensitized solar cell and the second electrode of the other dye-sensitized solar cell are connected on the outside of the sealing portion, the connection point between the transparent conductive film and the conductive material It is also possible to increase the area of the connection location between the second electrode and the conductive material. Furthermore, the extending part of the transparent conductive film in one dye-sensitized solar cell is outside the sealing part of the other dye-sensitized solar cell from the overhanging part and on the side of the main part of the other dye-sensitized solar cell It extends to the position. That is, the transparent conductive film of the dye-sensitized solar cell is provided in the immediate vicinity of the second electrode of the adjacent dye-sensitized solar cell. For this reason, it becomes possible to shorten a conductive material, and it becomes difficult for an operator's hand to be caught in a conductive material. As a result, it is possible to prevent an excessive stress from being applied to the connection portion between the conductive material and the second electrode, or the connection portion between the conductive material and the transparent conductive film, and to improve the connection reliability in the dye-sensitized solar cell module. It can be improved sufficiently. Further, since the conductive material is sufficiently prevented from coming into contact with the second electrode of the adjacent dye-sensitized solar cell, the adjacent second electrodes are sufficiently prevented from being electrically connected by the conductive material. The As a result, it is possible to sufficiently prevent malfunction of the dye-sensitized solar cell module.

  In the dye-sensitized solar cell module, the conductive material is preferably a metal film.

  In this case, the unevenness on the back surface side of the second electrode can be reduced. As a result, the dye-sensitized solar cell module can be stably installed on the flat surface.

  ADVANTAGE OF THE INVENTION According to this invention, the dye-sensitized solar cell module which can fully improve connection reliability while improving an aperture ratio, and can fully prevent a malfunctioning is provided.

It is a bottom view which shows one Embodiment of the dye-sensitized solar cell module of this invention. It is sectional drawing along the II-II line of FIG. It is a partially notched partial top view of FIG. It is a top view which shows the 1st sealing part of FIG. It is a top view which shows the 2nd sealing part of FIG. It is a top view which shows the 1st sealing part formation body for forming the 1st sealing part of FIG.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a bottom view showing an embodiment of the dye-sensitized solar cell module of the present invention, FIG. 2 is a cross-sectional view taken along the line II-II in FIG. 1, and FIG. It is a partial top view.

  As shown in FIG. 1, a dye-sensitized solar cell module (hereinafter sometimes referred to as “DSC module”) 100 includes a plurality (four in FIG. 1) of dye-sensitized solar cells (hereinafter referred to as “DSC”). The plurality of DSCs 50 are connected in series. Hereinafter, for convenience of description, the four DSCs 50 in the DSC module 100 may be referred to as DSCs 50A to 50D.

  As shown in FIG. 2, each of the plurality of DSCs 50 includes a working electrode 10, a counter electrode 20 that faces the working electrode 10 and has a metal substrate 21, and a sealing portion 30 </ b> A that joins the working electrode 10 and the counter electrode 20. The cell space formed by the working electrode 10, the counter electrode 20, and the annular sealing portion 30A is filled with an electrolyte 40.

  The working electrode 10 includes a transparent substrate 11 and a transparent conductive substrate 15 having a transparent conductive film 12 provided on the transparent substrate 11 and at least one oxide provided on the transparent conductive film 12 of the transparent conductive substrate 15. And a semiconductor layer 13. The oxide semiconductor layer 13 is disposed inside the annular sealing portion 30A. The transparent substrate 11 is used as a common transparent substrate for the DSCs 50A to 50D. An insulating material 14 is provided between the transparent substrate 11 and the sealing portion 30A. Hereinafter, for convenience of explanation, the transparent conductive film 12 corresponding to the DSCs 50A to 50D may be referred to as transparent conductive films 12A to 12D.

  In the DSC module 100, each of the transparent conductive films 12A to 12D of each DSC 50 has a rectangular main body 12a (see FIG. 1). The main body portion 12a has two side edge portions 12b along the arrangement direction X of the plurality of dye-sensitized solar cells 50A to 50D. As shown in FIG. 3, for example, in two adjacent DSCs 50A and 50B, the transparent conductive film 12B in one DSC 50B extends in the arrangement direction of the dye-sensitized solar cells 50A to 50D from both side edges 12b of the main body 12a. On the other hand, it has two projecting parts 12c projecting sideways and an projecting part 12d extending from the projecting part 12c to the adjacent DSC 50A side. Here, the extending part 12d extends to the position outside the sealing part 30A of the DSC 50A and to the side of the side edge part 12b of the main body part 12a of the DSC 50A. Specifically, the extending part 12d is disposed along the sealing part 30A of the DSC 50B and the sealing part 30A of the other DSC 50A. The two extending portions 12d are disposed so as to sandwich the main body portion 12a of the transparent conductive film 12A in the adjacent DSC 50A.

  The extending portion 12 d and the metal substrate 21 of the counter electrode 20 in the other DSC 50 </ b> A are connected via a conductive material 60. The conductive material 60 is disposed so as to pass over the sealing portion 30A. As the conductive material 60, a metal film is used in this embodiment. As a metal material constituting the metal film, for example, silver or copper can be used.

  In the DSC 50C as well, the transparent conductive film 12C has a protruding portion 12c and an extending portion 12d in addition to the main body portion 12a. Also in the DSC 50D, the transparent conductive film 12D includes a projecting portion 12c and an extending portion 12d in addition to the main body portion 12a.

  However, DSC 50A is already connected to DSC 50B, and there is no other DSC to be connected. For this reason, in the DSC 50A, the transparent conductive film 12A does not have the extending portion 12d.

  As shown in FIG. 2, the counter electrode 20 includes a metal substrate 21 and a catalyst layer 22 provided on the working electrode 10 side of the metal substrate 21 to promote the catalytic reaction. In two adjacent DSCs, the counter electrodes 20 are separated from each other. In the present embodiment, the second electrode is constituted by the counter electrode 20.

  The sealing portion 30A is provided between the transparent conductive substrate 15 and the counter electrode 20 so as to overlap the first sealing portion 31A and the annular first sealing portion 31A provided so as to overlap the insulating material 14. The second sealing portion 32A sandwiches the edge portion 20a of the counter electrode 20 together with the first sealing portion 31A. Then, as shown in FIG. 4, adjacent first sealing portions 31 </ b> A are integrated to form a first sealing portion 31. As shown in FIG. 5, the first sealing portion 31 and the second sealing portions 32 </ b> A are integrated between the adjacent counter electrodes 20 to constitute the second sealing portion 32. In addition, the thickness of the insulating material 14 is larger than the thickness of the transparent conductive film 12, and the melting point of the insulating material 14 is higher than the melting point of the first sealing portion 31A.

  As shown in FIG. 2, in the DSC module 100, the second sealing portion 32 has an adhesive portion 32c, and is bonded to the first sealing portion 31 by the adhesive portion 32c.

  According to the DSC module 100, the adjacent first sealing portions 31 </ b> A and the adjacent second sealing portions 32 </ b> A are integrated between the adjacent counter electrodes 20. Here, if the adjacent first sealing portions 31 </ b> A are not integrated, two adjacent sealing portions are exposed to the atmosphere between the adjacent DSCs 50. On the other hand, in the DSC module 100, since the adjacent first sealing portions 31A are integrated, there is one sealing portion exposed to the atmosphere between the adjacent DSCs 50. Further, since the first sealing portions 31A are integrated with each other, the penetration distance of moisture and the like from the atmosphere to the electrolyte 40 is extended. For this reason, it is possible to sufficiently reduce the amount of moisture and air entering from the outside of the DSC 50 between the adjacent DSCs 50. That is, the sealing ability of the DSC module 100 can be sufficiently improved. Further, according to the DSC module 100, the adjacent first sealing portions 31A are integrated. For this reason, even if the first sealing portions 31A are integrated with each other in a state where the sealing width is smaller than that of the first sealing portion 31A that is not integrated, a sufficient sealing width can be secured. That is, it is possible to sufficiently increase the adhesive strength between the first sealing portion 31A and the transparent conductive substrate 15 and the adhesive strength between the first sealing portion 31A and the counter electrode 20 while improving the aperture ratio. Become. As a result, even when the DSC module 100 is used at a high temperature and the electrolyte 40 expands and an excessive stress is applied from the inside to the outside of the first sealing portion 31A, the transparent conductive substrate 15 and the counter electrode 20 The first sealing portion 31A from peeling can be sufficiently suppressed.

  In the DSC module 100, the second sealing portion 32A is bonded to the first sealing portion 31A through the gap S between the adjacent counter electrodes 20, and the edge portion 20a of the counter electrode 20 is the first sealing. It is sandwiched between the portion 31A and the second sealing portion 32A. For this reason, even if the stress in the direction away from the working electrode 10 acts on the counter electrode 20, the separation is sufficiently suppressed by the second sealing portion 32A. Further, since the second sealing portion 32A is bonded to the first sealing portion 31A through the gap S between the adjacent counter electrodes 20, it is reliably prevented that the counter electrodes 20 of the adjacent DSC 50 contact each other. Is done.

  Furthermore, the thickness of the insulating material 14 is larger than the thickness of the transparent conductive film 12, and the insulating material 14 has a higher melting point than the first sealing portion 31A. In this case, the first sealing portion 31 </ b> A has a higher melting point than the insulating material 14. For this reason, for example, the dye-sensitized solar cell module 100 is used at a high temperature, the first sealing portion 31A is softened, and the distance between the transparent conductive substrate 15 and the counter electrode 20 may be reduced. At this time, even if the counter electrode 20 tries to approach the transparent conductive film 12, the thickness of the insulating material 14 is larger than the thickness of the transparent conductive film 12, and the insulating material 14 is larger than the first sealing portion 31A. Since it has a high melting point, contact between the counter electrode 20 and the transparent conductive film 12 is sufficiently prevented.

  In the DSC module 100, the transparent conductive film 12 in one DSC 50 has two projecting portions 12c and an extending portion 12d extending from each of the projecting portions 12c to the other DSC 50 side. The part 12d extends to the outside of the sealing part 30A of the DSC 50A and to a side position with respect to the side edge part 12b of the main body part 12a of the DSC 50A. Then, the extending portion 12 d and the metal substrate 21 of the counter electrode 20 in the other DSC 50 are connected via the conductive material 60. That is, in the DSC module 100, in two adjacent DSCs 50, the transparent conductive film 12 of one DSC 50 and the counter electrode 20 of the other DSC 50 include the sealing portions 30A of all the dye-sensitized solar cells 50A to 50D. Connected outside the light receiving area. In other words, a connection point that does not contribute to power generation in the DSC module 100 is provided outside the light receiving area. Therefore, the aperture ratio can be improved. In addition, since the transparent conductive film 12 of one DSC 50 and the counter electrode 20 of the other DSC 50 are connected outside the light receiving area, the connection portion between the transparent conductive film 12 and the conductive material 60, and the counter electrode 20 and the conductive material. It is also possible to increase the area of the connection point with 60. Further, the extending portion 12d of the transparent conductive film 12 in one DSC 50 is positioned laterally from the overhanging portion 12c to the outside of the sealing portion 30A of the other DSC 50A and to the side edge portion 12b of the main body portion 12a of the DSC 50A. It extends to. That is, the transparent conductive film 12A of the DSC 50B is provided in the immediate vicinity of the counter electrode 20 of the adjacent DSC 50A. For this reason, the conductive material 60 can be shortened, and the operator's hand is not easily caught by the conductive material 60. As a result, it is possible to prevent an excessive stress from being applied to the connection portion between the conductive material 60 and the counter electrode 20 or the connection portion between the conductive material 60 and the transparent conductive film 12, and the connection reliability in the DSC module 100 is sufficient. Can be improved.

  Further, in the DSC module 100, in two adjacent DSCs 50, the counter electrode 20 of one DSC 50 and the extending portion 12d of the transparent conductive film 12 of the other DSC 50 are connected by a conductive material 60 made of a metal film. For this reason, it is possible to reduce the unevenness on the surface of the counter electrode 20 opposite to the working electrode 1, and it is possible to stably install the DSC module 100 on a flat surface such as the inner wall surface of the case.

  Next, a method for manufacturing the DSC module 100 will be described.

  First, a transparent conductive substrate 15 formed by forming a transparent conductive film 12 on one transparent substrate 11 is prepared.

  The material which comprises the transparent substrate 11 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES) and the like. The thickness of the transparent substrate 11 is appropriately determined according to the size of the DSC module 100 and is not particularly limited, but may be in the range of 50 μm to 10000 μm, for example.

As a material constituting the transparent conductive film 12, for example, tin-doped indium oxide (Indium-Tin-Oxide: ITO), tin oxide (SnO ₂ ), fluorine-doped tin oxide (Fluorine-doped-Tin-Oxide: FTO), etc. Examples include conductive metal oxides. The transparent conductive film 12 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive film 12 is composed of a single layer, the transparent conductive film 12 is preferably composed of FTO because it has high heat resistance and chemical resistance. In addition, it is preferable to use a laminate composed of a plurality of layers as the transparent conductive film 12 because the characteristics of each layer can be reflected. Among these, it is preferable to use a laminate of a layer made of ITO and a layer made of FTO. In this case, the transparent conductive film 12 having high conductivity, heat resistance and chemical resistance can be realized. The thickness of the transparent conductive film 12 may be in the range of 0.01 μm to 2 μm, for example.

  As a method for forming the transparent conductive film 12, a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, a CVD method, or the like is used. Of these, the spray pyrolysis method is preferable from the viewpoint of apparatus cost.

Next, patterning is performed on the transparent conductive film 12 with, for example, a YAG laser or a CO ₂ laser as follows. That is, patterning is performed so that the four transparent conductive films 12A to 12D corresponding to the DSCs 50A to 50D have the rectangular main body portion 12a and the overhanging portion 12c. At this time, for the transparent conductive films 12B to 12D corresponding to the DSCs 50B to 50D, not only the rectangular main body part 12a and the overhanging part 12c but also an extending part 12d extending from the overhanging part 12c to the adjacent DSC 50 side. Patterning is performed to form.

  Next, the oxide semiconductor layer 13 is formed on the main body 12 a of the transparent conductive film 12. The oxide semiconductor layer 13 is formed by printing a porous oxide semiconductor layer forming paste containing oxide semiconductor particles, followed by firing.

The oxide semiconductor layer forming paste contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles. Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), silica (SiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), strontium titanate (SrTiO ₃ ), Tin oxide (SnO ₂ ), indium oxide (In ₃ O ₃ ), zirconium oxide (ZrO ₂ ), thallium oxide (Ta ₂ O ₅ ), lanthanum oxide (La ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), It consists of holmium oxide (Ho ₂ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), or two or more thereof.

  The thickness of the oxide semiconductor layer 13 may be, for example, 0.5 to 50 μm.

  As a method for printing the oxide semiconductor layer forming paste, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

  The firing temperature varies depending on the material of the oxide semiconductor particles, but is usually 350 ° C. to 600 ° C., and the firing time also varies depending on the material of the oxide semiconductor particles, but is usually 1 to 5 hours.

  Next, the insulating material 14 disposed between the adjacent DSCs 50 is fixed on the transparent substrate 11. The insulating material 14 is provided to prevent the transparent conductive film 12 on the transparent substrate 11 and the counter electrode 20 from coming into contact with each other and short-circuiting. Therefore, the insulating material 14 only needs to have a higher melting point than the first sealing portion 31A.

  As the insulating material 14, for example, an inorganic material such as low-melting glass, polyimide, an ultraviolet curable resin, a thermoplastic resin, or the like is used. Among these, an inorganic substance is preferable because it effectively prevents leakage of the electrolyte 40.

  The thickness of the insulating material 14 is usually 1 to 200 μm, preferably 3 to 10 μm.

  Thus, the working electrode 10 is obtained.

  Next, a photosensitizing dye is supported on the oxide semiconductor layer 13 of the working electrode 10. For this purpose, the working electrode 10 is immersed in a solution containing a photosensitizing dye, the dye is adsorbed on the oxide semiconductor layer 13, and then the excess dye is washed away with the solvent component of the solution, followed by drying. Thus, the photosensitizing dye may be adsorbed to the oxide semiconductor layer 13. However, even if the photosensitizing dye is adsorbed to the oxide semiconductor layer 13 by applying a solution containing the photosensitizing dye to the oxide semiconductor layer 13 and then drying the solution, the photosensitizing dye can be absorbed into the oxide semiconductor layer 13. 13 can be carried.

  Examples of the photosensitizing dye include a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, and the like, and organic dyes such as porphyrin, eosin, rhodamine, and merocyanine.

  Next, the electrolyte 40 is disposed on the oxide semiconductor layer 13.

The electrolyte 40 contains a redox couple such as I ⁻ / I ₃ ^— and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ⁻ and bromine / bromide ion pairs. A gelling agent may be added to the volatile solvent. The electrolyte 40 may be composed of an ionic liquid electrolyte made of a mixture of an ionic liquid and a volatile component. As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used. As such a room temperature molten salt, for example, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is preferably used. As the volatile component, the above and an organic solvent, 1-methyl-3-methyl imidazolium iodide, _LiI, and the like I 2, 4-t-butylpyridine.

  Next, as shown in FIG. 6, the 1st sealing part formation body 131 for forming the 1st sealing part 31 is prepared. The 1st sealing part formation body 131 can be obtained by preparing the sealing resin film of 1 sheet, and forming the square-shaped opening 131a according to the number of DSC50 in the sealing resin film. The first sealing portion forming body 131 has a structure in which a plurality of first sealing portion forming bodies 131A are integrated.

  Examples of the sealing resin film include resins such as ionomer, ethylene-vinyl acetic anhydride copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ultraviolet curable resin, and vinyl alcohol polymer. Is mentioned.

  Then, the first sealing portion forming body 131 is bonded onto the working electrode 10. At this time, the first sealing portion forming body 131 is bonded to the working electrode 10 so as to overlap the insulating material 14. The first sealing portion forming body 131 can be adhered to the working electrode 10 by heating and melting the first sealing portion forming body 131. The first sealing portion forming body 131 is bonded to the working electrode 1 so that the main body portion 12 a is disposed inside the first sealing portion forming body 131.

  Next, a plurality of counter electrodes 20 are prepared.

  As described above, the counter electrode 20 includes the metal substrate 21 and the conductive catalyst layer 22 that is provided on the working electrode 10 side of the metal substrate 21 and promotes the reduction reaction on the surface of the counter electrode 20.

  The metal substrate 21 is composed of, for example, a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, or tungsten, or a film formed of a conductive oxide such as ITO or FTO on the transparent substrate 11 described above. The thickness of the metal substrate 21 is appropriately determined according to the size of the DSC module 100 and is not particularly limited, but may be, for example, 0.005 mm to 0.1 mm.

  The catalyst layer 22 is composed of platinum, a carbon-based material, a conductive polymer, or the like. Here, carbon nanotubes are suitably used as the carbon-based material.

  Next, another first sealing portion forming body 131 described above is prepared. And each of the some counter electrode 20 is bonded together so that each opening 131a of the 1st sealing part formation body 131 may be plugged up.

  Next, the first sealing portion forming body 131 bonded to the counter electrode 20 and the first sealing portion forming body 131 bonded to the working electrode 10 are superposed and heated while pressurizing the first sealing portion forming body 131. Melt. Thus, the first sealing portion 31 is formed between the working electrode 10 and the counter electrode 20. The formation of the first sealing portion 31 may be performed under atmospheric pressure or under reduced pressure, but is preferably performed under reduced pressure.

  Next, as shown in FIG. 5, a second sealing portion 32 is prepared. The second sealing portion 32 has a structure in which a plurality of first sealing portions 32A are integrated. The second sealing portion 32 can be obtained by preparing a single sealing resin film and forming a rectangular opening 32a corresponding to the number of DSCs 50 in the sealing resin film. The second sealing portion 32 is bonded to the counter electrode 20 so as to sandwich the edge portion 20 a of the counter electrode 20 together with the first sealing portion 31. The adhesion of the second sealing portion 32 to the counter electrode 20 can be performed by heating and melting the second sealing portion 32.

  Examples of the sealing resin film include resins such as ionomer, ethylene-vinyl acetic anhydride copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ultraviolet curable resin, and vinyl alcohol polymer. Is mentioned. The constituent material of the sealing resin film for forming the second sealing portion preferably has a higher viscosity than the constituent material of the sealing resin film for forming the first sealing portion. In this case, the durability of the DSC module can be further improved.

  Finally, a paste containing a metal material constituting the conductive material 60 is prepared, and this paste is applied from the counter electrode 20 to the extending portion 12d of the transparent conductive film 12 of the adjacent DSC 50 and cured. At this time, from the viewpoint of avoiding an adverse effect on the photosensitizing dye, it is preferable to use a low-temperature curable paste that can be cured at a temperature of 90 ° C. or lower. Thus, a conductive material 60 that connects the counter electrode 20 and the transparent conductive film 12 of the adjacent DSC 50 is obtained (see FIG. 1).

  The DSC module 100 is obtained as described above.

  The present invention is not limited to the above embodiment. For example, the second sealing portion 32A is bonded to the first sealing portion 31A, but the second sealing portion 32A may not be bonded to the first sealing portion 31A.

  In the above embodiment, the second sealing portion 32A is provided, but the second sealing portion 32A is not necessarily required.

  Furthermore, the annular first sealing portions 31A of the adjacent DSCs 50 do not necessarily have to be integrated. That is, the annular first sealing portions 31A may be separated from each other.

  In the above embodiment, each of the transparent conductive films 12B to 12D has the two overhanging parts 12c. However, the transparent conductive films 12B to 12D do not need to have two overhanging parts 12c, and have only one overhanging part 12c. It may be. In this case, the transparent conductive films 12B to 12D have only one extending portion 12d.

  Furthermore, in the said embodiment, although the electrically conductive material 60 is comprised with the metal film, the electrically conductive material 60 is not restricted to a metal film, You may comprise with a jumper wire etc.

  Furthermore, in the above embodiment, the oxide semiconductor layer 13 is provided on the transparent conductive film 12, but may be provided on the metal substrate 21. In this case, the oxide semiconductor layer 13 and the metal substrate 21 constitute a working electrode, and the transparent substrate 11 and the transparent conductive film 12 constitute a counter electrode.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
First, a transparent conductive substrate was prepared by forming a transparent conductive film made of FTO having a thickness of 1 μm on a transparent substrate made of glass having a thickness of 1 mm. Then, patterning was performed so that four transparent conductive films arranged in a row were formed by a CO ₂ laser (V-460 manufactured by Universal System). In the patterning, the four transparent conductive films were formed so as to have 3 cm × 5 cm rectangular main body portions, and the interval between the main body portions was 0.5 mm. Of the four transparent conductive films, three transparent conductive films are formed of two protruding portions that protrude from the side edge portion of the main body portion and the transparent conductive film corresponding to the adjacent DSC from each of the two protruding portions. An extension portion extending to a side position with respect to the side edge portion of the main body portion is formed. At this time, the length of the overhang portion was 1 cm, and the width in the overhang direction was 3 mm. Further, the width of the extending part was 2 mm, and the length of the extending part in the extending direction was 2 cm.

  Next, an oxide semiconductor layer forming paste containing titania was applied onto the main body of the transparent conductive film and dried, followed by baking at 500 ° C. for 1 hour. Thus, a working electrode having the oxide semiconductor layer 13 was obtained.

  Next, an insulating material made of low-melting glass was baked after screen printing and formed between adjacent main body portions.

  Next, the working electrode is immersed overnight in a dye solution containing 0.3 mmol of a photosensitizing dye composed of N719 and a solvent in which acetonitrile and tert-butanol are mixed at a volume ratio of 1: 1. Then, it was taken out and dried, and a photosensitizing dye was supported on the oxide semiconductor layer.

  Next, an electrolyte made of iodine redox was applied on the oxide semiconductor layer and dried to place the electrolyte.

  Next, the 1st sealing part formation body for forming a 1st sealing part was prepared. Each of the first sealing portion forming bodies is prepared with a single sealing resin film made of a 12 cm × 5 cm × 50 μm ethylene-methacrylic acid copolymer (trade name: Nucrel, Mitsui / DuPont Polychemical). The resin film for sealing was obtained by forming four rectangular openings. At this time, each opening was set to have a size of 2.8 cm × 4.8 cm × 50 μm. As a result, a first sealing portion forming body having a width of 1 mm was obtained.

  And after mounting this 1st sealing part formation body on a working electrode, the 1st sealing part formation body was adhere | attached on the working electrode by heat-melting.

  Next, four counter electrodes were prepared. Each counter electrode was prepared by forming a catalyst layer made of platinum having a thickness of 10 nm on a 2.95 cm × 5 cm × 40 μm titanium foil by sputtering. In addition, another first sealing portion forming body was prepared, and this first sealing portion forming body was adhered to the surface of the counter electrode facing the working electrode in the same manner as described above.

  And the 1st sealing part formation object adhered to the working electrode and the 1st sealing part formation object adhered to the counter electrode were made to oppose, and the 1st sealing part formation object was piled up. And in this state, the 1st sealing part formation body was heat-melted, pressing the 1st sealing part formation body. Thus, the first sealing portion was formed between the working electrode and the counter electrode.

  Next, the 2nd sealing part was prepared. The second sealing portion prepares one sealing resin film made of maleic anhydride-modified polyethylene (trade name: Binnel, manufactured by DuPont) having a size of 13 cm × 6 cm × 50 μm. It was obtained by forming four rectangular openings. At this time, each opening was set to have a size of 2.8 cm × 4.8 cm × 50 μm. As a result, a second sealing portion having a width of the outer peripheral portion of 1.5 mm and a width of the partition portion partitioning the inner opening of the outer peripheral portion of 1 mm was obtained. The second sealing part was bonded to the counter electrode so as to sandwich the edge of the counter electrode together with the first sealing part. At this time, the first sealing portion and the second sealing portion were bonded to the counter electrode and the first sealing portion by heating and melting while pressing the second sealing portion against the counter electrode.

  Finally, a low temperature curing type silver paste (Fujikura Kasei Co., Ltd., D-500) is prepared, applied from the counter electrode over the extended portion of the transparent conductive film corresponding to the adjacent DSC, and cured at 30 ° C. for 12 hours. It was. Thus, a conductive material made of silver of 7 mm × 10 mm × 10 μm was formed. A DSC module was thus obtained.

(Comparative Example 1)
A transparent conductive film that does not have an extending part is formed, and the second sealing part is not used, and the first sealing part has a width of 1 mm and an opening of 2.8 mm × 4.8 mm 4 Other than having two square annular sealing parts, the interval between the sealing parts of adjacent DSCs is 2 mm, and the edge of the counter electrode and the transparent conductive film of the adjacent DSC are connected via a jumper wire between the sealing parts Produced a DSC module in the same manner as in Example 1.

(Comparative Example 2)
The sealing part and the counter electrode of the second and fourth DSCs from the first DSC on one end side of the four DSCs are shifted by 2 mm laterally with respect to the arrangement direction of the four DSCs, respectively. A DSC module was produced in the same manner as in Comparative Example 1 except that the transparent conductive film of DSC was exposed, and the exposed transparent conductive film was connected to the counter electrode of the adjacent DSC through the same conductive material as in Example 1. did.

With respect to the DSC modules obtained in Example 1, Comparative Example 1 and Comparative Example 2, the aperture ratio was measured. The results are shown in Table 1.

  As shown in Table 1, it was found that the DSC module obtained in Example 1 had a larger aperture ratio than the DSC modules obtained in Comparative Examples 1 and 2.

  In the DSC module of Example 1, in two adjacent DSCs, the counter electrode of one DSC and the extending portion of the transparent conductive film of the other DSC are connected by a metal film. For this reason, it is considered that there is no worry that the operator's hand will be caught, and the connection reliability can be sufficiently improved. Further, since the metal film is sufficiently prevented from contacting the counter electrode of the adjacent dye-sensitized solar cell, the adjacent counter electrodes are sufficiently prevented from being electrically connected by the metal film. As a result, it is considered possible to sufficiently prevent malfunction of the DSC module.

DESCRIPTION OF SYMBOLS 10 ... Working electrode 11 ... Transparent substrate 12 ... Transparent electrically conductive film 12a ... Main-body part 12c ... Overhang | projection part 12d ... Extension part 13 ... Oxide semiconductor layer 15 ... Transparent conductive substrate (1st electrode)
20 ... Counter electrode (second electrode)
DESCRIPTION OF SYMBOLS 21 ... Metal substrate 30, 30A ... Sealing part 50 ... Dye-sensitized solar cell 60 ... Conductive material 100 ... Dye-sensitized solar cell module.

Claims (2)

In a dye-sensitized solar cell module having a plurality of dye-sensitized solar cells connected in series,
The dye-sensitized solar cell is
A first electrode having a transparent conductive film provided on the transparent substrate and the transparent substrate and having a main body;
A second electrode facing the first electrode and including a metal substrate;
An oxide semiconductor layer provided on the first electrode or the second electrode;
An annular sealing portion for joining the first electrode and the second electrode,
The transparent substrate is composed of a common transparent substrate of the plurality of dye-sensitized solar cells,
In two adjacent dye-sensitized solar cells, the transparent conductive film in one dye-sensitized solar cell is
An overhanging portion that protrudes beyond the sealing portion laterally with respect to the arrangement direction of the plurality of dye-sensitized solar cells from the main body portion;
An extension portion extending from the overhang portion to the outside of the sealing portion of the other dye-sensitized solar cell and to a position on the side of the main body portion of the other dye-sensitized solar cell;
The extension part and the metal substrate of the second electrode in the other dye-sensitized solar cell are connected via a conductive material,
Dye-sensitized solar cell module. The dye-sensitized solar cell module according to claim 1, wherein the conductive material is a metal film.

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