JP5762053B2 - Dye-sensitized solar cell, method for producing the same, dye-sensitized solar cell module and method for producing the same - Google Patents

Description

  The present invention relates to a dye-sensitized solar cell, a manufacturing method thereof, a dye-sensitized solar cell module, and a manufacturing method thereof.

  The dye-sensitized solar cell module includes a plurality of dye-sensitized solar cells connected in series and electrically. Each dye-sensitized solar cell has a working electrode, a counter electrode facing the working electrode, and a sealing portion for joining them, and the working electrode includes a transparent substrate and a transparent conductive film formed thereon. And an oxide semiconductor layer provided over the transparent conductive film.

  In such a dye-sensitized solar cell module, as a method of connecting a plurality of dye-sensitized solar cells in series, a method described in Patent Document 1 has been conventionally known. In the method described in Patent Document 1, copper or nickel for connecting to another dye-sensitized solar cell in a region on the opposite side of the working electrode from the titanium counter electrode and outside the outer periphery of the sealing portion. On the other hand, a connection terminal is also bonded onto a transparent conductive film of an adjacent dye-sensitized solar cell, and these connection terminals are connected to each other via a conductive wire. In Patent Document 1, as a method of joining a connection terminal made of copper or nickel to a titanium counter electrode, the connection terminal is connected to the titanium counter electrode by applying ultrasonic waves to the connection terminal while pressurizing the titanium counter electrode with the connection terminal. A method of joining is described. The reason why the connection terminal is joined to the surface of the titanium counter electrode opposite to the working electrode is to inject electrons from the adjacent dye-sensitized solar cell or from the outside into the electrolyte through the titanium counter electrode.

International Publication No. 2009/13389

  However, the method described in Patent Document 1 has the following problems.

  That is, in the method described in Patent Document 1, a connection terminal made of copper or nickel is bonded to a region of the titanium counter electrode opposite to the working electrode and outside the outer periphery of the sealing portion. For this reason, a terminal must be joined to a very small space of the titanium counter electrode, and the connection strength is not necessarily sufficient. For this reason, the dye-sensitized solar cell module having this dye-sensitized solar cell has room for improvement in terms of connection reliability.

  In order to improve the connection reliability, it is conceivable to provide a connection terminal in a region inside the outer periphery of the sealing portion, that is, directly above the oxide semiconductor layer, on the surface of the titanium counter electrode opposite to the working electrode.

  However, in that case, since the joint portion of the connection terminal approaches the oxide semiconductor layer, the photosensitizing dye carried on the oxide semiconductor layer may be deteriorated.

  Therefore, a method for producing a dye-sensitized solar cell having excellent connection reliability while suppressing deterioration of the photosensitizing dye is required.

  The present invention has been made in view of the above matters, a dye-sensitized solar cell having excellent connection reliability while suppressing deterioration of a photosensitizing dye, a manufacturing method thereof, a dye-sensitized solar cell module, and a manufacturing thereof. It aims to provide a method.

  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.

That is, the present invention provides a method for producing a dye-sensitized solar cell module in which a plurality of dye-sensitized solar cells are connected in series and electrically, and the plurality of dye-sensitized solar cells are connected in series and electrically. A second electrode including a metal substrate made of a metal forming a passive film, and a first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate. A preparation step for preparing the oxide semiconductor layer forming step for forming an oxide semiconductor layer on the first electrode or the second electrode, a dye carrying step for carrying a photosensitizing dye on the oxide semiconductor layer, An electrolyte disposing step of disposing an electrolyte on the oxide semiconductor layer; a sealing step of sealing the electrolyte by a sealing portion with the first electrode and the second electrode facing each other; and the second electrode On a metal substrate The serial straight connecting member made of a metal having a lower resistance than the metal substrate on the side opposite to the first electrode, beyond upper the street the sealing portion on the inner region of the sealing portion of the second electrode wherein a connecting member fixing process and the method for manufacturing a dye-sensitized solar cell comprising of fixing to exit tension of a metal substrate, in the connecting member fixing process, bonded to the metal substrate by resistance welding the connecting member Te The connection member is fixed on the metal substrate by the manufacturing method of the dye-sensitized solar cell, and in the connecting step, one of the two dye-sensitized solar cells adjacent to each other A terminal provided on the first electrode of the other dye-sensitized solar cell in a state in which the connection member provided on the second electrode projects from the metal substrate to the other dye-sensitized solar cell side; Connect It is a manufacturing method of a dye-sensitized solar cell module.

According to this manufacturing method, the dye-sensitized solar cell is manufactured by the above-described manufacturing method, thereby obtaining a dye-sensitized solar cell in which deterioration of the photosensitizing dye is sufficiently suppressed and having excellent connection reliability. It is done. For this reason, when the metal substrate of the second electrode and the terminal of the first electrode of the adjacent dye-sensitized solar cell are connected in the connecting step, the dye-sensitized solar cell module having excellent photoelectric conversion characteristics and connection reliability. Can be obtained. According to this manufacturing method, the connecting member fixing process to fix the connecting member on the metal substrate by joining a metal substrate connecting member by a resistance welding which has a lower resistance than the metal substrate. Here, resistance welding generates heat at the contact portion between the connection member and the metal substrate by pressing the two electrodes against the connection member and / or the metal substrate and passing an electric current between them. In this method, both the connecting member and the metal substrate are melted by this heat to connect them. At this time, heat is generated only at the contact portion between the metal substrate and the connecting member. Further, in resistance welding, the time for supplying current is short (several milliseconds), so the time for generating heat is also short. For this reason, the place where heat is applied can be suppressed to a local region. Therefore, even when the connection member is fixed on the metal substrate of the second electrode after the sealing step, the deterioration of the photosensitizing dye carried on the oxide semiconductor layer can be sufficiently suppressed.

  Further, in the connecting member fixing step, the metal substrate and the connecting member are melted and joined, so that an alloy portion is formed between them. For this reason, the bonding strength between the metal substrate and the connection member is increased, and excellent connection reliability is obtained when a plurality of dye-sensitized solar cells obtained are connected in series to manufacture a dye-sensitized solar cell module. A dye-sensitized solar cell module can be obtained. Moreover, the contact resistance between a 2nd electrode and a connection member can also be reduced by providing an alloy part between a 2nd electrode and a connection member. Moreover, in the manufacturing method of this invention, since the place where heat is applied can be restrained to a local area | region by joining a connection member to a metal substrate by resistance welding, fixing a connection member to the inner area | region of a sealing part. Is also possible. In this case, the distance between the connecting member and the electrolyte that passes through the metal substrate having a larger resistance than that of the connecting member can be shortened, and the resistance between the connecting member and the electrolyte can be reduced.

  In the connection member fixing step, two electrodes for resistance welding are connected in the state in which the connection member is brought into contact with the surface of the metal substrate opposite to the first electrode in resistance welding. It is preferable that the contact is made by contacting the member and the surface of the metal substrate.

  In this case, when the second electrode and the connection member are connected by resistance welding, it is not necessary to press the two resistance welding electrodes against the surface on the first electrode side of the metal substrate of the second electrode. For this reason, the deformation | transformation in the surface at the side of the 1st electrode among metal substrates can fully be prevented. There is also an advantage that welding of the resistance welding electrode can be prevented on the surface of the metal substrate of the second electrode on the first electrode side.

  In the connecting member fixing step, resistance welding is preferably performed for 3 to 20 milliseconds.

  In this case, the thickness of the alloy portion becomes appropriate, and both the bonding strength and the resistance are improved between the connection member and the metal substrate.

  The thickness of the connecting member is preferably 9 to 200 μm.

  In this case, when the thickness of the connection member is 9 μm or more, the strength is sufficiently improved as compared with the case where the thickness is less than 9 μm, and the connection member is not easily deformed during resistance welding. On the other hand, when the thickness of the connecting member is 200 μm or less, the second electrode and the connecting member can be connected in a shorter time than when the thickness exceeds 200 μm. Moreover, the unevenness | corrugation of the surface on the opposite side to a 1st electrode among 2nd electrodes can be decreased, and it can install stably on a flat surface.

  The thickness of the second electrode is preferably 9 to 200 μm. If the thickness of the second electrode is 9 μm or more, the strength of the second electrode is greater than when the thickness is less than 9 μm. On the other hand, when the thickness of the second electrode is 200 μm or less, the second electrode and the connection member can be connected in a shorter time than when the thickness exceeds 200 μm. Further, the second electrode can be flexible.

  In the connecting step, the connecting member of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells and the terminal provided on the first electrode of the other dye-sensitized solar cell are resisted. It is preferable to connect directly by welding.

  In this case, the connecting member of one dye-sensitized solar cell of the two adjacent dye-sensitized solar cells and the terminal of the first electrode of the other dye-sensitized solar cell are compared with the case where solder or the like is used. In addition to being able to be easily joined, the connection strength can be improved and the contact resistance can also be reduced. Further, resistance welding is performed by locally applying an electrode for resistance welding when joining the connecting member of one dye-sensitized solar cell and the terminal of the first electrode of the other dye-sensitized solar cell. , Heat is generated only locally. For this reason, compared with the case where it joins using solder etc., degradation of the pigment and the sealing part carried by the oxide semiconductor layer is suppressed more fully.

Moreover, this invention is a dye-sensitized solar cell module formed by electrically connecting a plurality of dye-sensitized solar cells in series, and the dye-sensitized solar cell is provided on the transparent substrate and the transparent substrate. A first electrode having a transparent conductive film; a second electrode including a metal substrate made of a metal forming a passive film; an oxide semiconductor layer provided on the first electrode or the second electrode; the first electrode; An electrolyte provided between the second electrode, a sealing portion for joining the first electrode and the second electrode, and a surface of the second electrode opposite to the first electrode; A linear connecting member made of a metal having a lower resistance than that of the metal of the metal substrate, and in the dye-sensitized solar cell, the metal of the metal substrate is interposed between the second electrode and the connecting member. And an alloy of the connecting member metal. The connection member provided on the second electrode of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells provided with an alloy part, and the first electrode of the other dye-sensitized solar cell to be a terminal provided to connect the connection member, the second the other dye-sensitized solar from the metal substrate beyond upper street the sealing portion on the inner region of the sealing portion of the electrode This is a dye-sensitized solar cell module extending to the battery side.

According to this dye-sensitized solar cell module, each dye-sensitized solar cell has sufficiently suppressed deterioration of the dye and has excellent connection reliability. For this reason, the dye-sensitized solar cell module which has the outstanding photoelectric conversion characteristic and connection reliability is implement | achieved. According to this invention, since the alloy part made of an alloy of the metal of the second electrode and the metal of the connection member is provided between the second electrode and the connection member, the second electrode and the connection member Connection strength is increased, and excellent connection reliability is obtained. Moreover, the contact resistance between a 2nd electrode and a connection member can also be reduced by providing an alloy part between a 2nd electrode and a connection member.

Te above dye-sensitized solar cell module odor, between the said connecting member terminals, it is preferable that an alloy portion formed of an alloy of a metal constituting the terminals and the metal constituting the connecting member is provided .

  In this case, the connection strength between the terminal and the connection member is increased, and excellent connection reliability is obtained. Moreover, the contact resistance between a terminal and a connection member can also be reduced by providing an alloy part between a terminal and a connection member.

  ADVANTAGE OF THE INVENTION According to this invention, degradation of a photosensitizing dye is fully suppressed and the dye-sensitized solar cell which has the outstanding connection reliability, its manufacturing method, a dye-sensitized solar cell module, and its manufacturing method are provided.

It is a fragmentary sectional view which shows one Embodiment of the dye-sensitized solar cell module of this invention. It is the elements on larger scale of FIG. It is a fragmentary sectional view which shows the process of joining the connection member of FIG. 1 to the metal substrate. It is a fragmentary sectional view which shows other embodiment of the dye-sensitized solar cell module of this invention.

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

  First Embodiment First, a first embodiment of the dye-sensitized solar cell module of the present invention will be described. FIG. 1 is a partial cross-sectional view showing an embodiment of the dye-sensitized solar cell module of the present invention.

  As shown in FIG. 1, the dye-sensitized solar cell module 100 has a plurality (two in FIG. 1) of dye-sensitized solar cells 50, and the plurality of dye-sensitized solar cells 50 are connected in series and electrically. Has been. Hereinafter, for convenience of explanation, two adjacent dye-sensitized solar cells 50 in the dye-sensitized solar cell module 100 may be referred to as dye-sensitized solar cells 50A and 50B.

  First, the dye-sensitized solar cell 50A will be described.

  The dye-sensitized solar cell 50A includes a working electrode 10, a counter electrode 20 facing the working electrode 10, a sealing portion 30 that joins the working electrode 10 and the counter electrode 20, and the working electrode 10, the counter electrode 20, and an annular sealing portion. 30 and an electrolyte 40 filled in a cell space formed by 30.

  The working electrode 10 includes a transparent substrate 11 and a transparent conductive substrate 15 made of a transparent conductive film 12 provided on the transparent substrate 11, and an oxide semiconductor layer 13 provided on the transparent conductive film 12 of the transparent conductive substrate 15. And a wiring portion 17 provided so as to surround each of the oxide semiconductor layers 13 on the transparent conductive film 12. The wiring portion 17 includes a current collecting wiring 14 provided on the transparent conductive film 12 and a wiring protective layer 16 that covers the current collecting wiring 14. A photosensitizing dye is supported on the oxide semiconductor layer 13. A terminal 90 connected to the current collector wiring 14 is provided on the transparent conductive film 12 and outside the sealing portion 30, and a solder 70 is provided on the terminal 90. In the present embodiment, the first electrode is constituted by the transparent conductive substrate 15.

  The transparent substrate 11 of the dye-sensitized solar cell 50A is a transparent substrate common to all the dye-sensitized solar cells 50A and 50B in the dye-sensitized solar cell module 100.

  On the other hand, the counter electrode 20 includes a metal substrate 21 that forms a passive state and a catalyst layer 22 that is provided on the working electrode 10 side of the metal substrate 21 and promotes a catalytic reaction. A connecting member 60 having a lower resistance than the metal substrate 21 is provided on the surface of the counter electrode 20 opposite to the working electrode 10 on the metal substrate 21. In the present embodiment, the connection member 60 is provided only on a part of the metal substrate 21. Here, as shown in FIG. 2, between the connection member 60 and the metal substrate 21 of the counter electrode 20, there is an alloy portion 65 made of an alloy of the metal constituting the metal substrate 21 and the metal constituting the connection member 60. Is provided. As shown in FIG. 1, solder 70 is provided on the connection member 60. In the present embodiment, the second electrode is constituted by the counter electrode 20.

  The dye-sensitized solar cell 50B adjacent to the dye-sensitized solar cell 50A also has the same configuration as the dye-sensitized solar cell 50A.

  The dye-sensitized solar cell 50A and the dye-sensitized solar cell 50B are connected by a conductive wire 80. Specifically, one end of the conductive wire 80 is connected to the connecting member 60 of the dye-sensitized solar cell 50A by the solder 70, and the other end of the conductive wire 80 is connected to the terminal 90 of the dye-sensitized solar cell 50B by the solder 70. It is connected.

  According to the dye-sensitized solar cell module 100, the alloy part 65 made of an alloy of the metal constituting the metal substrate of the counter electrode 20 and the metal of the connection member 60 is provided between the counter electrode 20 and the connection member 60. . For this reason, the connection strength between the counter electrode 20 and the connection member 60 is increased, and the connection reliability is excellent. By providing the alloy part 65 between the counter electrode 20 and the connection member 60, the contact resistance between the counter electrode 20 and the connection member 60 can also be reduced.

  Hereinafter, the working electrode 10, the photosensitizing dye, the counter electrode 20, the sealing portion 30, the electrolyte 40, the connection member 60, the solder 70, the conductive wire 80, and the terminal 90 will be described in detail.

(Working electrode)
As described above, the working electrode 10 is provided on the transparent conductive substrate 15 including the transparent substrate 11 and the transparent conductive film 12 provided on the transparent substrate 11, and the transparent conductive film 12 of the transparent conductive substrate 15. And a porous oxide semiconductor layer 13 on which a sensitizing dye is supported.

  The transparent substrate 11 is composed of a substrate made of a light transmissive material. Examples of such materials include glass, polyethylene terephthalate (PET), polycarbonate (PC), polyethersulfone (PES), polyethylene naphthalate (PEN), and are usually used as a transparent substrate for photoelectric conversion elements. Any material can be used. The transparent substrate 11 is appropriately selected from these in consideration of resistance to the electrolyte 40 and the like. Further, the transparent substrate 11 is preferably a base material that is as excellent in light transmittance as possible, and more preferably a base material having a light transmittance of 90% or more.

The transparent conductive film 12 is preferably a thin film made of a conductive metal oxide so that the transparency of the working electrode 10 is not significantly impaired. Examples of such conductive metal oxides include indium tin oxide (ITO), fluorine-added tin oxide (FTO), and tin oxide (SnO ₂ ). Further, 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 ITO or FTO from the viewpoint of easy film formation and low manufacturing cost, and has high heat resistance and chemical resistance. From the viewpoint of having, it is more preferable that it is composed of FTO.

  Moreover, it is preferable that the transparent conductive film 12 is formed of a laminated body including a plurality of layers because the characteristics of each layer can be reflected. Among these, a laminated film in which a film made of FTO is laminated on a film made of ITO is preferable. In this case, the transparent conductive film 12 having high conductivity, heat resistance, and chemical resistance can be realized, and a transparent conductive substrate with low light absorption in the visible range and high conductivity can be configured. The thickness of the transparent conductive film 12 may be in the range of 0.01 μm to 2 μm, for example.

The oxide semiconductor for forming the porous oxide semiconductor layer 13 is not particularly limited, and any oxide semiconductor can be used as long as it is usually used for forming a porous oxide semiconductor layer for a photoelectric conversion element. be able to. Examples of such an oxide semiconductor include titanium oxide (TiO ₂ ), silica (SiO ₂ ), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), and niobium oxide (Nb ₂ O). ₅ ), strontium titanate (SrTiO ₃ ) 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 ), holmium oxide (Ho ₂ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), and aluminum oxide (Al ₂ O ₃ ). These can be used alone or in combination of two or more.

  The average particle diameter of these oxide semiconductor particles is 1-1000 nm, the surface area of the oxide semiconductor covered with the dye is increased, that is, the field for photoelectric conversion is increased, and more electrons are generated. This is preferable. The porous oxide semiconductor layer 13 is preferably configured by stacking oxide semiconductor particles having different particle size distributions. In this case, light can be repeatedly reflected in the semiconductor layer, and incident light that escapes to the outside of the porous oxide semiconductor layer 13 can be reduced, and light can be efficiently converted into electrons. The thickness of the porous oxide semiconductor layer 13 may be, for example, 0.5 to 50 μm. In addition, the porous oxide semiconductor layer 13 can also be comprised with the laminated body of the some oxide semiconductor which consists of a different material.

  Examples of the photosensitizing dye include a ruthenium complex containing a bipyridine structure, a terpyridine structure or the like as a ligand, a metal-containing complex such as polyphylline or phthalocyanine, and an organic dye such as eosin, rhodamine or merocyanine. The thing which shows the behavior suitable for a use and a semiconductor to be used can be selected without particular limitation. Specifically, N3, N719, a black dye, or the like can be used.

(Counter electrode)
The counter electrode 20 includes a metal substrate 21 that forms a passive state and a catalyst layer 22 that promotes a reduction reaction. As the metal constituting the metal substrate 21 that forms the passivity, for example, a material having durability in the electrolyte 40 such as titanium, nickel, niobium, aluminum, tungsten, or SUS can be used. The catalyst layer 22 is made of platinum or carbon.

(Sealing part)
The sealing part 30 connects the working electrode 10 and the counter electrode 20, and the electrolyte 40 between the working electrode 10 and the counter electrode 20 is sealed by being surrounded by the sealing part 30. Examples of the material constituting the sealing portion 30 include ionomer, ethylene-vinyl acetic anhydride copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ultraviolet curable resin, and vinyl alcohol polymer. Is mentioned. In addition, the sealing part 30 may be comprised only with resin, and may be comprised with resin and an inorganic filler.

(Electrolytes)
The electrolyte 40 is formed by impregnating the porous oxide semiconductor layer 13 with an electrolytic solution, or after impregnating the porous oxide semiconductor layer 13 with the electrolytic solution, the electrolytic solution is appropriately gelled. Gelled (quasi-solidified) using an agent and formed integrally with the porous oxide semiconductor layer 13, or a gel electrolyte containing an ionic liquid, oxide semiconductor particles, or conductive particles Can be used.

  As said electrolyte solution, what melt | dissolved electrolyte components, such as an iodine, iodide ion, and tertiary butyl pyridine, in organic solvents, such as ethylene carbonate and methoxyacetonitrile, is used. Examples of the gelling agent used for gelling the electrolytic solution include polyvinylidene fluoride, a polyethylene oxide derivative, and an amino acid derivative.

Although it does not specifically limit as said ionic liquid, Room temperature meltable salt which is a liquid at room temperature and made the compound which has the quaternized nitrogen atom into a cation or an anion is mentioned. Examples of the cation of the room temperature melting salt include quaternized imidazolium derivatives, quaternized pyridinium derivatives, quaternized ammonium derivatives and the like. Examples of the anion of the room temperature molten salt include BF ₄ ⁻ , PF ₆ ⁻ , F (HF) _n ⁻ , bistrifluoromethylsulfonylimide [N (CF ₃ SO ₂ ) ₂ ⁻ ], iodide ions, and the like. Specific examples of the ionic liquid include salts composed of a quaternized imidazolium cation and iodide ion or bistrifluoromethylsulfonylimide ion.

  The oxide semiconductor particles are not particularly limited in terms of the type and particle size of the substance, but those that are excellent in miscibility with an electrolytic solution mainly composed of an ionic liquid and that gel the electrolytic solution are used. . In addition, the oxide semiconductor particles are required to have excellent chemical stability against other coexisting components contained in the electrolyte 40 without reducing the conductivity of the electrolyte 40. In particular, even when the electrolyte 40 includes a redox pair such as iodine / iodide ions or bromine / bromide ions, the oxide semiconductor particles are preferably those that do not deteriorate due to an oxidation reaction.

Examples of such oxide semiconductor particles include TiO ₂ , SnO ₂ , WO ₃ , ZnO, Nb ₂ O ₅ , In ₂ O ₃ , ZrO ₂ , Ta ₂ O ₅ , La ₂ O ₃ , SrTiO ₃ , Y ₂ O. ₃ , Ho ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ , Al ₂ O ₃ are preferably selected from one or a mixture of two or more, and titanium dioxide fine particles (nanoparticles) are particularly preferable. The average particle diameter of the titanium dioxide is preferably about 2 nm to 1000 nm.

As the conductive particles, conductive particles such as conductors and semiconductors are used. The range of the specific resistance of the conductive particles is preferably 1.0 × 10 ⁻² Ω · cm or less, and more preferably 1.0 × 10 ⁻³ Ω · cm or less. Further, the type and particle size of the conductive particles are not particularly limited, and those that are excellent in miscibility with an electrolytic solution mainly composed of an ionic liquid and that gel the electrolytic solution are used. Such conductive particles are required to have excellent chemical stability with respect to other coexisting components contained in the electrolyte 40 because the conductivity is not easily lowered in the electrolyte 40. In particular, even when the electrolyte 40 contains an oxidation-reduction pair such as iodine / iodide ions or bromine / bromide ions, an electrolyte that does not deteriorate due to an oxidation reaction or the like is preferable.

  Examples of such conductive particles include those composed mainly of carbon, and specific examples include particles such as carbon nanotubes, carbon fibers, and carbon black. All methods for producing these substances are known, and commercially available products can also be used.

(Connecting member)
A connection member 60 is formed on the surface of the counter electrode 20 opposite to the working electrode 10 side, that is, on the surface of the metal substrate 21 of the first electrode 10. The connection member 60 is for connecting the two dye-sensitized solar cells 50 to each other. As the metal constituting the connection member 60, a metal having a resistance lower than that of the counter electrode 20 is used. Examples of such a metal include copper, silver, nickel, and the like. However, it is preferable to use copper because it is excellent in conductivity and solder wettability.

  The connecting member 60 is preferably provided in a portion of the counter electrode 20 that faces the electrolyte 40. In this case, it is possible to shorten the distance passing through the metal substrate 21 having a resistance higher than that of the connection member 60 between the connection member 60 and the electrolyte 40, thereby reducing the resistance between the connection member 60 and the electrolyte 40. It becomes possible.

  (Solder) As the solder 70, for example, a high melting point solder can be used. The high melting point solder has a melting point of 200 ° C. or higher (for example, 210 ° C. or higher). As such a high melting point solder, Sn-Cu type, Sn-Ag type, Sn-Ag-Cu type, Sn-Au type, Sn-Sb type, Sn-Pb type (Pb content is more than 85% by mass, for example) ) And the like. One of these may be used alone, or two or more may be used in combination.

  As the solder 70, it is also possible to use a solder having a lower melting point than the high melting point solder (hereinafter sometimes referred to as a low melting point solder). As the low melting point solder, for example, a solder having a melting point of less than 200 ° C. is preferably used. Examples of such solder include eutectic type (for example, Sn-Pb), lead-free type (for example, Sn-Ag, Sn-Cu, Sn-Ag-Cu, Sn-Zn, Sn-Zn-B). Is mentioned.

  By using the low melting point solder, it is possible to suppress the photosensitizing dye carried on the porous oxide semiconductor layer 13 or the electrolyte 40 from becoming high temperature when the conductive wire 80 and the connection member 60 are soldered. Further, deterioration of the photosensitizing dye and the electrolyte 40 can be suppressed.

(Conductive wire)
Examples of the material constituting the conductive wire 80 include metals such as gold, silver, copper, platinum, and aluminum.

  Next, the manufacturing method of the dye-sensitized solar cell module 100 shown in FIG. 1 is demonstrated.

  First, the working electrode 10 and the counter electrode 20 are prepared (preparation process).

  The working electrode 10 can be obtained by the following process. First, a transparent conductive film 12 is formed on one surface of the transparent substrate 11 to obtain a transparent conductive substrate 15.

  Examples of the method for forming the transparent conductive film 12 on the transparent substrate 11 include thin film formation methods such as sputtering, CVD (chemical vapor deposition), spray pyrolysis (SPD), and vapor deposition. Of these, the spray pyrolysis method is preferable. By forming the transparent conductive film 12 by spray pyrolysis, the haze rate can be easily controlled. Further, the spray pyrolysis method is preferable because a vacuum system is unnecessary, and thus the manufacturing process can be simplified and the cost can be reduced.

  Next, the porous oxide semiconductor layer 13 is formed on the transparent conductive film 12 in the counter electrode 20 (oxide semiconductor layer forming step).

  As a method for forming the porous oxide semiconductor layer 13, for example, a dispersion in which commercially available oxide semiconductor particles are dispersed in a desired dispersion medium or a colloidal solution that can be prepared by a sol-gel method is used as necessary. After adding a desired additive, the coating is performed by a known coating method such as a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, or a spray coating method, and then a void is formed by heat treatment or the like. It is possible to apply a method to make it.

  Next, the terminal 90 formed on the working electrode 10 is formed, for example, by applying a silver paste by printing or the like, and heating and baking.

  Next, a photosensitizing dye is supported on the porous oxide semiconductor layer 13 (dye supporting process).

  As a method for supporting the photosensitizing dye on the porous oxide semiconductor layer 13, first, a dye solution for supporting the dye, for example, a trace amount with respect to a solvent in which acetonitrile and t-butanol are 1: 1 in volume ratio. A solution prepared by adding N3 dye powder was prepared in advance.

  Next, in a solution containing a photosensitizing dye as a solvent in a petri dish-like container, heat treatment is separately performed at about 120 to 150 ° C. in an electric furnace to form the porous oxide semiconductor layer 13. The working electrode 10 is immersed, and immersed in a dark place day and night (approximately 20 hours). Thereafter, the working electrode 10 on which the porous oxide semiconductor layer 13 is formed is taken out of the solution containing the photosensitizing dye, and washed with a mixed solution of acetonitrile and t-butanol. As a result, the working electrode 10 having the porous oxide semiconductor layer 13 carrying the photosensitizing dye is obtained.

  On the other hand, to prepare the counter electrode 20, first, a metal substrate 21 that forms a passive state is prepared. Then, a catalyst layer 22 made of platinum or the like is formed on the surface of the prepared metal substrate 21. The catalyst layer 22 is formed by a sputtering method or the like. Thereby, the counter electrode 20 having the metal substrate 21 and the catalyst layer 22 can be obtained.

  Next, the electrolyte 40 is apply | coated on the porous oxide semiconductor layer 13, and the electrolyte 40 is arrange | positioned (electrolyte arrangement | positioning process).

  Next, the working electrode 10 and the counter electrode 20 are opposed to each other, and the electrolyte 40 is sealed by the sealing portion 30 (sealing process).

  For this purpose, first, a resin or its precursor for forming the sealing portion 30 is formed on the working electrode 10. At this time, the resin or its precursor is formed so as to surround the porous oxide semiconductor layer 13 of the working electrode 10. When the resin is a thermoplastic resin, the molten resin is applied on the working electrode 10 and then naturally cooled at room temperature, or a film-like resin is brought into contact with the working electrode 10 and the resin is heated and melted by an external heat source. Then, the resin can be obtained by natural cooling at room temperature. As the thermoplastic resin, for example, an ionomer or an ethylene-methacrylic acid copolymer is used. When the resin is an ultraviolet curable resin, an ultraviolet curable resin that is a precursor of the resin is applied on the working electrode 10. When the resin is a water-soluble resin, an aqueous solution containing the resin is applied on the working electrode 10. For example, a vinyl alcohol polymer is used as the water-soluble resin.

  Next, a resin or a precursor thereof for forming the sealing portion 30 is formed on the counter electrode 20. The resin or its precursor on the counter electrode 20 is formed at a position overlapping with the resin or its precursor on the working electrode 10 when the working electrode 10 and the counter electrode 20 face each other. The resin on the counter electrode 20 or its precursor may be formed in the same manner as the resin or its precursor formed on the working electrode 10.

  Next, the electrolyte 40 is filled in a region surrounded by the resin or its precursor on the working electrode 10.

  Then, the working electrode 10 and the counter electrode 20 are opposed to each other, and the resin on the counter electrode 20 and the working electrode 11 are overlapped. Thereafter, when the resin is a thermoplastic resin in a reduced pressure environment, the resin is heated and melted to bond the working electrode 10 and the counter electrode 20 together. In this way, the sealing part 30 is obtained. When the resin is an ultraviolet curable resin, the ultraviolet curable resin of the resin on the counter electrode 20 and the working electrode 10 are overlapped, and then the ultraviolet curable resin is cured by ultraviolet rays, whereby the sealing portion 30 is obtained. When the resin is a water-soluble resin, after the laminate is formed, the finger is dried at room temperature and then dried in a low-humidity environment, whereby the sealing portion 30 is obtained.

  Next, the connection member 60 having a lower resistance than that of the metal substrate 21 is fixed on the surface of the counter electrode 20 opposite to the working electrode 10 in the metal substrate 21 (connection member fixing step).

  The connection member 60 is fixed to the metal substrate 21 as follows. First, the connection member 60 is disposed on the surface of the counter electrode 20 opposite to the working electrode 10.

  Next, the metal substrate 21 and the connection member 60 are joined by resistance welding. Here, as shown in FIG. 3, resistance welding is performed by pressing the two resistance welding electrodes 110 </ b> A and 110 </ b> B against the connection member 60 and the metal substrate 21, or pressing either the connection member 60 or the metal substrate 21. By applying a current between them, heat is generated at the contact portion between the connection member 60 and the metal substrate 21, and both the connection member 60 and the metal substrate 21 are melted by this heat to connect the two. is there. At this time, heat is generated only at the contact portion between the metal substrate 21 and the connection member 60. Further, in resistance welding, the time for supplying current is short (several milliseconds), so the time for generating heat is also short. For this reason, the place where heat is applied can be suppressed to a local region. Therefore, even when the connection member 60 is formed on the metal substrate 21 of the counter electrode 20 after the sealing step, deterioration of the photosensitizing dye carried on the oxide semiconductor layer 13 can be sufficiently suppressed.

  At this time, since the metal substrate 21 forms a passive state, when the connection member 60 having a lower resistance than that of the metal substrate 21 is used, the contact resistance between the metal substrate 21 and the connection member 60 during resistance welding. Becomes larger. For this reason, the part where the metal substrate 21 and the connection member 60 are in contact with each other is easily melted by heat. When the voltage applied between the two electrodes 110 </ b> A and 110 </ b> B is turned off, the melted portion is solidified to form the alloy portion 65. Therefore, the bonding strength between the metal substrate 21 and the connection member 60 can be sufficiently improved. For this reason, when manufacturing the dye-sensitized solar cell module 100 by connecting the obtained several dye-sensitized solar cells 50 in series, obtaining the dye-sensitized solar cell module 100 which has the outstanding connection reliability. Can do. Moreover, the contact resistance between the counter electrode 20 and the connection member 60 can also be reduced by providing the alloy part 65 between the metal substrate 21 of the counter electrode 20 and the connection member 60. Further, by joining the connecting member 60 to the metal substrate 21 by resistance welding, a place where heat is applied can be suppressed to a local region, so that the connecting member 60 can be fixed to the inner region of the sealing portion 30. is there. In this case, it is possible to shorten the distance passing through the metal substrate 21 having a resistance higher than that of the connection member 60 between the connection member 60 and the electrolyte 40, thereby reducing the resistance between the connection member 60 and the electrolyte 40. It becomes possible.

  As shown in FIG. 3, when fixing the connection member 60 to the metal substrate 21 of the counter electrode 20, resistance welding is performed by bringing the connection member 60 into contact with the surface of the metal substrate 21 opposite to the working electrode 10. In this state, the two resistance welding electrodes 110A and 110B are preferably brought into contact with the connection member 60 and the surface of the metal substrate 21, respectively.

  In this case, when the counter electrode 20 and the connection member 60 are connected by resistance welding, the two resistance welding electrodes 110A and 100B do not need to be pressed against the surface of the metal substrate 21 of the counter electrode 20 on the working electrode 10 side. For this reason, the deformation | transformation in the surface by the side of the working electrode 10 among metal substrates 21 can fully be prevented. In addition, there is an advantage that welding of the resistance welding electrodes 110A and 110B to the surface of the metal substrate 21 on the working electrode 10 side can be prevented.

  The resistance welding is preferably performed for 3 to 20 milliseconds, more preferably 5 to 7 milliseconds. In this case, the connection strength between the counter electrode 20 and the connection member 60 can be improved more sufficiently, the thickness of the alloy portion 65 becomes appropriate, and the resistance between the connection member 60 and the metal substrate 21 is more sufficiently increased. Can be lowered.

  The thickness of the counter electrode 20 is not particularly limited, but is preferably 9 to 200 μm, and more preferably 20 to 100 μm. When the thickness of the counter electrode 20 is 9 μm or more, the strength is sufficiently improved as compared with the case where the thickness is less than 9 μm, and deformation during resistance welding becomes difficult. On the other hand, when the thickness of the counter electrode 20 is 200 μm or less, the counter electrode 20 and the connection member 60 can be connected in a shorter time than when the counter electrode 20 exceeds 200 μm. Further, the counter electrode 20 can be flexible.

  The thickness of the connection member 60 is not particularly limited, but is preferably 9 to 200 μm, and more preferably 20 to 100 μm.

  In this case, when the thickness of the connection member 60 is 9 μm or more, the strength is sufficiently improved as compared with the case where the thickness is less than 9 μm, and the connection member 60 is not easily deformed during resistance welding. On the other hand, when the thickness of the connecting member 60 is 200 μm or less, the counter electrode 20 and the connecting member 60 can be connected in a shorter time than when the thickness exceeds 200 μm. Moreover, the unevenness | corrugation of the surface on the opposite side to the working electrode 10 among the counter electrodes 20 can be decreased, and it can install stably on a flat surface.

  Although the current applied between the two resistance welding electrodes 110A and 110B depends on the combination of the connecting member 60 and the metal substrate 21, it cannot be generally stated, but is usually 0.5 to 5 kA and 1 to 3 kA. Preferably there is.

  Also, the current application time cannot be generally specified, but is usually 3 to 20 milliseconds, preferably 5 to 10 milliseconds.

  Furthermore, although the distance between the electrodes for resistance welding cannot be generally specified, it is usually 0.5 to 20 mm, and preferably 1 to 10 mm seconds.

  Next, the solder 70 is brought into contact with the connecting member 60 and melted, and then cooled. In this way, the solder 70 is joined to the connection member 60. Also, the solder 70 is brought into contact with the terminal 90 and melted, and then cooled. In this way, the solder 70 is joined to the terminal 90.

  In this way, the dye-sensitized solar cell 50A shown in FIG. 1 is obtained.

  Similarly, the dye-sensitized solar cell 50B is manufactured.

  Next, conductive wires 80 such as lead wires are prepared, and the dye-sensitized solar cells 50 </ b> A and 50 </ b> B are connected by the conductive wires 80. Specifically, one end of the conductive wire 80 is brought into contact with the solder 70 while being melted, and is fixed to the connection member 60 with the solder 70. Next, the other end of the conductive wire 80 is brought into contact with the solder 70 while being melted, and is fixed to the terminal 90 with the solder 70.

  Thus, the dye-sensitized solar cell module 100 is obtained.

  According to the method for manufacturing the dye-sensitized solar cell module 100, the dye-sensitized solar cell 50 is manufactured by the above-described manufacturing method, so that deterioration of the photosensitizing dye is sufficiently suppressed and excellent connection reliability is achieved. A dye-sensitized solar cell 50 having the following can be obtained. For this reason, in the connection step, when the metal substrate 21 of the counter electrode 20 and the terminal 90 of the working electrode 10 of the adjacent dye-sensitized solar cell 50 are connected, the dye-sensitized solar having excellent photoelectric conversion characteristics and connection reliability. The battery module 100 can be obtained.

Second Embodiment
Next, a second embodiment of the dye-sensitized solar cell module of the present invention will be described. In addition, the same code | symbol is attached | subjected to the component same or equivalent to 1st Embodiment, and the overlapping description is abbreviate | omitted.

  FIG. 4 is a cross-sectional view showing a second embodiment of the dye-sensitized solar cell module of the present invention. The dye-sensitized solar cell module 200 of the present embodiment is different from the dye-sensitized solar cell module 100 of the first embodiment in terms of the counter electrode and the connection state between the dye-sensitized solar cells 50A and 50B.

That is, as shown in FIG. 4, in the dye-sensitized solar cell module 200 of the present embodiment, the dye-sensitized solar cell 50 </ b > B is fixed to the surface of the counter electrode 20 on the side opposite to the working electrode 10. The connecting member 260 is further provided. In the present embodiment, the connection member 260 is linearly provided on a part of the metal substrate 21. The connecting member 260 is made of metal. Then, the edge 260a of the connecting member 260 Te overhanging the 50 A side dye-sensitized solar cell of the next beyond the sealing portion 30 are bonded directly to the terminal 90.

  In this case, since it becomes possible to connect between the dye-sensitized solar cells 50 adjacent to each other with a sufficiently small resistance as compared with the case where the connecting member 260 and the terminal 90 are joined using solder or the like, the voltage drop is reduced. It hardly happens. In addition, since electrons flowing from the terminal 90 can be brought close to the electrolyte 40 through the connection member 260 having a lower resistance than the metal substrate 21, the resistance from the connection member 260 to the electrolyte 40 can be reduced.

  At this time, the connection member 260 can be fixed to the metal substrate 21 of the counter electrode 20 by resistance welding. Specifically, both the two resistance welding electrodes may be pressed against the surface of the metal substrate 21 opposite to the working electrode 10 to apply a voltage between the two resistance welding electrodes.

  Even when the connection member 260 is formed on the metal substrate 21 of the counter electrode 220 as described above, the deterioration of the photosensitizing dye carried on the porous oxide semiconductor layer 13 can be sufficiently suppressed as in the first embodiment. it can. Furthermore, the connection reliability of the dye-sensitized solar cell module 200 obtained can be improved.

  Further, the connection between the edge 260a of the connection member 260 and the terminal 90 is preferably performed by resistance welding.

  In this case, the edge 260a of the connecting member 260 provided on the counter electrode 20 of one of the two dye-sensitized solar cells 50A and 50B adjacent to the other and the transparent of the other dye-sensitized solar cell 50B. The terminal 90 provided on the conductive substrate 15 can be simply joined without using solder or the like, the connection strength can be improved, and the contact resistance can also be reduced. In resistance welding, when the connecting member 260 of one dye-sensitized solar cell 50A and the terminal 90 of the transparent conductive substrate 15 of the other dye-sensitized solar cell 50B are joined, the electrode for resistance welding is locally used. Heat is generated locally, so heat is generated only locally. For this reason, compared with the case where it joins using solder etc., degradation of the pigment carried by oxide semiconductor layer 13 and a sealing part is controlled more fully. Note that resistance welding between the edge portion 260a of the connection member 260 and the terminal 90 also applies a voltage between the two resistance welding electrodes by pressing the two resistance welding electrodes against the surface of the connection member 260 in the same manner as described above. do it.

  The present invention is not limited to the above embodiment. For example, although the oxide semiconductor layer 13 is provided on the transparent conductive film 12 in the first and second embodiments, it 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 1 μm thick transparent conductive film made of FTO on the surface of a transparent substrate made of glass having a surface dimension of 50 mm × 50 mm and a thickness of 4 mm. Then, the transparent conductive film was patterned by etching.

  Next, an oxide semiconductor layer forming paste (manufactured by Solaronix, Ti Nanoxide-T) was repeatedly applied and dried three times with a screen printing machine on the transparent conductive film, and then 1 ° C. at 500 ° C. in an electric furnace. The porous oxide semiconductor layer was formed by time sintering.

  Next, using a commercially available silver paste for thick film, it was applied on the transparent conductive film so as to surround the porous oxide semiconductor layer, and then dried. This application and drying were repeated three times with a screen printer. Then, it sintered at 500 degreeC with the electric furnace for 1 hour. Next, a glass paste for protecting the wiring was further applied to a region where the electrolyte was in contact, and then dried. This application and drying were repeated three times and sintered in an electric furnace for 1 hour. Thus, a working electrode was obtained.

The working solution obtained as described above contains a mixed solvent of acetonitrile and tert-butanol mixed at 1: 1 (volume ratio), and a dye solution having a ruthenium dye (N719) concentration of 0.3 mM. Then, the dye was adsorbed on the porous semiconductor layer, and then the excess dye was washed away with the mixed solvent and dried to adsorb the photosensitizing dye to the porous semiconductor layer.

  On the other hand, the counter electrode was prepared as follows.

  First, a Ti plate having a thickness of 200 μm was prepared, and Pt was vapor-deposited on the Ti plate using a three-dimensional RF sputtering apparatus to obtain a counter electrode.

  Next, a quadrangular annular resin sheet (width 2 mm, thickness 50 μm) made of an ethylene-methacrylic acid copolymer (trade name: Nucrel, manufactured by Mitsui DuPont Polychemical Co., Ltd.) is placed on the working electrode. The resin sheet was fixed on the working electrode by heating and melting at 150 ° C.

  Next, a volatile electrolyte using methoxyacetonitrile as a solvent was injected on the working electrode and inside the sealing portion.

  Then, the counter electrode was overlapped with the sealing portion with the catalyst film facing the working electrode, and the peripheral portions of the counter electrode and the working electrode were thermocompression bonded. Thus, a dye-sensitized solar cell was obtained.

  Next, on the surface of the counter electrode opposite to the working electrode, a connecting member made of copper having a thickness of 100 μm and a dimension of 20 mm × 50 mm is arranged, and the connecting member and the counter electrode titanium foil are joined by resistance welding. I let you. In resistance welding, two electrodes were pressed against the titanium foil and the connection member, respectively, and a current of 1.0 kA was applied between the resistance welding electrodes for 10 milliseconds. At this time, the distance between the two resistance welding electrodes was 5 mm.

  Next, the Sn—Ag—Cu-based solder was brought into contact with the connecting member, melted, and then cooled. In this way, the solder was joined to the connecting member. Similarly, the solder was brought into contact with the terminals, and after being melted, it was cooled. Thus, the solder was joined to the terminal.

  Thus, a dye-sensitized solar cell was obtained.

  In the same manner as described above, other three dye-sensitized solar cells were also produced.

  Next, lead wires were prepared, and dye-sensitized solar cells were connected by the lead wires. Specifically, one end of the lead wire was brought into contact with the solder while being melted, and fixed to the connecting member with the solder. Next, the other end of the lead wire was brought into contact while melting the solder, and was fixed to the terminal with the solder. Thus, a dye-sensitized solar cell module was obtained.

(Comparative Example 1)
A dye-sensitized solar cell module was produced in the same manner as in Example 1 except that the connecting member was joined to the titanium foil while applying ultrasonic vibration.

  Further, connection reliability of the dye-sensitized solar cell modules obtained in Example 1 and Comparative Example 1 was examined. For connection reliability, the temperature cycle test defined in JIS C8938 A-1 was performed 200 cycles. In addition, the presence or absence of the peeling of a weld part was made into the evaluation item, and the thing without peeling was set as the pass.

The dye-sensitized solar cell modules obtained in Example 1 and Comparative Example 1 were examined for deterioration of the dye. The deterioration of the dye was judged by the naked eye based on whether or not the color of the dye had changed before and after bonding. When the color was clearly changed, it was determined that there was deterioration.

  As shown in Table 1, the dye-sensitized solar cell module obtained in Example 1 has higher connection strength than the dye-sensitized solar cell module of Comparative Example 1, and does not peel even after the temperature cycle test. I understood that. In addition, about the comparative example 1, it turned out that resistance has increased with peeling. In Example 1, no deterioration of the dye was observed, whereas in Comparative Example 1, deterioration of the dye was observed.

DESCRIPTION OF SYMBOLS 10 ... Working electrode 11 ... Transparent substrate 12 ... Transparent conductive film 13 ... Oxide semiconductor layer 15 ... Transparent conductive substrate (1st electrode)
60, 260 ... connecting member 20, 320 ... counter electrode (second electrode)
DESCRIPTION OF SYMBOLS 21 ... Metal substrate 30 ... Sealing part 50, 50A, 50B ... Dye-sensitized solar cell 100, 200 ... Dye-sensitized solar cell module

Claims (8)

In the method for producing a dye-sensitized solar cell module in which a plurality of dye-sensitized solar cells are electrically connected in series,
A connection step of electrically connecting the plurality of dye-sensitized solar cells in series and
The dye-sensitized solar cell,
Preparing a first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate, and a second electrode including a metal substrate made of a metal forming a passive film;
An oxide semiconductor layer forming step of forming an oxide semiconductor layer on the first electrode or the second electrode;
A dye carrying step of carrying a photosensitizing dye on the oxide semiconductor layer;
An electrolyte disposing step of disposing an electrolyte on the oxide semiconductor layer;
A sealing step of sealing the electrolyte by a sealing portion with the first electrode and the second electrode facing each other;
A linear connecting member made of a metal having a lower resistance than the metal substrate on the surface of the second electrode opposite to the first electrode on the metal substrate is sealed in the second electrode. a method of manufacturing a dye-sensitized solar cell and a connection member fixing step of the upper inner region of the part beyond the upper as the sealing portion and fixed to exit tension of the metal substrate, in the connecting member fixing step , Manufactured by a method for manufacturing a dye-sensitized solar cell for fixing the connection member on the metal substrate by joining the connection member to the metal substrate by resistance welding,
In the connection step, the connection member provided on the second electrode of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells is moved from the metal substrate to the other dye-sensitized solar cell side. The manufacturing method of the dye-sensitized solar cell module connected with the terminal provided in the said 1st electrode of said other dye-sensitized solar cell in the overhanging state.   In the connecting step, the connecting member of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells and the terminal provided on the first electrode of the other dye-sensitized solar cell are resisted. The manufacturing method of the dye-sensitized solar cell module of Claim 1 directly connected by welding.   In the connecting member fixing step, in resistance welding, the two electrodes are brought into contact with the surface of the connecting member and the surface of the metal substrate, respectively, with the connecting member in contact with the metal substrate. The manufacturing method of the dye-sensitized solar cell module of Claim 1 or 2 performed by this.   The manufacturing method of the dye-sensitized solar cell module as described in any one of Claims 1-3 which performs resistance welding for 3 to 20 milliseconds in the said connection member fixing process.   The manufacturing method of the dye-sensitized solar cell module as described in any one of Claims 1-4 whose thickness of the said connection member is 9-200 micrometers.   The manufacturing method of the dye-sensitized solar cell module as described in any one of Claims 1-5 whose thickness of a said 2nd electrode is 9-200 micrometers. A dye-sensitized solar cell module formed by electrically connecting a plurality of dye-sensitized solar cells in series,
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on the transparent substrate;
A second electrode including a metal substrate made of a metal that forms a passive film;
An oxide semiconductor layer provided on the first electrode or the second electrode;
An electrolyte provided between the first electrode and the second electrode;
A sealing portion for joining the first electrode and the second electrode;
A linear connection member made of a metal having a resistance lower than that of the metal of the metal substrate, provided on the surface of the second electrode opposite to the first electrode;
In the dye-sensitized solar cell, an alloy portion made of an alloy of a metal of the metal substrate and a metal of the connection member is provided between the second electrode and the connection member.
Of the two adjacent dye-sensitized solar cells, the connection member provided on the second electrode of one dye-sensitized solar cell, and a terminal provided on the first electrode of the other dye-sensitized solar cell; Is connected,
Said connecting member, wherein the sealing portion of the dye-sensitized solar on inner regions beyond upper street the sealing portion protrudes from the metal substrate to the other dye-sensitized solar cell side of the second electrode Battery module. The dye-sensitized solar cell module according to claim 7, wherein an alloy portion made of an alloy of a metal constituting the connection member and a metal constituting the terminal is provided between the connection member and the terminal. .

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