JP2014075314A - Dye-sensitized solar cell and dye-sensitized solar cell module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell and a dye-sensitized solar cell module which have excellent photoelectric conversion characteristics and excellent connection reliability.SOLUTION: A dye-sensitized solar cell 50 includes: a first electrode 15 having a transparent substrate 11, a transparent conductive film 12 provided on the transparent substrate 11, and current collecting wiring 14 provided on the transparent conductive film 12; a second electrode 20 facing the first electrode 15; an oxide semiconductor layer 13 provided on the first electrode 15 or the second electrode 20; a photosensitizing dye carried on the oxide semiconductor layer 13; and an electrolyte 40 provided between the first electrode 15 and the second electrode 20. The current collecting wiring 14 contains a glass component and has a first current collecting wiring part 14c to which a conductive member 23 is connected and second current collecting wiring parts 14a and 14b to which the conductive member 23 is not connected. The content of the glass component in the first current collecting wiring part 14c is higher than that in the second current collecting wiring parts 14a and 14b.

Description

  The present invention relates to a dye-sensitized solar cell and 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 a connecting portion. The working electrode is provided on the transparent substrate, the transparent conductive film formed thereon, the oxide semiconductor layer provided on the transparent conductive film, and on the transparent conductive film and around the oxide semiconductor layer. Current collector wiring. As such a dye-sensitized solar cell module, the thing of the following patent document 1 is known, for example. In the following Patent Document 1, in two adjacent dye-sensitized solar cells, the edge of the counter electrode of one dye-sensitized solar cell extends beyond the connecting portion, and the extending portion passes through the conductive member. A dye-sensitized solar cell module connected to the transparent conductive film of the other dye-sensitized solar cell is disclosed.

International Publication No. 2009/144949

  However, the dye-sensitized solar cell module described in Patent Document 1 described above has the following problems.

  That is, in the dye-sensitized solar cell module described in Patent Document 1, a part of the current collecting wiring of the other dye-sensitized solar cell may be used as the conductive member. In this case, if excessive stress is applied between the extension of the counter electrode of one dye-sensitized solar cell and the other dye-sensitized solar cell, the extension of the counter electrode of one dye-sensitized solar cell becomes the other In some cases. Therefore, the dye-sensitized solar cell module described in Patent Document 1 has room for improvement in terms of connection reliability.

  The dye-sensitized solar cell module is required to have excellent photoelectric conversion characteristics.

  Therefore, a dye-sensitized solar cell module having excellent photoelectric conversion characteristics and connection reliability has been demanded.

  This invention is made | formed in view of the said situation, and it aims at providing the dye-sensitized solar cell and dye-sensitized solar cell module which have the outstanding photoelectric conversion characteristic and connection reliability.

  The present inventors examined the cause of the above problem in the dye-sensitized solar cell module described in Patent Document 1. As a result, when the extension of the counter electrode of one dye-sensitized solar cell peels from the other dye-sensitized solar cell, the current collector wiring of the other dye-sensitized solar cell accompanies the extension of the counter electrode. Therefore, the present inventors considered that the adhesion between the current collector wiring and the transparent conductive film may be insufficient. Here, in order to improve the adhesiveness between a current collection wiring and a transparent conductive film, it is possible to increase the content rate of the glass component in a current collection wiring. However, simply increasing the glass component content in the current collector wiring tends to collect glass components near the interface between the transparent conductive film and the current collector wiring. It is considered that the resistance between the two increases and the photoelectric conversion characteristics deteriorate. The above-mentioned problem also occurs when a current extraction wiring is connected to the current collecting wiring in one dye-sensitized solar cell, and this wiring is peeled off from the dye-sensitized solar cell. obtain. Therefore, as a result of further earnest studies, the present inventors have found that the above-described problems can be solved by the following invention.

  That is, the present invention includes a transparent substrate, a transparent conductive film provided on the transparent substrate, a first electrode having a current collector wiring provided on the transparent conductive film, a second electrode facing the first electrode, An oxide semiconductor layer provided on the first electrode or the second electrode, a photosensitizing dye supported on the oxide semiconductor layer, and an electrolyte provided between the first electrode and the second electrode. The current collector wiring includes a glass component and includes a first current collector wiring portion for connecting a conductive member, and a second current collector wiring portion to which the conductive member is not connected, and the first current collector wiring In the dye-sensitized solar cell, the glass component content in the wiring portion is larger than the glass component content in the second current collecting wiring portion.

  According to this invention, the content rate of the glass component in the 1st current collection wiring part for connecting conductive members, such as a connection member for connecting with the next dye-sensitized solar cell, and current extraction wiring, It is larger than the content rate of the glass component of the 2nd current collection wiring part to which a conductive member is not connected. For this reason, about the 1st current collection wiring part for connecting a conductive member, adhesiveness with a transparent conductive film can be improved. For this reason, even if an electrically conductive member is connected to the 1st current collection wiring part and an excessive stress is added between an electrically conductive member and current collection wiring, exfoliation of current collection wiring from a transparent conductive film is fully controlled. . Therefore, the dye-sensitized solar cell of the present invention can have excellent connection reliability. On the other hand, since the content rate of the glass component in the 1st current collection wiring part for connecting a conductive member is larger than the content rate of the glass component of the 2nd current collection wiring part, a transparent conductive film and the 1st current collection wiring part However, the resistance between the transparent conductive film and the second current collector wiring portion can be kept low. For this reason, the current generated in the oxide semiconductor layer can sufficiently flow from the second current collector wiring portion to the other dye-sensitized solar cell via the first current collector wiring portion. Therefore, the dye-sensitized solar cell of the present invention can have excellent photoelectric conversion characteristics.

  The present invention also provides a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically, wherein the dye-sensitized solar cell is a transparent substrate, A first electrode having a transparent conductive film provided on the transparent substrate and a current collecting wiring provided on the transparent conductive film; a second electrode opposed to the first electrode; and the first electrode or the second electrode. An oxide semiconductor layer provided on the oxide semiconductor layer, a photosensitizing dye carried on the oxide semiconductor layer, and an electrolyte provided between the first electrode and the second electrode. A connecting member for electrically connecting the second electrode of one dye-sensitized solar cell of the solar cells and the current collector wiring of the first electrode of the other dye-sensitized solar cell; The other dye-sensitized solar cell The current collecting wiring has a first current collecting wiring portion to which the connecting member is connected and containing a glass component, and a second current collecting wiring portion to which the connecting member is not connected, and the first current collecting wiring portion This is a dye-sensitized solar cell module in which the glass component content is higher than the glass component content of the second current collector wiring portion.

  According to this invention, the content rate of the glass component in the 1st current collection wiring part to which a connection member is connected is larger than the content rate of the glass component of the 2nd current collection wiring part. For this reason, about the 1st current collection wiring part to which a connection member is connected, adhesiveness with a transparent conductive film can be improved. For this reason, even if an excessive stress is applied between the connection member and the current collector wiring, peeling of the current collector wiring from the transparent conductive film is sufficiently suppressed. Therefore, the dye-sensitized solar cell module of the present invention can have excellent connection reliability. On the other hand, since the content rate of the glass component in the 1st current collection wiring part to which a connection member is connected is larger than the content rate of the glass component of the 2nd current collection wiring part, a transparent conductive film, the 1st current collection wiring part, However, the resistance between the transparent conductive film and the second current collector wiring portion can be kept low. For this reason, the current generated in the oxide semiconductor layer can sufficiently flow from the second current collector wiring portion to the other dye-sensitized solar cell via the first current collector wiring portion. Therefore, the dye-sensitized solar cell module of the present invention can have excellent photoelectric conversion characteristics.

  In the said dye-sensitized solar cell, it is preferable that the content rate of the said glass component in a said 1st current collection wiring part is 4-10 mass%.

  In this case, as compared with the case where the glass component content in the first current collector wiring portion is less than 4% by mass, the separation of the first current collector wiring portion from the transparent conductive film can be more effectively suppressed. it can. On the other hand, when the content rate of the glass component in the 1st current collection wiring part exists in the said range, compared with the case where the content rate of the glass component in the 1st current collection wiring part exceeds 10 mass%, the 1st current collection wiring part. The volume resistance of the electric wiring part itself can be further reduced.

  In the said dye-sensitized solar cell, the difference of the content rate of the said glass component in the said 1st current collection wiring part and the content rate of the said glass component in the said 2nd current collection wiring part is 1-10 mass%. Preferably there is.

  In this case, compared with the case where the difference between the glass component content in the first current collector wiring portion and the glass component content in the second current collector wiring portion is less than 1% by mass, Separation of the first current collector wiring portion can be more effectively suppressed. On the other hand, compared with the case where the difference of the content rate of the glass component in a 1st current collection wiring part and the content rate of the glass component in a 2nd current collection wiring part exceeds 10 mass%, a more superior photoelectric conversion characteristic is obtained. Can be realized.

  In the dye-sensitized solar cell, the metal contained in the first current collector wiring portion between the first current collector wiring portion and the connection member or the conductive member of the other dye-sensitized solar cell; It is preferable that an alloy portion made of an alloy with a metal contained in the connection member or the conductive member is provided.

  In this case, the connection between the connecting member or the conductive member and the first current collecting wiring portion is strengthened by the alloy portion, and the peeling of the connecting member or the conductive member from the first current collecting wiring portion is sufficiently suppressed.

  Moreover, in the dye-sensitized solar cell, it is preferable that the first current collecting wiring portion includes a void, and a void ratio, which is a ratio of the void occupied in the first current collecting wiring portion, is 30% or less.

  In this case, the volume resistance can be further reduced as compared with the case where the porosity exceeds 30%.

  In the present invention, the “porosity” refers to the ratio of the area of the void in the current collecting wiring when the cross section of the current collecting wiring is observed with a scanning electron microscope (SEM).

  ADVANTAGE OF THE INVENTION According to this invention, the dye-sensitized solar cell and dye-sensitized solar cell module which have the outstanding photoelectric conversion characteristic and connection reliability are provided.

It is a top 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 partial top view which shows the working electrode of FIG. It is a fragmentary sectional view showing the state where current collection wiring and a connection member are connected. It is a fragmentary sectional view showing the state where a metal substrate and a connection member are connected.

  Hereinafter, an embodiment of the dye-sensitized solar cell module of the present invention will be described in detail with reference to FIG. FIG. 1 is a plan view showing a first embodiment of the dye-sensitized solar cell module of the present invention.

  As shown in FIG. 1, the dye-sensitized solar cell module 200 has two dye-sensitized solar cell module units 100A and 100B. The dye-sensitized solar cell module units 100A and 100B are connected in series and electrically. The dye-sensitized solar cell module units 100A and 100B have a plurality of dye-sensitized solar cells 50, and the plurality of dye-sensitized solar cells 50 are connected in series and electrically.

  Here, the two dye-sensitized solar cell module units 100A and 100B are arranged so that the arrangement directions of the dye-sensitized solar cells 50 in each of the two dye-sensitized solar cell module units 100A and 100B are parallel to each other. ing. Hereinafter, for convenience of explanation, the four dye-sensitized solar cells 50 in the dye-sensitized solar cell module unit 100A are referred to as the dye-sensitized solar cells 50A to 50D and the four dye-sensitized solar cells in the dye-sensitized solar cell module unit 100B. 50 may be referred to as dye-sensitized solar cells 50E to 50H.

  2 is a cross-sectional view taken along line II-II in FIG. 1, FIG. 3 is a partial plan view showing the working electrode in FIG. 1, and FIG. 4 shows a state where the current collector wiring and the connection member are connected. FIG. 5 is a partial cross-sectional view showing a state in which the metal substrate and the connection member are connected.

  As shown in FIG. 2, each of the plurality of dye-sensitized solar cells 50 includes a working electrode 10, a counter electrode 20 facing the working electrode 10, and a connecting portion 30 that connects the working electrode 10 and the counter electrode 20. The cell space formed by the working electrode 10, the counter electrode 20, and the connecting portion 30 is filled with an electrolyte 40.

  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 a plurality of oxide semiconductors provided on the transparent conductive film 12 of the transparent conductive substrate 15. The wiring layer 17 is provided on the transparent conductive film 12 so as to surround each of the plurality of oxide semiconductor layers 13. The wiring portion 17 is provided between the connecting portion 30 and the transparent conductive film 12, and the current collection wiring 14 provided on the transparent conductive film 12 and the wiring protection layer 16 that protects the current collection wiring 14 from the electrolyte 40. And have. In the present embodiment, the first electrode is constituted by the transparent conductive substrate 15 and the wiring portion 17.

  The transparent substrate 11 is a transparent substrate common to all the dye-sensitized solar cells 50A to 50H in the dye-sensitized solar cell module 200.

  As shown in FIG. 3, in the working electrode 10, the current collector wiring 14 has a square annular outer peripheral portion 14 a and a plurality of partition portions (finger wirings) 14 b that partition the inner opening of the outer peripheral portion 14 a, The oxide semiconductor layer 13 is surrounded by the portion 14a and the partition portion 14b. Further, the current collecting wiring 14 has a land portion 14 c provided inside the outer peripheral portion 14 a on the side of the adjacent dye-sensitized solar cell 50 in the outer peripheral portion 14 a which is an edge portion of the current collecting wiring 14. In the present embodiment, the outer peripheral portion 14a and the partition portion 14b constitute a second current collecting wiring portion, and the land portion 14c constitutes a first current collecting wiring portion.

  On the other hand, as shown in FIG. 2, the counter electrode 20 is configured by a laminate of a metal substrate 21 and a catalyst layer 22 that is provided on the transparent conductive substrate 15 side of the metal substrate 21 and promotes a catalytic reaction. In the present embodiment, the second electrode is constituted by the counter electrode 20.

  In the counter electrode 20, a notch 24 is formed at a position facing the land portion 14c.

  On the other hand, a concave portion 33 is formed in the connecting portion 30 of each dye-sensitized solar cell 50 so as to surround the land portion 14c.

  Then, as shown in FIG. 2, the metal substrate 21 of the counter electrode 20 of one of the two dye-sensitized solar cells 50 and the current collecting wiring of the other dye-sensitized solar cell 50. The 14 land portions 14 c are connected by the connection member 23. The connection member 23 is made of a metal foil, and a fixing portion 23 a fixed to a part of the metal substrate 21 on the side opposite to the transparent conductive substrate 15, a fixing portion 23 a and a land portion 14 c of the current collector wiring 14. Are electrically connected to each other and a non-fixed portion 23 b that is not fixed to the metal substrate 21.

  In the present embodiment, for example, the fixing portion 23a of the connecting member 23 is fixed to the metal substrate 21 of the counter electrode 20 of the dye-sensitized solar cell 50B, and the non-fixing portion 23b of the connecting member 23 is connected to the dye-sensitized solar cell 50C. The concave portion 33 of the portion 30 is directly connected to the land portion 14 c which is a part of the current collecting wiring 14. Here, the non-fixed portion 23b is in a slack state. For this reason, a gap is formed between the portion of the non-fixed portion 23 b facing the metal substrate 21 and the metal substrate 21.

  Two adjacent dye-sensitized solar cells 50A and 50B, two adjacent dye-sensitized solar cells 50B and 50C, two dye-sensitized solar cells 50C and 50D, two dye-sensitized solar cells 50E and 50F, two Similarly, in the dye-sensitized solar cells 50F and 50G and the two dye-sensitized solar cells 50G and 50H, the fixing portion 23a of the connection member 23 is one of the two adjacent dye-sensitized solar cells 50. The non-fixed portion 23b of the connecting member 23 fixed to the metal substrate 21 of the counter electrode 20 of the solar cell 50 is a part of the current collector wiring 14 in the concave portion 33 of the connecting portion 30 of the other dye-sensitized solar cell 50C. The land portion 14c is directly connected, and the non-fixed portion 23b is in a relaxed state.

  Of the land portions 14c of the dye-sensitized solar cells 50A to 50H, the land portion 14c to which the non-fixed portion 23b of the connecting member 23 is connected contains a glass component, and the glass component in the land portion 14c is contained. The rate is larger than the content rate of the glass component in the outer peripheral part 14a and the partition part 14b.

  As shown in FIG. 4, between the non-fixed portion 23b and the land portion 14c of the connection member 23, an alloy portion 60 made of an alloy of a metal constituting the non-fixed portion 23b and a metal constituting the land portion 14c. Is provided. Further, as shown in FIG. 5, an alloy portion 65 made of an alloy of the metal constituting the fixing portion 23 a and the metal constituting the metal substrate 21 is provided between the fixing portion 23 a of the connecting member 23 and the metal substrate 21. It has been.

  As shown in FIG. 1, in the dye-sensitized solar cell module unit 100A, the non-fixed portion 23b of the connecting member 23 is in the same direction with respect to the counter electrode 20 (from the dye-sensitized solar cell 50A to the dye-sensitized solar cell 50D). It protrudes toward the direction). On the other hand, in the dye-sensitized solar cell module unit 100B, the non-fixed portion 23b of the connecting member 23 protrudes in the same direction (the direction from the dye-sensitized solar cell 50E toward the dye-sensitized solar cell 50H) to the counter electrode 20. Yes. That is, in the dye-sensitized solar cell module unit 100A and the dye-sensitized solar cell module unit 100B, the protruding directions of the non-fixed portions 23b of the connection member 23 are opposite to each other.

  Further, the dye-sensitized solar cell 50E in the dye-sensitized solar cell module unit 100B, that is, the dye-sensitized solar cell 50 arranged at the end of the dye-sensitized solar cell module unit 100B has a land portion of the current collecting wiring 14. A connection terminal 70 is provided at 14c. The connection terminal 70 and the connection member 23 fixed to the counter electrode 20 of the dye-sensitized solar cell 50 </ b> D are connected via a conductive member 110 provided along the surface of the transparent substrate 11. The conductive member 110 connects the dye-sensitized solar cell module unit 100A and the dye-sensitized solar cell module unit 100B in series. As a material constituting the conductive member 110, for example, copper, silver, nickel, or the like is used. Further, examples of the shape of the conductive member 110 include a tape shape and a wire shape. The tape shape is preferably used because the thickness of the dye-sensitized solar cell module 200 can be reduced during use.

  Further, the dye-sensitized solar cell 50 </ b> A of the dye-sensitized solar cell module unit 100 </ b> A is also provided with a connection terminal 70 on the land portion 14 c in the current collecting wiring 14 of the working electrode 10.

  Next, the effect of the dye-sensitized solar cell module 200 described above will be described.

  According to the dye-sensitized solar cell module 200, the glass component content in the land portion 14c to which the connecting member 23 is connected is such that the glass component in the outer peripheral portion 14a and the partition portion 14b of the current collector wiring 14 is contained. Is greater than the rate. For this reason, about the land part 14c to which the connection member 23 is connected, adhesiveness with the transparent conductive film 12 can be improved. For this reason, even if an excessive stress is applied between the connection member 23 and the current collector wiring 14 due to the transparent substrate 11 being bent, peeling of the current collector wiring 14 from the transparent conductive film 12 is sufficiently suppressed. Is done. Therefore, the dye-sensitized solar cell module 200 can have excellent connection reliability. On the other hand, since the content rate of the glass component in the land part 14c to which the connection member 23 is connected is larger than the content rate of the glass component in the outer peripheral part 14a and the partition part 14b of the current collector wiring 14, the transparent conductive film 12 However, the resistance between the transparent conductive film 12, the outer peripheral portion 14a, and the partition portion 14b can be kept low. Therefore, the current generated in the oxide semiconductor layer 13 can be sufficiently supplied from the outer peripheral portion 14a and the partition portion 14b to the other dye-sensitized solar cell 50 through the land portion 14c. Therefore, the dye-sensitized solar cell module 200 can have excellent photoelectric conversion characteristics.

  Further, when the transparent substrate 11 is bent, the two dye-sensitized solar cells 50 of the two adjacent dye-sensitized solar cells 50 are collected by the current collecting wiring 14 of the transparent conductive substrate 15 of one of the dye-sensitized solar cells 50. The connection member 23 fixed to the surface on the opposite side of the transparent conductive substrate 15 in the metal substrate 21 of the counter electrode 20 is pulled. At this time, the loosened non-fixed portion 23b of the connection member 23 can be expanded. That is, the non-fixed portion 23b is not immediately in a tension state. For this reason, the stress applied between the connection member 23 and the current collector wiring 14 is reduced, and the connection member 23 is sufficiently suppressed from peeling from the current collector wiring 14. As a result, the dye-sensitized solar cell module 200 can have excellent connection reliability.

  In the dye-sensitized solar cell module 200, the connection member 23 is made of a metal foil and has flexibility. Therefore, the transparent substrate 11 is bent, and the metal of the counter electrode 20 of the two dye-sensitized solar cells 50 is formed by the transparent conductive substrate 15 of one of the two dye-sensitized solar cells 50 adjacent to the transparent substrate 11. When the connecting member 23 fixed to the substrate 21 is pulled, the non-fixed portion 23b is easily spread. For this reason, the stress applied between the connection member 23 and the transparent conductive substrate 15 is further reduced, and the connection member 23 is more sufficiently suppressed from peeling off from the transparent conductive substrate 15. As a result, the dye-sensitized solar cell module 200 can have better connection reliability. Moreover, since the connection member 23 consists of metal foil, the connection member 23 has the outstanding durability. For this reason, even if the dye-sensitized solar cell module 200 is used in an environment with a large temperature change and stress is repeatedly applied to the connection member 23, the breakage of the connection member 23 is sufficiently suppressed over a long period of time. Furthermore, since the connecting member 23 is made of a metal foil, it is possible to reduce the resistance between the adjacent dye-sensitized solar cells 50.

  Furthermore, in the dye-sensitized solar cell module 200, a recess 33 is provided outside the connecting portion 30 of the dye-sensitized solar cell 50, and the fixing portion 23 a of the connection member 23 is provided between the two adjacent dye-sensitized solar cells 50. One of the current collector wirings 14 is fixed to the metal substrate 21 of the counter electrode 20 of one of the dye-sensitized solar cells 50, and the non-fixed portion 23 b of the connecting member 23 is in the recess 33 of the other dye-sensitized solar cell 50. It is joined to the land part 14c which is a part. For this reason, without significantly reducing the aperture ratio of the dye-sensitized solar cell module 200, the non-fixed portion 23b of the connecting member 23, and the current collector wiring 14 of the transparent conductive substrate 15 of the other dye-sensitized solar cell 50 The area of the connecting portion can be made sufficiently large.

  Thus, the dye-sensitized solar cell module 200 has excellent connection reliability. For this reason, it is not necessary to widen the width in the non-fixed portion 23b of the connecting member 23. For this reason, it becomes possible to make small about the area of the connection location for connecting the non-fixed part 23b of the connection member 23, and the land part 14c of the other dye-sensitized solar cell 50, and it can improve an aperture ratio. It becomes possible. In particular, in the dye-sensitized solar cell module 200, the land portion 14 c is provided inside the outer peripheral portion 14 a that is an edge portion of the current collecting wiring 14. For this reason, the clearance gap between the counter electrodes 20 of two adjacent dye-sensitized solar cells 50 can be made small. That is, the area of the area that does not contribute to power generation can be reduced. For this reason, according to the dye-sensitized solar cell module 200, compared with the case where the land part 14c is provided in the outer side of the outer peripheral part 14a which is an edge part of the current collection wiring 14, an aperture ratio can be made higher.

  Further, in the dye-sensitized solar cell module 200, between the non-fixed portion 23b and the land portion 14c of the connection member 23, an alloy of a metal constituting the non-fixed portion 23b and a metal constituting the land portion 14c. An alloy part 60 is provided. For this reason, the bonding between the non-fixed portion 23b of the connection member 23 and the land portion 14c, which is a part of the current collecting wiring 14, is strengthened, and the non-fixed portion 23b of the connecting member 23 is more sufficiently peeled from the current collecting wiring 14. To be suppressed.

  Further, in the dye-sensitized solar cell module 200, an alloy portion made of an alloy of a metal constituting the fixing portion 23 a and a metal constituting the metal substrate 21 is provided between the fixing portion 23 a of the connection member 23 and the metal substrate 21. 65 is provided. For this reason, the bonding between the fixing portion 23 of the connection member 23 and the metal substrate 21 is strengthened, and peeling of the fixing portion 23a of the connection member 23 from the metal substrate 21 is more sufficiently suppressed.

  Furthermore, in two adjacent dye-sensitized solar cells 50, in one dye-sensitized solar cell 50, a notch 24 is formed at a position facing the land portion 14c. For this reason, it is assumed that the connection member 23 moves with respect to the land portion 14c joined thereto due to an object colliding with one of the two adjacent dye-sensitized solar cells 50. However, the connecting member 23 can escape into the notch 24. For this reason, the contact between the connecting member 23 and the counter electrode 20 of the adjacent dye-sensitized solar cell 50 can be sufficiently prevented.

  The dye-sensitized solar cell module 200 includes dye-sensitized solar cell module units 100A and 100B, and the dye solar cell module units 100A and 100B are connected in series and electrically with each other. In each of the dye-sensitized solar cell module units 100A and 100B, the protruding directions of the connecting member 23 with respect to the counter electrode 20 are the same, and two adjacent dye-sensitized solar cell modules are arranged so that the arrangement directions are parallel to each other. In the units 100A and 100B, the protruding directions of the connecting member 23 are opposite to each other.

  Therefore, in two adjacent dye-sensitized solar cell module units 100A and 100B, the land portion 14c of the dye solar cell 50E constituting one dye-sensitized solar cell module unit 100B and the other dye-sensitized solar cell module The connecting member 23 of the dye-sensitized solar cell 50D constituting the unit 100A can be arranged on the same side with respect to the arrangement direction of the dye-sensitized solar cell module units 100A and 100B. That is, the land portion 14c of the dye solar cell 50E constituting one dye-sensitized solar cell module unit 100B and the connecting member 23 of the dye-sensitized solar cell 50D constituting the other dye-sensitized solar cell module unit 100A. It is possible to connect outside the light receiving area. For this reason, according to the dye-sensitized solar cell module 200, the land part 14c of the dye solar cell 50E which comprises one dye-sensitized solar cell module unit 100B, and the other dye-sensitized solar cell module unit 100A are comprised. The dye-sensitized solar cell 50D can be connected in series without decreasing the aperture ratio.

  Next, the working electrode 10. The photosensitizing dye, the counter electrode 20, the connection member 23, the coupling part 30, and the electrolyte 40 will be described in detail.

(Working electrode)
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 dye-sensitized solar cell 100 and is not particularly limited, but may be in the range of 50 to 10,000 μm, for example.

Examples of the material constituting the transparent conductive film 12 include tin-doped indium oxide (Indium-Tin-Oxide: ITO), tin oxide (SnO ₂ ), and fluorine-doped tin oxide (Fluorine-doped-Tin-Oxide: FTO). 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. The thickness of the transparent conductive film 12 may be in the range of 0.01 to 2 μm, for example.

The oxide semiconductor layer 13 includes 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 described above, the current collector wiring 14 has the outer peripheral portion 14a, the partition portion 14b, and the land portion 14c.

  The land part 14c contains a glass component. As the glass component, for example, glass frit (glass powder) can be used. Although the content rate of the glass component in the land part 14c should just be larger than the content rate of the glass component in the outer peripheral part 14a and the partition part 14b, specifically, the content rate of the glass component in the land part 14c is It is preferable that it is 4-10 mass%. In this case, peeling of the land portion 14c from the transparent conductive film 12 can be more effectively suppressed as compared with the case where the glass component content in the land portion 14c is less than 4% by mass. On the other hand, when the content ratio of the glass component in the land portion 14c is within the above range, the volume resistance of the land portion 14c itself is lowered as compared with the case where the content ratio of the glass component in the land portion 14c exceeds 10 mass%. The power generation efficiency can be increased.

  The glass component content in the land portion 14c is more preferably 4 to 7% by mass.

  The land portion 14c may or may not include a gap. When the land portion 14c includes a void, the void ratio, which is the proportion of the void in the land portion 14c, is not particularly limited, but is preferably 30% or less. In this case, the volume resistance of the land portion 14c can be further reduced as compared with the case where the porosity exceeds 30%. The porosity in the land portion 14c is more preferably 20% or less. However, the porosity in the land portion 14c is preferably 1% or more.

  Although the outer peripheral part 14a and the partition part 14b do not need to contain the glass component, it is preferable that a glass component is included. When the outer peripheral part 14a and the partition part 14b contain a glass component, the thing similar to the glass component contained in the land part 14c can be used as a glass component. Moreover, the content rate of the glass component in the outer peripheral part 14a and the partition part 14b should just be smaller than the content rate of the glass component in the land part 14c, Although it does not restrict | limit, Usually, it is 0.5-3 mass%, Preferably Is 1-2% by mass.

  The material constituting the wiring protective layer 16 is not particularly limited as long as it can protect the current collecting wiring 14 from the electrolyte 40. For example, the material is composed of a resin material or an inorganic material.

  Examples of the resin material include ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, modified polyolefin resins such as ethylene-vinyl alcohol copolymers, ultraviolet curable resins, and vinyl alcohol polymers. Etc.

  Examples of the inorganic material include inorganic insulating materials such as a lead-free transparent low melting point glass frit. As the low melting point glass frit, one having a softening point of 150 to 550 ° C. can be used.

(Photosensitizing dye)
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.

(Counter electrode)
As described above, the counter electrode 20 is composed of a laminate of the metal substrate 21 and the catalyst layer 22.

  The metal board | substrate 21 should just be comprised with the metal. Examples of such metals include metals having corrosion resistance and having a passive film such as titanium, nickel, platinum, molybdenum, SUS, and tungsten.

  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.

(Connecting member)
The metal foil is preferably made of a metal having a resistance lower than that of the metal substrate 21, and an example of such a metal is copper.

(Connecting part)
In the present embodiment, a material having a sealing ability is used as the connecting portion 30. That is, in this embodiment, the connection part 30 functions as a sealing part. Examples of materials having such a sealing ability include modified polyolefin resins and ultraviolet curable resins including, for example, ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, and the like. And resins such as vinyl alcohol polymers. These can be used alone or in combination of two or more.

(Electrolytes)
The electrolyte 40 is usually composed of an electrolytic solution, and this electrolytic solution contains an oxidation-reduction pair such as I ⁻ / I ₃ ^— and an organic solvent. As an organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, glutaronitrile, methacrylonitrile, isobutyronitrile, Phenylacetonitrile, acrylonitrile, succinonitrile, oxalonitrile, pentanitrile, adiponitrile and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ⁻ and other pairs such as redox pairs such as bromine / bromide ions, zinc complexes, iron complexes, and cobalt complexes.

The electrolyte 40 may include an ionic liquid electrolyte made of a mixture of the ionic liquid and the organic solvent as a volatile component, instead of the organic solvent. The electrolyte 40 may include an ionic liquid instead of the organic solvent. 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. Examples of such a room temperature molten salt include 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide. Id, dimethyl imidazolium iodide, ethyl methyl imidazolium iodide, dimethyl propyl imidazolium iodide, butyl methyl imidazolium iodide, or methyl propyl imidazolium iodide is preferably used. In addition, the electrolyte 40 may use a mixture of the ionic liquid and the organic solvent instead of the organic solvent. An additive can be added to the electrolyte 40. As the _{additive, LiI, I 2, 4-} t- butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butyl-benzimidazole and the like. Further, as the electrolyte 40, a nano-composite gel electrolyte, which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , carbon nanotubes, etc. into the electrolyte, may be used, and polyvinylidene fluoride may be used. Alternatively, an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.

  Next, the manufacturing method of the said dye-sensitized solar cell module 200 is demonstrated.

  First, a laminate in which a transparent conductive film is formed on one transparent substrate 11 is prepared.

  As a method for forming the transparent conductive film, a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, a CVD method, or the like is used.

  Next, the transparent conductive film is divided into a plurality of transparent conductive films 12 separated from each other by laser processing or etching. Thus, the transparent conductive substrate 15 is obtained.

  Next, the oxide semiconductor layer 13 is formed on each of the divided transparent conductive films 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 includes a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles described above.

  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 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, a paste containing a conductive material such as silver is applied on the transparent conductive film 12. At this time, two types of paste are prepared. Specifically, a first paste for forming the land portion 14c and a second paste for forming the outer peripheral portion 14a and the partition portion 14b are prepared. Here, the second paste is prepared such that the glass component content in the second paste is greater than the glass component content in the first paste. The first paste is applied so as to form a land portion 14c provided inside the outer peripheral portion 14a, and the second paste is applied to the outer peripheral portion 14a and the outer peripheral portion 14a as shown in FIG. The partition portion 14b that partitions the inner opening is formed. And the 1st paste and the 2nd paste are baked, and the land part 14c, the outer peripheral part 14a, and the partition part 14b are formed. Thus, the current collecting wiring 14 is obtained.

  Next, the current collector wiring 14 is covered with a wiring protective layer 16 such as a low melting point glass frit. At this time, the wiring protective layer 16 covers the outer peripheral portion 14 a and the partition portion 14 b and does not cover the land portion 14 c that is not in contact with the electrolyte 40. Thus, the wiring portion 17 is obtained by the current collecting wiring 14 and the wiring protective layer 16.

  Thus, a plurality of working electrodes 10 are obtained.

  Next, a connection part forming body for forming the same number of annular connection parts 30 as the number of dye-sensitized solar cells 50 is prepared. As the ring-shaped connecting portion forming body, an opening in which the oxide semiconductor layer 13 is surrounded and a recess 33 is formed outside the connecting portion forming body is used.

  And this connection part formation body is adhere | attached on the current collection wiring 14 of the working electrode 10. FIG. At this time, the connecting portion forming body is bonded to the land portion 14c of the current collecting wiring 14 so that the concave portion 33 formed in the connecting portion forming body faces the land portion 14c. In addition, you may adhere | attach the connection part formation body of the same shape on the surface of the counter electrode 20. FIG. Adhesion of the connecting portion forming body to the current collector wiring 14 or the counter electrode 20 can be performed by heating and melting the connecting portion forming body.

  Next, a photosensitizing dye is supported on the oxide semiconductor layers 13 of the plurality of working electrodes 10. For this purpose, the working electrode 10 is immersed in a solution containing a photosensitizing dye, the photosensitizing dye is adsorbed on the oxide semiconductor layer 13, and then the excess photosensitizer is added with the solvent component of the solution. The photosensitizing dye may be adsorbed to the oxide semiconductor layer 13 by washing away the dye and drying it. 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.

  Next, the electrolyte 40 is disposed on the oxide semiconductor layers 13 of the plurality of working electrodes 10. The electrolyte 40 can be disposed by a printing method such as screen printing.

  Next, a plurality of counter electrodes 20 are prepared. Each counter electrode 20 is formed with a notch 24 that is aligned with the recess 33 of the connecting portion forming body.

  On the other hand, a metal foil for forming the connection member 23 is prepared.

  Next, one end of the metal foil is connected to the metal substrate 21 of one of the two dye-sensitized solar cells 50 adjacent to the dye-sensitized solar cell 50.

  Thereafter, each of the plurality of counter electrodes 20 is bonded to the connecting portion forming body so as to close the opening of the connecting portion forming body. At this time, the notch 24 of each counter electrode 20 is aligned with the concave portion 33 of the connecting portion forming body. Thus, a plurality of dye-sensitized solar cells 50 are obtained.

  Next, the other end of the metal foil is connected to the land portion 14 c of the current collecting wiring 14 in the working electrode 10. In this way, the connection member 23 made of metal foil is obtained. Of the connecting member 23, the portion fixed to the metal substrate 21 is a fixed portion 23a, and the portion fixed to the land portion 14c is a non-fixed portion 23a. At this time, the other end of the metal foil is connected to the land portion 14c so that the non-fixed portion 23b is loosened.

  The metal foil can be connected to the metal substrate 21 or the land portion 14c by, for example, resistance welding. In resistance welding, for example, two resistance welding electrodes are pressed against at least one of the metal foil and the metal substrate 21 or at least one of the metal foil and the land portion 14c, and a current is passed between the two, thereby causing the metal substrate 21 to flow. Alternatively, heat is generated at the contact portion between the land portion 14c and the metal foil, and both the metal substrate 21 or the land portion 14c and the metal foil are melted by this heat to connect the two. At this time, heat is generated only in the contact portion between the metal substrate 21 or the land portion 14c and the metal foil. In resistance welding, the current is usually supplied for a short time (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 metal foil is bonded to the metal substrate 21 or the land portion 14c after the dye-sensitized solar cell 50 is obtained, the deterioration of the photosensitizing dye carried on the oxide semiconductor layer 13 is sufficiently suppressed. be able to.

  At this time, if the resistance of the metal substrate 21 or the land portion 14c is different from the resistance of the metal foil, the contact resistance between the metal foil and the metal substrate 21 or the land portion 14c increases. For this reason, the portion where the metal foil and the metal substrate 21 or the land portion 14c come into contact with each other is easily melted by heat. When the voltage applied between the two electrodes is turned off, the melted portion is solidified to form the alloy portion 60 and the alloy portion 65 as shown in FIGS. Accordingly, the bonding strength between the connection member 23 and the metal substrate 21 or the land portion 14c can be sufficiently improved. Further, by providing the alloy part 60 and the alloy part 65 between the connection member 23 and the metal substrate 21 or the land part 14c, the contact resistance between the connection member 23 and the metal board 21 or the land part 14c is also reduced. Can do.

  Resistance welding is preferably performed for 3 to 20 milliseconds, more preferably 5 to 7 milliseconds. In this case, the connection strength between the connection member 23 and the metal substrate 21 or the land portion 14c can be sufficiently improved, and the thickness of the alloy portion 60 and the alloy portion 65 becomes appropriate, so that the metal substrate 21 or the land portion The resistance between 14c and the connection member 23 can be made sufficiently lower.

  The thickness of the connecting member 23 is not particularly limited, but is preferably 9 to 200 μm, and more preferably 20 to 100 μm. When the thickness of the connecting member 23 is 9 μm or more, the strength is greater than when the thickness is less than 9 μm, and deformation is difficult during resistance welding. On the other hand, when the thickness of the connecting member 23 is 200 μm or less, the connecting member 23 and the metal substrate 21 or the land portion 14c can be connected in a shorter time than when the thickness exceeds 200 μm.

  The thickness of the land portion 14c of the current collecting wiring 14 is not particularly limited, but is preferably 0.1 to 50 μm, and more preferably 1 to 30 μm.

  In this case, when the thickness of the land portion 14c of the current collecting wiring 14 is 0.1 μm or more, the strength is greater than when the land portion 14c is less than 0.1 μm, and deformation during resistance welding is difficult. On the other hand, when the thickness of the land portion 14c of the current collector wiring 14 is 50 μm or less, the connection member 23 and the land portion 14c can be connected in a shorter time than when the land portion 14c exceeds 50 μm.

  Although the current applied between the two resistance welding electrodes depends on the combination of the connecting member 23 and the metal substrate 21 or the land portion 14c, it cannot be generally stated, but is usually 0.01 to 3 kA, 0 It is preferable that it is 1-2 kA.

  Also, the current application time cannot be generally specified, but is usually 3 to 20 milliseconds, preferably 5 to 7 milliseconds.

  Furthermore, although the distance between the electrodes for resistance welding cannot be generally specified, it is usually 0.3 to 20 mm, preferably 0.5 to 10 mm.

  Thus, dye-sensitized solar cell module units 100A and 100B are obtained.

  Next, the connection terminals 70 are connected to the land portions 14c in the current collecting wiring 14 of the dye-sensitized solar cells 50A and 50E, respectively. The connection terminal 70 can connect a member such as silver, copper, or nickel to the land portion 14c using a method such as resistance welding. The connection terminal 70 may be formed simultaneously with the current collector wiring 14 by a screen printing method using the same material as that for the current collector wiring 14 when the current collector wiring 14 is formed.

  Finally, the conductive member 110 is connected to the connection terminal 70 connected to the dye-sensitized solar cell 50E and the connection member 23 of the dye-sensitized solar cell 50D. The conductive member 110 can be connected to the connection terminal 70 and the connection member 23 by, for example, resistance welding.

  The dye-sensitized solar cell module 200 is obtained as described above.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, each coupling portion 30 of the dye-sensitized solar cell 50 is provided with a recess 33, and in the recess 33, the connection portion 23 of the connecting member 23 that connects two adjacent dye-sensitized solar cells 50 is land. Although it is joined to the portion 14 c, the connecting portion 30 may not be provided with the recess 33.

  Moreover, in the said embodiment, although the alloy part 60 is provided between the non-fixing part 23b and the land part 14c of the connection member 23, the alloy part 60 does not necessarily need to be provided.

  Moreover, in the said embodiment, although the alloy part 65 is provided between the fixing | fixed part 23a and the metal substrate 21 of the connection member 23, the alloy part 65 does not necessarily need to be provided.

  Furthermore, in the said embodiment, although the connection member 23 is comprised by metal foil, if the connection member 23 is a material which has flexibility, it will be materials other than metal foil (for example, a carbon plate, a resin film with a transparent conductive film) ) Can also be used.

  Moreover, in the said embodiment, although the non-fixed part 23b of the connection member 23 is bent, the non-fixed part 23b does not need to bend.

  Furthermore, in the said embodiment, although the connection member 23 is being fixed to the metal substrate 21 as another member, a part of metal substrate 21 may serve as the connection member 23.

  Furthermore, in the said embodiment, although the transparent substrate 11 is a common transparent substrate in all the dye-sensitized solar cells 50A-50H in the dye-sensitized solar cell module 200, the transparent substrate 11 is a dye-sensitized solar cell module. In 200, all the dye-sensitized solar cells 50A to 50H may not be a common transparent substrate. That is, each of all the dye-sensitized solar cells 50 </ b> A to 50 </ b> H may have the transparent substrate 11 individually.

  Moreover, in the said embodiment, although the dye-sensitized solar cell module 200 has two dye-sensitized solar cell module units 100A and 100B, it is not restricted to two, One may be sufficient and three or more may be sufficient Good. In the above embodiment, each of the dye-sensitized solar cell module units 100A and 100B includes four dye-sensitized solar cells 50, but the dye-sensitized solar cell in each of the dye-sensitized solar cell module units 100A and 100B. The number of 50 is not limited to four, and may be any number as long as it is plural.

  Furthermore, in the said embodiment, although the protrusion direction of the connection member 23 with respect to the counter electrode 20 is the same in each of dye-sensitized solar cell module unit 100A, 100B, it is not necessary to be the same and it is mutually different. May be.

  Furthermore, in the said embodiment, although dye-sensitized solar cell module unit 100A, 100B is mutually connected in series, these may be connected in parallel.

  Furthermore, in the above embodiment, the counter electrode 20 includes the metal substrate 21, but the counter electrode 20 does not necessarily need to include the metal substrate 21. For example, the counter electrode 20 may have a transparent conductive film formed on the transparent substrate 11 instead of the metal substrate 21.

  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.

Furthermore, in the said embodiment, although the land part 14c is supposed to exist inside the outer peripheral part 14a, the part of the outer peripheral part 14a which touches the land part 14c may be comprised with the material similar to the land part 14c. .
Furthermore, in the said embodiment, although the connection part 30 functions as a sealing part, a cover layer is further provided so that the counter electrode 20 of the several dye-sensitized solar cell 50 may be opposed, a cover layer, and a transparent conductive substrate 15 is connected by a sealing portion provided so as to surround the plurality of dye-sensitized solar cells 50, and the dye sensitization has a structure in which the electrolyte 40 is disposed between the cover layer and the transparent conductive substrate 15. In the solar cell module, the connecting portion 30 may not function as a sealing portion.

  Furthermore, although the said embodiment demonstrated the dye-sensitized solar cell module 100 which has multiple dye-sensitized solar cells 50, the dye-sensitized solar cell module 100 is one dye-sensitized solar cell 50 (for example, dye-sensitized solar cell). The battery 50C) may be used alone. In this case, a current extraction wiring (not shown) for extracting current to the outside is connected to the land portion 14c which is the first current collecting wiring portion. Even in this case, the content rate of the glass component in the land portion 14c to which the current extraction wiring is connected is larger than the content rate of the glass component in the outer peripheral portion 14a and the partition portion 14b of the current collection wiring 14. . For this reason, the adhesiveness with the transparent conductive film 12 can be improved about the land part 14c to which the electric current extraction wiring is connected. For this reason, even if an excessive stress is applied between the current extraction wiring and the current collection wiring 14 due to bending of the transparent substrate 11, the current collection wiring 14 is sufficiently separated from the transparent conductive film 12. It is suppressed. Therefore, the dye-sensitized solar cell 50 can have excellent connection reliability. On the other hand, since the content rate of the glass component in the land portion 14c to which the current extraction wiring is connected is larger than the content rate of the glass component in the outer peripheral portion 14a and the partition portion 14b of the current collecting wiring 14, the transparent conductive film However, the resistance between the transparent conductive film 12, the outer peripheral portion 14a, and the partition portion 14b can be kept low. For this reason, the current generated in the oxide semiconductor layer 13 can sufficiently flow from the outer peripheral portion 14a and the partition portion 14b to the outside through the land portion 14c. Therefore, the dye-sensitized solar cell 50 can have excellent photoelectric conversion characteristics.

  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 prepared by forming a transparent conductive film having a thickness of 1 μm made of FTO on the surface of a transparent substrate made of glass having a surface dimension of 500 mm × 500 mm and a thickness of 4 mm was prepared. Then, the transparent conductive film was patterned by etching, and the transparent conductive film was divided into eight transparent conductive films.

  Next, on each transparent conductive film, an oxide semiconductor layer forming paste (manufactured by JGC Catalysts & Chemicals Co., Ltd., PST-18NR) was applied with a screen printer, and then sintered at 500 ° C. for 1 hour in an electric furnace. Thus, a porous oxide semiconductor layer was formed.

  Next, the 1st paste for forming the land part 14c and the 2nd paste for forming the outer peripheral part 14a and the partition part 14b were prepared. Here, the 1st paste contains silver, the glass component which consists of glass frit, the solvent which consists of terpineol, and ethyl cellulose, and the content rate of the glass component in the land part 14c obtained by baking of a 1st paste will be 7 mass%. Prepared as follows. As the second paste, a commercially available silver paste (GL6000X-14 manufactured by Fukuda Metal Foil Industry Co., Ltd.) having a glass component content of 2% by mass in the outer peripheral part 14a and the partition part 14b obtained by firing was prepared. First, the second paste was applied so as to surround the porous oxide semiconductor layer, and then dried. Next, the first paste was applied to the inside of the portion of the applied second paste that forms the outer peripheral portion 14a, and then dried. And about each of the 1st paste and the 2nd paste, this application | coating and drying were repeated 3 times with the screen printer. Thereafter, the first paste and the second paste were sintered in an electric furnace at 500 ° C. for 1 hour. In this way, the current collection wiring which consists of a land part, an outer peripheral part, and a partition part was formed. At this time, when a cross section of the land portion was observed with an SEM, voids were present and the void ratio was 18%.

  Next, a glass paste for forming a wiring protective layer for protecting the current collecting wiring was applied to a region where the electrolyte and the current collecting wiring were in contact, and then dried. This coating and drying were repeated three times, and the wiring protective layer forming glass paste was sintered in an electric furnace at 500 ° C. for 1 hour. In this way, eight working electrodes were 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. The photosensitizing dye was adsorbed to the porous semiconductor layer by immersing the dye in the room temperature for 24 hours, allowing the dye to be adsorbed on the porous semiconductor layer, washing away excess dye with the mixed solvent, and drying. .

  On the other hand, eight counter electrodes were prepared as follows.

  That is, first, a metal substrate made of a rolled titanium foil having a thickness of 200 μm was prepared, and Pt was deposited on one surface of the metal substrate by sputtering to obtain a counter electrode. In this way, eight counter electrodes were prepared.

  Next, seven metal foils for forming a connecting member made of copper having a thickness of 200 μm, a length of 10 cm, and a width of 1 cm are prepared, and a portion of each of the metal foils for forming a connecting member having a length of 2 cm is composed of seven counter electrode metal substrates. Each was fixed by resistance welding. At this time, in resistance welding, the two electrodes were both pressed against the metal foil for connecting member formation, and a current of 1.0 kA was applied between the resistance welding electrodes for 10 milliseconds. At this time, the interval between the two resistance welding electrodes was 1 mm.

  Next, on each of the eight working electrodes, a square 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.) The resin sheet was fixed on each of the eight working electrodes by heating and melting at 150 ° C.

  A square annular resin sheet (width 2 mm, thickness 50 μm) made of an ethylene-methacrylic acid copolymer (trade name: Nucrel, Mitsui / DuPont Polychemical Co., Ltd.) is also provided on each catalyst layer side of the eight counter electrodes. The resin sheet was placed and fixed on each of the eight counter electrodes by heating and melting at 150 ° C.

  Next, a volatile electrolyte using methoxyacetonitrile (MPN) as a solvent was injected on each working electrode and inside the resin sheet.

  And the resin sheet fixed on each counter electrode and the resin sheet fixed on each working electrode were piled up, and these resin sheets were pressure-bonded while heating at 150 ° C. In this way, a connection part was formed between each working electrode and each counter electrode, and eight dye-sensitized solar cells were obtained.

  Next, the 3 cm long portion of the non-fixed portion of the connection member fixed to the counter electrode was joined to the current collecting wiring of the adjacent dye-sensitized solar cell by resistance welding. In resistance welding, the two electrodes were both pressed against a 3 cm long portion of the non-fixed portion of the connection member, and a current of 1.0 kA was applied between the resistance welding electrodes for 10 milliseconds. At this time, the interval between the two resistance welding electrodes was 1 mm. Also, at this time, the non-fixed part was in a loose state. In this way, a connecting member for connecting two adjacent dye-sensitized solar cells was formed.

  Thus, a dye-sensitized solar cell module composed of one dye-sensitized solar cell module unit including eight dye-sensitized solar cells was obtained.

(Example 2)
The pigment content in the same manner as in Example 1 except that the glass component content in the land portion 14c was changed to 5% by mass as shown in Table 1 and the porosity in the land portion was changed to that shown in Table 1. A sensitized solar cell module was produced.

(Example 3)
The content of the glass component in the land portion 14c was changed to 4% by mass as shown in Table 1, and the pigment was changed in the same manner as in Example 1 except that the porosity in the land portion was changed as shown in Table 1. A sensitized solar cell module was produced.

Example 4
The content rate of the glass component in the land portion 14c was changed to 9% by mass as shown in Table 1, and the porosity in the land portion 14c was changed to that shown in Table 1 in the same manner as in Example 1. A dye-sensitized solar cell module was produced.

(Example 5)
As shown in Table 1, the content ratio of the glass component in the land portion 14c and the glass component content in the outer peripheral portion 14a and the partition portion 14b are changed to 5 mass% and 3 mass%, respectively. A dye-sensitized solar cell module was produced in the same manner as in Example 1 except that the void ratio was as shown in Table 1.

(Example 6)
As shown in Table 1, the glass component content in the land portion 14c and the glass component content in the outer peripheral portion 14a and the partition portion 14b were changed to 4% by mass and 0.5% by mass, respectively. A dye-sensitized solar cell module was produced in the same manner as in Example 1 except that the porosity in the part 14c was as shown in Table 1.

(Example 7)
The connection of the metal foil for forming the connecting member to the metal substrate and the connection of the metal foil for forming the connecting member to the current collector wiring are performed by soldering with a soldering iron set at 230 ° C. Except for the above, a dye-sensitized solar cell module was produced in the same manner as in Example 1. As the solder, lead-free solder (manufactured by Ishikawa Metal Co., Ltd.) was used.

(Example 8)
As shown in Table 1, the content ratio of the glass component in the land portion 14c is changed to 4% by mass, and the porosity in the land portion 14c is set as shown in Table 1 and for forming a connection member to the metal substrate. The same as in Example 1 except that the connection of the metal foil and the connection of the metal foil for forming the connection member to the current collector wiring are performed by soldering with a soldering iron set at 230 ° C. Thus, a dye-sensitized solar cell module was produced. As the solder, lead-free solder (manufactured by Ishikawa Metal Co., Ltd.) was used.

(Comparative Example 1)
By changing the content of the glass component in the land portion 14c to 2% by mass as shown in Table 1, the content of the glass component in the land portion 14c is changed to that of the glass component in the outer peripheral portion 14a and the partition portion 14b. A dye-sensitized solar cell module was produced in the same manner as in Example 1 except that the content was the same as the content rate and the porosity in the land portion 14c was as shown in Table 1.

(Comparative Example 2)
By changing the glass component content in the land part 14c and the glass component content in the outer peripheral part 14a and the partition part 14b to 7% by mass and 7% by mass, respectively, as shown in Table 1, Example 1 except that the glass component content in the portion 14c is the same as the glass component content in the outer peripheral portion 14a and the partition portion 14b, and the porosity in the land portion 14c is as shown in Table 1. In the same manner as in Example 1, a dye-sensitized solar cell module was produced.

(Comparative Example 3)
By changing the content of the glass component in the land portion 14c and the content of the glass component in the outer peripheral portion 14a and the partition portion 14b to 4% by mass and 4% by mass, respectively, as shown in Table 1, Example 1 except that the glass component content in the portion 14c is the same as the glass component content in the outer peripheral portion 14a and the partition portion 14b, and the porosity in the land portion 14c is as shown in Table 1. In the same manner as in Example 1, a dye-sensitized solar cell module was produced.

(Comparative Example 4)
By changing the glass component content in the land part 14c and the glass component content in the outer peripheral part 14a and the partition part 14b to 2% by mass and 5% by mass, respectively, as shown in Table 1, Example 1 except that the glass component content in the part 14c is smaller than the glass component content in the outer peripheral part 14a and the partition part 14b, and the porosity in the land part 14c is as shown in Table 1. In the same manner, a dye-sensitized solar cell module was produced.

(Comparative Example 5)
By changing the content of the glass component in the land portion 14c to 2% by mass as shown in Table 1, the content of the glass component in the land portion 14c is changed to that of the glass component in the outer peripheral portion 14a and the partition portion 14b. A dye-sensitized solar cell module was produced in the same manner as in Example 7 except that the content was the same as the content rate and the porosity in the land portion 14c was as shown in Table 1.

(Comparative Example 6)
By changing the content rate of the glass component in the outer peripheral part 14a and the partition part 14b to 4 mass% as shown in Table 1, the content rate of the glass component in the land part 14c is changed in the outer peripheral part 14a and the partition part 14b. A dye-sensitized solar cell module was produced in the same manner as in Example 8 except that the content of the glass component was the same as that shown in Table 1 and the porosity of the land portion 14c was as shown in Table 1.

(Connection reliability)
Connection reliability was examined for the dye-sensitized solar cell modules obtained in Examples 1 to 8 and Comparative Examples 1 to 6. Specifically, in a state where the transparent substrate of the dye-sensitized solar cell module is inclined at 45 degrees with respect to the horizontal plane, the connecting member is pulled in the vertical direction, and the strength until the land portion 14c peels from the transparent conductive film is examined. It was. At this time, the pulling speed was 300 mm / min. The results are shown in Table 1. Here, the acceptance criteria were as follows.
Pass: Strength is 5N or more. Fail: Strength is less than 5N.

(Photoelectric conversion characteristics)
About the photoelectric conversion characteristic, the shape factor (henceforth "FF") measured about the dye-sensitized solar cell module obtained in Examples 1-8 and Comparative Examples 1-6 was made into the parameter | index. The results are shown in Table 1. Here, the acceptance criteria were as follows.

Pass: FF is 0.65 or more Fail: FF is less than 0.65

  From the results shown in Table 1, the dye-sensitized solar cell modules obtained in Examples 1 to 8 passed both the photoelectric conversion characteristics and the connection reliability. On the other hand, the dye-sensitized solar cell modules of Comparative Examples 1 to 8 failed in at least one of photoelectric conversion characteristics and connection reliability.

  From the above, it was confirmed that the dye-sensitized solar cell module of the present invention has excellent photoelectric conversion characteristics and connection reliability.

DESCRIPTION OF SYMBOLS 10 ... Working electrode 11 ... Transparent substrate 12 ... Transparent electrically conductive film 13 ... Oxide semiconductor layer 14 ... Current collection wiring 14a ... Outer peripheral part (2nd current collection wiring part)
14b ... Partition part (second current collector wiring part)
14c ... Land part (1st current collection wiring part)
15 ... Transparent conductive substrate (first electrode)
17 ... Wiring part 20 ... Counter electrode (second electrode)
DESCRIPTION OF SYMBOLS 23 ... Connection member 30 ... Connection part 50,50A-50H ... Dye-sensitized solar cell 60 ... Alloy part 100A, 100B ... Dye-sensitized solar cell module unit 200 ... Dye-sensitized solar cell module

Claims (9)

A first electrode having a transparent substrate, a transparent conductive film provided on the transparent substrate, and a current collector wiring provided on the transparent conductive film;
A second electrode facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
A photosensitizing dye carried on the oxide semiconductor layer;
An electrolyte provided between the first electrode and the second electrode,
The current collector wiring is
A first current collector wiring portion including a glass component for connecting the conductive member;
A second current collector wiring portion to which the conductive member is not connected;
The dye-sensitized solar cell, wherein the glass component content in the first current collector wiring portion is larger than the glass component content in the second current collector wiring portion.   The dye-sensitized solar cell according to claim 1, wherein a content ratio of the glass component in the first current collector wiring portion is 4 to 10% by mass.   The difference of the content rate of the said glass component in a said 1st current collection wiring part and the content rate of the said glass component in a said 2nd current collection wiring part is 1-10 mass%. Dye-sensitized solar cell. The first current collector wiring portion includes a gap;
The dye-sensitized solar cell as described in any one of Claims 1-3 whose porosity in a said 1st current collection wiring part is 30% or less. In a dye-sensitized solar cell module having a dye-sensitized solar cell module unit including a plurality of dye-sensitized solar cells connected in series and electrically,
The dye-sensitized solar cell is
A first electrode having a transparent substrate, a transparent conductive film provided on the transparent substrate, and a current collector wiring provided on the transparent conductive film;
A second electrode facing the first electrode;
An oxide semiconductor layer provided on the first electrode or the second electrode;
A photosensitizing dye carried on the oxide semiconductor layer;
An electrolyte provided between the first electrode and the second electrode,
Connection for electrically connecting the second electrode of one dye-sensitized solar cell of two adjacent dye-sensitized solar cells and the current collector wiring of the first electrode of the other dye-sensitized solar cell Members are provided,
The current collector wiring of the other dye-sensitized solar cell is
A first current collector wiring portion connected to the connecting member and containing a glass component;
A second current collector wiring portion to which the connection member is not connected;
The dye-sensitized solar cell module, wherein a content ratio of the glass component in the first current collecting wiring portion is larger than a content ratio of the glass component in the second current collecting wiring portion.   The dye-sensitized solar cell module according to claim 5, wherein a content ratio of the glass component in the first current collector wiring portion is 4 to 10% by mass.   The difference of the content rate of the said glass component in a said 1st current collection wiring part and the content rate of the said glass component in a said 2nd current collection wiring part is 1-10 mass%. Dye-sensitized solar cell module. The first current collector wiring portion includes a gap;
The dye-sensitized solar cell module according to any one of claims 5 to 7, wherein a porosity of the first current collecting wiring portion is 30% or less. An alloy made of an alloy of a metal contained in the first current collecting wiring portion and a metal contained in the connecting member between the first current collecting wiring portion and the connecting member of the other dye-sensitized solar cell. The dye-sensitized solar cell module according to any one of claims 5 to 8, wherein a portion is provided.

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