JPWO2014034913A1 - Dye-sensitized solar cell element for low illumination - Google Patents

Abstract

The low-illuminance dye-sensitized solar cell element includes at least one dye-sensitized solar cell, a first current extraction unit for extracting current from at least one dye-sensitized solar cell, and at least one dye-sensitized solar cell. A dye-sensitized solar cell, the first electrode having a transparent substrate, a transparent conductive film provided on the transparent substrate, and the first electrode. A second electrode having a metal substrate, an oxide semiconductor layer provided on the first electrode or the second electrode, and an annular sealing portion for joining the first electrode and the second electrode, The current extraction unit is included in the transparent conductive film of one dye-sensitized solar cell among the at least one dye-sensitized solar cell, and the second current extraction unit is included in at least one dye-sensitized solar cell. Of one dye-sensitized solar cell Is electrically connected to the metal substrate of the second electrode, the first current extraction portion and the second current extraction portion are arranged next to each other.

Description

  The present invention relates to a dye-sensitized solar cell element for low illuminance.

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

  The dye-sensitized solar cell element generally includes at least one dye-sensitized solar cell, and each dye-sensitized solar cell includes a working electrode, a counter electrode, and an annular sealing portion that connects the working electrode and the counter electrode. And. The working electrode includes a transparent substrate, a transparent conductive film formed thereon, and an oxide semiconductor layer provided on the transparent conductive film.

  As such a dye-sensitized solar cell element, for example, an element described in Patent Document 1 below is known. Patent Document 1 below discloses a dye-sensitized solar cell module having a plurality of dye-sensitized solar cells connected in series. In the dye-sensitized solar cell module of Patent Document 1 below, an extraction electrode is connected to the counter electrode of one of the dye-sensitized solar cells at both ends of the plurality of dye-sensitized solar cells, and the other dye-sensitized solar cell is used. An extraction electrode is connected to the conductive film of the solar cell. Here, the two extraction electrodes are arranged so as to face in opposite directions.

  Further, as a dye-sensitized solar cell element, for example, an element described in Patent Document 2 below is known. In Patent Document 2 below, in two adjacent dye-sensitized solar cells, a conductive member extending from the counter electrode of one dye-sensitized solar cell and a transparent conductive film of the other dye-sensitized solar cell are adjacent to each other. A dye-sensitized solar cell module connected between stops is disclosed.

JP 2012-9374 A International Publication No. 2009/13389

  By the way, in recent years, dye-sensitized solar cell elements have come to be used not only outdoors but also under low illuminance such as indoors. Dye-sensitized solar cell elements suitable for use under low illuminance Is also being developed. Since the dye-sensitized solar cell element for low illuminance is mainly intended for indoor use, it is extremely important to save space for the dye-sensitized solar cell element for low illuminance.

  However, in the dye-sensitized solar cell module described in Patent Document 1, the two extraction electrodes are arranged so as to face in opposite directions. For this reason, in the dye-sensitized solar cell module described in Patent Document 1, it is necessary to prepare two connectors in order to extract current from the extraction electrode, and to connect each connector to each of the two extraction electrodes. For this reason, when installing a dye-sensitized solar cell module, the space for accommodating two connectors was required. Therefore, the dye-sensitized solar cell module described in Patent Document 1 has room for improvement in terms of space saving when intended for use under low illuminance.

  On the other hand, a dye-sensitized solar cell module for low illuminance is also required to have excellent photoelectric conversion characteristics.

  The dye-sensitized solar cell module may be housed in a case having an opening. In this case, the dye-sensitized solar cell module is arranged so that the light-receiving surfaces of all the dye-sensitized solar cells are accommodated inside the opening. Accordingly, the larger the total area of the light receiving surface in the area inside the opening, the higher the aperture ratio.

  Having such a high aperture ratio is of course not only a dye-sensitized solar cell module used outdoors, but also a dye-sensitized solar cell module having a small size such that the power generation current of one dye-sensitized solar cell is less than 500 mA. And a dye-sensitized solar cell module used in a place with relatively low illuminance such as indoors. In particular, small-size dye-sensitized solar cell modules and dye-sensitized solar cell modules used in places with relatively low illuminance have a smaller light-receiving area than light-sensitive solar cell modules used outdoors. The amount is small. For this reason, in a dye-sensitized solar cell module, it is calculated | required to have especially high aperture ratio so that electric power generation may be performed efficiently.

  However, in the dye-sensitized solar cell module described in Patent Document 2, a conductive member extending from the counter electrode of one dye-sensitized solar cell in two adjacent dye-sensitized solar cells and the other dye-sensitized solar cell. The transparent conductive film is connected between the adjacent sealing portions. That is, the connection location where the edge of the counter electrode is connected to the transparent conductive film is present in the light receiving area inside the opening of the case described above. For this reason, it does not contribute to power generation by the area of the connection location, and the aperture ratio becomes low. In particular, the area required for the connection site is usually almost the same for a dye-sensitized solar cell module having a large light receiving area and a small dye-sensitized solar cell module. For this reason, when the connection location between two adjacent dye-sensitized solar cells is within the light receiving area, the dye-sensitized solar cell module having a smaller light receiving area has a lower aperture ratio. Here, in order to obtain a high aperture ratio, it is conceivable to reduce the area of the connection portion. However, in this case, the bonding strength at the connection location is lowered, and the connection reliability is lowered. Therefore, in the dye-sensitized solar cell module described in Patent Document 1, it is difficult to obtain a higher aperture ratio.

  Thus, the dye-sensitized solar cell module described in Patent Document 2 has room for improvement in terms of improving the aperture ratio.

  Moreover, in the dye-sensitized solar cell module of the said patent document 2, the connection of adjacent dye-sensitized solar cells is performed between adjacent sealing parts. For this reason, a gap exists between two adjacent sealing portions, and the two adjacent sealing portions are respectively exposed to the gap. For this reason, moisture and air in the atmosphere are likely to enter the inside of the dye-sensitized solar cell. Therefore, the dye-sensitized solar cell module described in Patent Document 2 has room for improvement in terms of durability.

  The present invention has been made in view of the above circumstances, and has as its first object to provide a low-illuminance dye-sensitized solar cell element capable of saving space while having excellent photoelectric conversion characteristics. To do.

  The second object of the present invention is to provide a dye-sensitized solar cell element that can improve the aperture ratio and has excellent durability.

  The inventors of the present invention have made extensive studies in order to achieve the first object. First, in order to save the space of the dye-sensitized solar cell element, it is conceivable to reduce the number of connectors connected to the extraction electrode to one. For this purpose, the two extraction electrodes in the dye-sensitized solar cell element may be arranged adjacent to each other. However, in the dye-sensitized solar cell module described in Patent Document 1, in order to arrange the two extraction electrodes so as to be adjacent to each other, one of the dye-sensitized solar cells at both ends of the plurality of dye-sensitized solar cells. A part of the transparent conductive film of the dye-sensitized solar cell is stretched, an extraction electrode is provided at the tip of the stretched part, and the other of the dye-sensitized solar cells at both ends of the plurality of dye-sensitized solar cells It arrange | positions so that it may adjoin to the extraction electrode connected to this dye-sensitized solar cell. In this case, even if the amount of generated current increases, there is no particular problem as long as the resistance of the extended portion can be lowered. However, if the generated current becomes too large, there is a limit even if the resistance of the transparent conductive film is reduced. As a result, the photoelectric conversion characteristics are degraded. For this reason, it has been considered that it is practically difficult to arrange the two extraction electrodes so as to be adjacent to each other. However, when the dye-sensitized solar cell module is used under a low illuminance, the present inventors have found that the two extraction electrodes in the dye-sensitized solar cell module are adjacent to each other because the generated current is sufficiently small. Even if it arrange | positions so that it may fit, it thought that the fall of a photoelectric conversion characteristic could fully be suppressed. Thus, the present inventors have completed the present invention.

  That is, the present invention provides at least one dye-sensitized solar cell, a first current extraction unit for extracting current from the at least one dye-sensitized solar cell, and extracts current from the at least one dye-sensitized solar cell. A first electrode having a transparent substrate, a transparent conductive film provided on one surface of the transparent substrate, and a first electrode having a second current extraction portion for opposing the first electrode. A second electrode having a metal substrate, an oxide semiconductor layer provided on the first electrode or the second electrode, and an annular sealing portion for joining the first electrode and the second electrode. The first current extraction unit is included in the transparent conductive film of one of the at least one dye-sensitized solar cell, and the second current extraction unit is the at least One color One of the sensitized solar cells is electrically connected to the metal substrate of the second electrode of the dye-sensitized solar cell, and is disposed so that the first current extraction portion and the second current extraction portion are adjacent to each other. This is a dye-sensitized solar cell element for low illuminance.

  According to the low-illuminance dye-sensitized solar cell element, the first current extraction portion and the second current extraction portion are arranged adjacent to each other. For this reason, it becomes possible to make the number of the connectors for taking out an electric current outside from the 1st electric current extraction part and the 2nd electric current extraction part one. In other words, it is possible to integrate a connector for extracting current from the first current extraction unit and the second current extraction unit. For this reason, according to the dye-sensitized solar cell element for low illuminance of the present invention, space saving can be achieved. Moreover, when the dye-sensitized solar cell element for low illuminance of the present invention is used under low illuminance, the generated current is small. For this reason, a part of the transparent conductive film of one dye-sensitized solar cell of at least one dye-sensitized solar cell is replaced with the first of the dye-sensitized solar cells of at least one dye-sensitized solar cell. Even if it arrange | positions as a 1st electric current extraction part adjacent to the 2nd electric current extraction part electrically connected to the metal substrate of 2 electrodes, the fall of photoelectric conversion performance can fully be suppressed.

  The low-illuminance dye-sensitized solar cell element may further include a back sheet that covers the at least one dye-sensitized solar cell on the one surface side of the transparent substrate.

  In the low-illuminance dye-sensitized solar cell element, an insulating connecting portion is provided on the entire periphery of the back sheet, and the low-illuminance dye-sensitized solar cell element includes the transparent substrate and the connecting portion. And a separation part provided so as to surround the transparent conductive film of at least one dye-sensitized solar cell and to form a gap between the transparent conductive film and the separation part Preferably, the first current extraction part and the second current extraction part are provided so as to form an annular structure, and a part of the gap is disposed inside the connection part.

  In this case, the back sheet prevents moisture from entering a part of the gap. For this reason, it is possible to sufficiently prevent the moisture from adhering to the transparent conductive film due to the moisture that has entered the gaps in the part. For this reason, a short circuit is sufficiently prevented from occurring in the dye-sensitized solar cell.

  In the low-illuminance dye-sensitized solar cell element, the first current extraction portion and the second current extraction portion are arranged around one dye-sensitized solar cell of the at least one dye-sensitized solar cell. The metal substrate of the second electrode of the one dye-sensitized solar cell of the at least one dye-sensitized solar cell and the second current extraction unit are connected by a second connection unit. May be.

  In this case, for example, when the dye-sensitized solar cell element for low illuminance has a plurality of dye-sensitized solar cells arranged in a line along a certain direction, a part of the plurality of dye-sensitized solar cells is dye-sensitized. The solar cell is folded halfway, and one of the dye-sensitized solar cells at both ends of a plurality of dye-sensitized solar cells is arranged so that the dye-sensitized solar cell at one end and the dye-sensitized solar cell at the other end are adjacent to each other Compared to the case of connecting two adjacent dye-sensitized solar cells, it is possible to shorten the installation area of connection terminals provided along a plurality of dye-sensitized solar cells, thereby saving more space. Can be achieved. In addition, the number of dye-sensitized solar cells can be selected to be either even or odd, and the number of dye-sensitized solar cells can be freely determined, thereby improving the degree of design freedom. it can. In addition, according to the dye-sensitized solar cell element for low illuminance of the present invention, when the dye-sensitized solar cell element for low illuminance is used in a low illuminance environment, the generated current is usually small. Even if the dye-sensitized solar cell element for low illuminance further has a second connection portion for connecting the metal substrate of the second electrode of the dye-sensitized solar cell on the other end side and the second current extraction portion, A decrease in conversion characteristics can be sufficiently suppressed.

  The low-illuminance dye-sensitized solar cell element preferably further includes a second current collector wiring provided on the second connection portion and having a lower resistance than the second connection portion.

  In this case, since the second current collection wiring has a lower resistance than the second connection portion, it is possible to sufficiently suppress the deterioration of the photoelectric conversion characteristics even when the generated current becomes large.

  In the low illuminance dye-sensitized solar cell element, it is preferable that the second current collecting wiring is disposed so as not to intersect with a peripheral edge portion of the back sheet.

  In this case, the current collecting wiring is generally porous and has air permeability, and gas such as water vapor is permeable, but the second current collecting wiring does not intersect with the peripheral portion of the back sheet. If it arrange | positions in this way, it can prevent that water vapor | steam etc. penetrate | invade from the exterior into the space inside a back seat | sheet through the 2nd current collection wiring. As a result, the dye-sensitized solar cell element can have excellent durability. In addition, since the second current collector wiring has a lower resistance than the transparent conductive film, it is possible to sufficiently suppress the deterioration of the photoelectric conversion characteristics even when the generated current increases.

  In the low-illuminance dye-sensitized solar cell element, it is preferable that the second connection portion is disposed on an inner side than a peripheral edge portion of the back sheet.

  In this case, moisture can be sufficiently prevented from entering the back sheet from the outside of the back sheet. For this reason, it is possible to sufficiently prevent moisture from adhering to the second connection portion, and increase in resistance of the second connection portion and short circuit between the second connection portion and the transparent conductive film of the dye-sensitized solar cell are sufficient. To be prevented.

  In the low-illuminance dye-sensitized solar cell element, the first current extraction portion and the second current extraction portion are arranged around one dye-sensitized solar cell of the at least one dye-sensitized solar cell. A main body provided at the inner side of the annular sealing portion, and the main body, wherein the transparent conductive film of one dye-sensitized solar cell of the at least one dye-sensitized solar cell is disposed; You may further have a 1st connection part which connects a said 1st electric current extraction part.

  In this case, for example, when the dye-sensitized solar cell element for low illuminance has a plurality of dye-sensitized solar cells arranged in a line along a certain direction, a part of the plurality of dye-sensitized solar cells is dye-sensitized. The solar cell is folded halfway, and one of the dye-sensitized solar cells at both ends of a plurality of dye-sensitized solar cells is arranged so that the dye-sensitized solar cell at one end and the dye-sensitized solar cell at the other end are adjacent to each other Compared to the case where the two dye-sensitized solar cells are connected to each other, it is possible to further shorten the installation area of the connection terminals provided along the plurality of dye-sensitized solar cells, thereby saving more space. Can be achieved. In addition, the number of dye-sensitized solar cells can be selected to be either even or odd, and the number of dye-sensitized solar cells can be freely determined, thereby improving the degree of design freedom. it can. In addition, according to the dye-sensitized solar cell element for low illuminance of the present invention, when the dye-sensitized solar cell element for low illuminance is used in a low illuminance environment, the generated current is usually small. Even if the dye-sensitized solar cell element for low illuminance further includes a first connection part for connecting the main body part and the first current extraction part, it is possible to sufficiently suppress the deterioration of the photoelectric conversion characteristics.

  The low-illuminance dye-sensitized solar cell element is provided along the first connection portion on at least the first connection portion of one of the at least one dye-sensitized solar cell. It is preferable to further include a first current collector wiring having a lower resistance than the first connection portion.

  In this case, since the first current collection wiring has a lower resistance than the first connection portion, it is possible to sufficiently suppress the deterioration of the photoelectric conversion characteristics even when the generated current becomes large.

  In the low-illuminance dye-sensitized solar cell element, it is preferable that the first current-collecting wiring is disposed so as not to intersect with a peripheral edge portion of the back sheet.

  In this case, the current collecting wiring is generally porous and has air permeability, and gas such as water vapor is permeable, but the first current collecting wiring does not intersect with the peripheral portion of the backsheet. If it arrange | positions in this way, it can prevent that water vapor | steam etc. penetrate | invade from the exterior into the space inside a back seat | sheet through the 1st current collection wiring. As a result, the dye-sensitized solar cell element can have excellent durability. In addition, since the first current collector wiring has a resistance lower than that of the transparent conductive film, it is possible to sufficiently suppress the deterioration of the photoelectric conversion characteristics even when the generated current is increased.

  Further, the low-illuminance dye-sensitized solar cell element includes a plurality of the dye-sensitized solar cells, the transparent substrate is formed of a common transparent substrate of the plurality of dye-sensitized solar cells, and two adjacent two The second electrodes of the dye-sensitized solar cell are spaced apart from each other, and the sealing portion includes an annular first sealing portion provided between the first electrode and the second electrode, and is adjacent to each other. The first sealing portions of two matching dye-sensitized solar cells are integrated to form a first integrated sealing portion, and the first integrated sealing portion includes an annular portion and an annular portion. A width of an adhesive portion between the partition portion of the first integrated sealing portion and the surface on the first electrode side of the second electrode is the first integrated. It is preferable that the width of the bonding portion between the annular portion of the sealing portion and the surface of the second electrode on the first electrode side is narrower.

  According to this dye-sensitized solar cell element, the width of the bonding portion between the partition portion of the first integrated sealing portion and the surface on the first electrode side of the second electrode is the annular shape of the first integrated sealing portion. It is narrower than the width of the bonded portion between the portion and the surface of the second electrode on the first electrode side. For this reason, the aperture ratio in a dye-sensitized solar cell element can be improved more fully. Moreover, in the dye-sensitized solar cell element of this invention, the 1st sealing part of two adjacent dye-sensitized solar cells is integrated, and the 1st integrated sealing part is comprised. Here, if the first sealing portions of the two adjacent dye-sensitized solar cells are not integrated, the first sealing portion exposed to the atmosphere between the adjacent dye-sensitized solar cells. There are two places. On the other hand, in the dye-sensitized solar cell element, the adjacent first sealing portions are integrated to form the first integrated sealing portion, and therefore, between the adjacent dye-sensitized solar cells. The first sealing portion exposed to the atmosphere is one place. That is, between the adjacent dye-sensitized solar cells, the sealing part exposed to the atmosphere is only one part of the partition part of the first integrated sealing part. Moreover, since the first sealing portions are integrated with each other, the penetration distance of moisture and the like from the atmosphere to the electrolyte is extended. For this reason, the quantity of the water | moisture content and air which penetrate | invade from the exterior of a dye-sensitized solar cell can be fully reduced between adjacent dye-sensitized solar cells. That is, the sealing ability of the dye-sensitized solar cell element can be sufficiently improved. Moreover, according to the dye-sensitized solar cell element, adjacent first sealing portions are integrated. For this reason, the width | variety of the adhesion part with the partition part of a 1st integrated sealing part and the surface by the side of a 1st electrode among 2nd electrodes is the 1st among the annular part of a 1st integrated sealing part, and a 2nd electrode. Even if it is narrower than the width of the bonding portion with the surface on the one electrode side, it is possible to ensure a sufficient sealing width in the partition portion. That is, according to the dye-sensitized solar cell element of the present invention, the adhesive strength between the first sealing portion and the first electrode and the adhesive strength between the first sealing portion and the second electrode are improved while improving the aperture ratio. It can be made sufficiently large. As a result, the aperture ratio can be improved, and when the dye-sensitized solar cell element is used at a high temperature, the electrolyte expands and an excessive stress is applied from the inside to the outside of the first sealing portion. However, peeling of the 1st sealing part from the 1st electrode and the 2nd electrode can fully be controlled, and it becomes possible to have outstanding durability.

  In the said dye-sensitized solar cell element, it is preferable that the width | variety of the said partition part is 100% or more and less than 200% of the width | variety of the said annular part.

  In this case, in the partition part of the first integrated sealing part, since the width of the partition part is 100% or more of the width of the annular part, the width of the partition part is less than 100% of the width of the annular part. Thus, the penetration distance of moisture and the like from the atmosphere to the electrolyte is further extended. For this reason, it can suppress more fully that a water | moisture content penetrate | invades from the exterior through the partition part between adjacent dye-sensitized solar cells. On the other hand, compared with the case where the width | variety of a partition part exceeds 200% of the width | variety of an annular part, an aperture ratio can be improved more.

  In the dye-sensitized solar cell element, the sealing portions of the plurality of dye-sensitized solar cells are provided so as to overlap the first sealing portion, and together with the first sealing portion, the second electrode It is preferable to further include an annular second sealing portion that sandwiches the edge portion, and the second sealing portion is integrated to form a second integrated sealing portion.

  In this case, even if a stress in a direction away from the first electrode acts on the second electrode, the separation is sufficiently suppressed by the second sealing portion or the second integrated sealing portion.

  The low-illuminance dye-sensitized solar cell element includes a plurality of the dye-sensitized solar cells, the plurality of dye-sensitized solar cells are connected in series and electrically, and the plurality of dye-sensitized solar cells Among them, the dye-sensitized solar cell connected to the adjacent dye-sensitized solar cell further includes a connection terminal provided on the transparent conductive film, and the transparent conductive film is formed of the annular sealing portion. A dye sensitizing one of two adjacent dye-sensitized solar cells, having a main body provided on the inner side, and a protruding part protruding from the main body to the outside of the sealing part and provided with the connection terminal The connection terminal in the solar cell and the metal substrate of the second electrode in the other dye-sensitized solar cell are connected via a conductive material, the connection terminal is connected to the conductive material, and the sealing portion Conductive material that extends along a certain direction on the outside A conductive material non-connecting portion extending along a certain direction from the conductive material connecting portion outside the sealing portion, and the width of the conductive material non-connecting portion is the width of the conductive material connecting portion. Narrower is preferred.

  When the dye-sensitized solar cell element is placed in an environment with a large temperature change, the wider the connection terminal provided on the protrusion of the transparent conductive film, the more the connection terminal peels from the protrusion of the transparent conductive film. It becomes easy. In that respect, in the dye-sensitized solar cell element of the present invention, the conductive material non-connection portion of the connection terminals has a narrower width than the conductive material connection portion connected to the conductive material. For this reason, a conductive material non-connection part among connection terminals becomes difficult to exfoliate from a projection part of a transparent conductive film. Therefore, even if the conductive material connecting portion is peeled off from the protruding portion of the transparent conductive film, the conductive material non-connecting portion is not peeled off from the protruding portion of the transparent conductive film, and the connection to the protruding portion can be maintained. Further, even when the conductive material connecting portion is separated from the protruding portion of the transparent conductive film, the dye-sensitized solar cell element can operate normally. Therefore, according to the dye-sensitized solar cell element of the present invention, connection reliability can be improved. In addition, the conductive material connected to the metal substrate of the second electrode in one dye-sensitized solar cell among the two adjacent dye-sensitized solar cells is connected to the conductive material on the protrusion in the other dye-sensitized solar cell. The conductive material connecting portion is provided outside the sealing portion on the protruding portion. That is, two adjacent dye-sensitized solar cells are connected to each other outside the sealing portion. For this reason, according to the dye-sensitized solar cell element of this invention, it becomes possible to improve an aperture ratio.

  In addition, as a result of intensive studies to achieve the second object, the present inventors have found that the second object can be achieved by the following invention.

  That is, the present invention includes a plurality of dye-sensitized solar cells, and the dye-sensitized solar cell includes a first electrode, a second electrode facing the first electrode, the first electrode, or the second electrode. An oxide semiconductor layer provided on the electrode, an annular sealing portion for joining the first electrode and the second electrode, and a space surrounded by the first electrode, the second electrode, and the sealing portion The transparent substrate is formed of a common transparent substrate of the plurality of dye-sensitized solar cells, and the second electrodes of two adjacent dye-sensitized solar cells are separated from each other. The sealing portion has an annular first sealing portion provided between the first electrode and the second electrode, and the first sealing of two adjacent dye-sensitized solar cells. Are integrated to form a first integrated sealing portion, and the first integrated sealing Has an annular part and a partition part for partitioning the opening in the annular part, and an adhesive part between the partition part of the first integrated sealing part and the surface on the first electrode side of the second electrode The width of the first integrated sealing portion is narrower than the width of the bonding portion between the second electrode and the surface on the first electrode side of the second electrode. It is a solar cell element.

  According to this dye-sensitized solar cell element, the width of the bonding portion between the partition portion of the first integrated sealing portion and the surface on the first electrode side of the second electrode is the annular shape of the first integrated sealing portion. It is narrower than the width of the bonded portion between the portion and the surface of the second electrode on the first electrode side. For this reason, the aperture ratio in a dye-sensitized solar cell element can be improved more fully. Moreover, in the dye-sensitized solar cell element of this invention, the 1st sealing part of two adjacent dye-sensitized solar cells is integrated, and the 1st integrated sealing part is comprised. Here, if the first sealing portions of the two adjacent dye-sensitized solar cells are not integrated, the first sealing portion exposed to the atmosphere between the adjacent dye-sensitized solar cells. There are two places. On the other hand, in the dye-sensitized solar cell element, the adjacent first sealing portions are integrated to form the first integrated sealing portion, and therefore, between the adjacent dye-sensitized solar cells. The first sealing portion exposed to the atmosphere is one place. That is, between the adjacent dye-sensitized solar cells, the sealing part exposed to the atmosphere is only one part of the partition part of the first integrated sealing part. Moreover, since the first sealing portions are integrated with each other, the penetration distance of moisture and the like from the atmosphere to the electrolyte is extended. For this reason, the quantity of the water | moisture content and air which penetrate | invade from the exterior of a dye-sensitized solar cell can be fully reduced between adjacent dye-sensitized solar cells. That is, the sealing ability of the dye-sensitized solar cell element can be sufficiently improved. Moreover, according to the dye-sensitized solar cell element, adjacent first sealing portions are integrated. For this reason, the width | variety of the adhesion part with the partition part of a 1st integrated sealing part and the surface by the side of a 1st electrode among 2nd electrodes is the 1st among the annular part of a 1st integrated sealing part, and a 2nd electrode. Even if it is narrower than the width of the bonding portion with the surface on the one electrode side, it is possible to ensure a sufficient sealing width in the partition portion. That is, according to the dye-sensitized solar cell element of the present invention, the adhesive strength between the first sealing portion and the first electrode and the adhesive strength between the first sealing portion and the second electrode are improved while improving the aperture ratio. It can be made sufficiently large. As a result, the aperture ratio can be improved, and when the dye-sensitized solar cell element is used at a high temperature, the electrolyte expands and an excessive stress is applied from the inside to the outside of the first sealing portion. However, peeling of the 1st sealing part from the 1st electrode and the 2nd electrode can fully be controlled, and it becomes possible to have outstanding durability.

  In the said dye-sensitized solar cell element, it is preferable that the width | variety of the said partition part is 100% or more and less than 200% of the width | variety of the said annular part.

  In this case, in the partition part of the first integrated sealing part, since the width of the partition part is 100% or more of the width of the annular part, the width of the partition part is less than 100% of the width of the annular part. Thus, the penetration distance of moisture and the like from the atmosphere to the electrolyte is further extended. For this reason, it can suppress more fully that a water | moisture content penetrate | invades from the exterior through the partition part between adjacent dye-sensitized solar cells. On the other hand, compared with the case where the width | variety of a partition part exceeds 200% of the width | variety of an annular part, an aperture ratio can be improved more.

  In the dye-sensitized solar cell element, the sealing portions of the plurality of dye-sensitized solar cells are provided so as to overlap the first sealing portion, and together with the first sealing portion, the second electrode It is preferable to further include an annular second sealing portion that sandwiches the edge portion, and the second sealing portion is integrated to form a second integrated sealing portion.

  In this case, even if a stress in a direction away from the first electrode acts on the second electrode, the separation is sufficiently suppressed by the second sealing portion or the second integrated sealing portion.

  In the dye-sensitized solar cell element, the width of the bonding portion between the partition portion of the first integrated sealing portion and the surface of the second electrode on the first electrode side is the first integrated seal. It is preferable that it is 25% or more and less than 100% of the width of the bonding portion between the annular portion of the stop portion and the surface of the second electrode on the first electrode side.

  In this case, in this case, it is possible to have more excellent durability as compared with the case where the width P of the bonded portion is less than 25% of the width Q of the bonded portion.

  In the present invention, “low illuminance” refers to illuminance of 10,000 lux or less.

  According to the present invention, a low-illuminance dye-sensitized solar cell element capable of saving space while having excellent photoelectric conversion characteristics is provided.

It is a cut surface end view showing a first embodiment of a dye-sensitized solar cell element of the present invention. It is a top view which shows a part of 1st Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows the pattern of the transparent conductive film in the dye-sensitized solar cell element of FIG. It is a top view which shows the 1st integrated sealing part of FIG. It is a top view which shows the 2nd integrated sealing part of FIG. FIG. 3 is a cross-sectional end view taken along line VI-VI in FIG. 2. It is a top view which shows the working electrode which formed the connection part for fixing a back seat | sheet. It is a top view which shows the 1st integrated sealing part formation body for forming the 1st integrated sealing part of FIG. It is a top view which shows a part of 2nd Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows a part of 3rd Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows a part of 4th Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows a part of 5th Embodiment of the dye-sensitized solar cell element of this invention.

  Hereinafter, a preferred embodiment of the dye-sensitized solar cell element of the present invention will be described in detail with reference to FIGS. FIG. 1 is a cross-sectional end view showing a first embodiment of the dye-sensitized solar cell element of the present invention, and FIG. 2 is a plan view showing a part of the first embodiment of the dye-sensitized solar cell element of the present invention. 3 is a plan view showing the pattern of the transparent conductive film in the dye-sensitized solar cell element of FIG. 1, FIG. 4 is a plan view showing the first integrated sealing portion of FIG. 1, and FIG. FIG. 6 is a cross-sectional end view taken along line VI-VI in FIG. 2.

  As shown in FIG. 1, a low-illuminance dye-sensitized solar cell module (hereinafter also referred to as “DSC module”) 100 as a dye-sensitized solar cell element includes a plurality of transparent substrates 11 (in FIG. 1). 4) a dye-sensitized solar cell (hereinafter may be referred to as “DSC”) 50, and a back sheet 80 provided so as to cover the DSC 50 on the one surface 11a side of the transparent substrate 11. An insulating connecting portion 14 is provided on the entire periphery of the peripheral edge portion 80 a of the backsheet 80. As shown in FIG. 2, the plurality of DSCs 50 are connected in series by a conductive material 60P. Hereinafter, for convenience of description, the four DSCs 50 in the DSC module 100 may be referred to as DSCs 50A to 50D.

  As shown in FIG. 1, each of the plurality of DSCs 50 includes a working electrode 10, a counter electrode 20 that faces the working electrode 10, and an annular sealing portion 30 </ b> A that joins the working electrode 10 and the counter electrode 20. A cell space formed by the working electrode 10, the counter electrode 20, and the annular sealing portion 30A is filled with an electrolyte 40.

  The counter electrode 20 includes a metal substrate 21 and a catalyst layer 22 provided on the working electrode 10 side of the metal substrate 21 to promote a catalytic reaction. In two adjacent DSCs 50, the counter electrodes 20 are separated from each other. In the present embodiment, the second electrode is constituted by the counter electrode 20.

  As shown in FIGS. 1 and 2, the working electrode 10 includes a transparent substrate 11, a transparent conductive film 12 provided on one surface 11 a of the transparent substrate 11, and an insulating material 33 provided on the one surface 11 a of the transparent substrate 11. It has a conductive substrate 15, at least one oxide semiconductor layer 13 provided on the transparent conductive film 12 of the transparent conductive substrate 15, and a connection terminal 16 provided on the transparent conductive film 12. The oxide semiconductor layer 13 is disposed inside the annular sealing portion 30A. The transparent substrate 11 is used as a common transparent substrate for the DSCs 50A to 50D. In the present embodiment, the first electrode is configured by the transparent conductive substrate 15.

  As shown in FIGS. 2 and 3, the transparent conductive film 12 is composed of transparent conductive films 12 </ b> A to 12 </ b> F that are provided in an insulated state. That is, the transparent conductive films 12A to 12F are arranged with the groove 90 interposed therebetween. Here, the transparent conductive films 12A to 12D constitute the plurality of DSCs 50A to 50D, respectively. The transparent conductive film 12E is arranged so as to be bent along the sealing portion 30A. The transparent conductive film 12F is an annular transparent electrode film 12 for fixing the peripheral edge portion 80a of the back sheet 80, and constitutes a separation portion (see FIG. 2).

  As shown in FIG. 3, each of the transparent conductive films 12A to 12D includes a rectangular main body portion 12a having a side edge portion 12b, and a protruding portion 12c protruding sideways from the side edge portion 12b of the main body portion 12a. Have.

  As shown in FIG. 2, the protruding portion 12c of the transparent conductive film 12C among the transparent conductive films 12A to 12D extends from the protruding portion 12d and the protruding portion 12d that protrude laterally with respect to the arrangement direction X of the DSCs 50A to 50D. And a counter part 12e facing the main body part 12a of the adjacent DSC 50D via the groove 90.

  Also in the DSC 50B, the protruding portion 12c of the transparent conductive film 12B has a protruding portion 12d and a facing portion 12e. Also in the DSC 50A, the protruding portion 12c of the transparent conductive film 12A has a protruding portion 12d and a facing portion 12e.

  The DSC 50D is already connected to the DSC 50C, and there is no other DSC 50 to be connected. For this reason, in the DSC 50D, the protruding portion 12c of the transparent conductive film 12D does not have the facing portion 12e. That is, the protruding portion 12c of the transparent conductive film 12D is configured only by the overhang portion 12d.

  However, the transparent conductive film 12D connects the first current extraction part 12f for extracting the current generated in the DSC module 100 to the outside, the first current extraction part 12f, and the main body part 12a, and the transparent conductive films 12A to 12C. And a first connecting portion 12g extending along the side edge portion 12b. The first current extraction portion 12f is disposed around the DSC 50A and on the opposite side of the transparent conductive film 12B with respect to the transparent conductive film 12A.

  On the other hand, the transparent conductive film 12E also has a second current extraction portion 12h for extracting the current generated in the DSC module 100 to the outside. The second current extraction portion 12h is around the DSC 50A and is formed of a transparent conductive film. It is arranged on the opposite side to the transparent conductive film 12B with respect to 12A. The transparent conductive film 12E further includes a second connection portion 12i that connects the second current extraction portion 12h and the metal substrate 21 of the counter electrode 20 of the DSC 50A. In the present embodiment, the second connection portion 12i is disposed in an L shape between the annular coupling portion 14 and the main body portion 12a of the transparent conductive film 12A of the DSC 50A. The first current extraction portion 12f and the second current extraction portion 12h are arranged adjacent to each other through the groove 90 around the DSC 50A. Here, the groove 90 is formed along the edge of the first groove 90A formed along the outer shape of the annular sealing portion 30A and the portion of the transparent conductive film 12 excluding the main body portion 12a. The second groove 90 </ b> B intersects with the peripheral edge 80 a of the sheet 80. Since the first groove 90 </ b> A is formed along the outer shape of the annular sealing portion 30 </ b> A, in addition to the groove formed along the edge of the main body portion 12 a of the transparent conductive film 12, A groove formed along the edge of the portion excluding the main body 12a is also included. When the DSC module 100 has the back sheet 80, the first groove 90A is a groove formed inside the inner peripheral edge of the annular connecting portion 14, and the second groove 90B is an annular connecting part. The groove formed outside the inner peripheral edge of the portion 14 is said. The transparent conductive film 12F described above forms an annular structure together with the first current extraction portion 12f and the second current extraction portion 12h.

  Moreover, the connection terminal 16 is provided on each protrusion part 12c and transparent conductive film 12E of transparent conductive film 12A-12C. In the present embodiment, in the transparent conductive films 12A to 12C, at least the conductive material connection portion 16A among the connection terminals 16 is provided on the facing portion 12e of the protruding portion 12c, and the main body portion of the adjacent DSC 50 to be connected. 12a. In the transparent conductive film 12E, the conductive material connection portion 16A of the connection terminals 16 faces the main body portion 12a of the adjacent DSC 50A to be connected. Each connection terminal 16 is connected to the conductive material 60P and is connected to the conductive material connection portion 16A extending along the sealing portion 30A outside the sealing portion 30A, and is not connected to the conductive material 60P, and is sealed from the conductive material connection portion 16A. A conductive material non-connecting portion 16B extending along the sealing portion 30A outside the stop portion 30A. The width of the conductive material non-connecting portion 16B is narrower than the width of the conductive material connecting portion 16A. Here, the widths of the conductive material connecting portion 16A and the conductive material non-connecting portion 16B are constant. Note that the width of the conductive material connecting portion 16A is the length in the direction orthogonal to the extending direction of the conductive material connecting portion 16A and means the narrowest width among the widths of the conductive material connecting portion 16A. The width of the portion 16B is the length in a direction orthogonal to the extending direction of the conductive material non-connecting portion 16B and means the narrowest width among the widths of the conductive material non-connecting portion 16B.

  The conductive material connecting portion 16A of the connection terminal 16 provided on the protruding portion 12c of the transparent conductive film 12C in the DSC 50C and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50D are connected via the conductive material 60P. The conductive material 60P is disposed so as to pass over the sealing portion 30A. Similarly, the conductive material connection portion 16A of the connection terminal 16 in the DSC 50B and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50C are connected via the conductive material 60P, and adjacent to the conductive material connection portion 16A of the connection terminal 16 in the DSC 50A. The metal substrate 21 of the counter electrode 20 in the DSC 50B is connected via a conductive material 60P. Further, the conductive material connecting portion 16A of the connection terminal 16 on the transparent conductive film 12E and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50A are connected via a conductive material 60P. That is, the second connection portion 12i of the transparent conductive film 12E and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50A are connected via the connection terminal 16 and the conductive material 60P.

  External connection terminals 18a and 18b are provided on the first current extraction portion 12f and the second current extraction portion 12h, respectively.

  As shown in FIG. 1, the sealing part 30A is provided so as to overlap the first sealing part 31A and the annular first sealing part 31A provided between the transparent conductive substrate 15 and the counter electrode 20, It has the 2nd sealing part 32A which clamps the edge 20a of the counter electrode 20 with 31 A of 1st sealing parts. As shown in FIG. 4, adjacent first sealing portions 31 </ b> A are integrated to form a first integrated sealing portion 31. In other words, the first integrated sealing portion 31 includes an annular portion (hereinafter referred to as “annular portion”) 31 a that is not provided between two adjacent counter electrodes 20 and two adjacent counter electrodes 20. A portion (hereinafter referred to as a “partition portion”) 31 b that is provided between them and partitions the inner opening 31 c of the annular portion 31 a. Further, as shown in FIG. 5, the second sealing portions 32 </ b> A are integrated between the adjacent counter electrodes 20 to constitute a second integrated sealing portion 32. The second integrated sealing portion 32 is provided between an annular portion (hereinafter referred to as “annular portion”) 32 a that is not provided between two adjacent counter electrodes 20 and two adjacent counter electrodes 20. And a portion (hereinafter referred to as “partition portion”) 32b that partitions the inner opening 32c of the annular portion 32a.

  Further, as shown in FIG. 1, a glass is interposed between the first sealing portion 31 </ b> A and the groove 90 so as to enter the groove 90 between the adjacent transparent conductive films 12 </ b> A to 12 </ b> F and straddle the adjacent transparent conductive film 12. An insulating material 33 made of frit is provided. More specifically, the insulating material 33 enters the first groove 90A formed along the edge of the main body 12a of the transparent conductive film 12 in the groove 90, and the main body forming the first groove 90A. The edge of the part 12 is also covered. However, in the present embodiment, the groove formed along the edge of the first groove 90 </ b> A excluding the main body 12 a of the transparent conductive film 12 is not covered with the insulating material 33.

  As shown in FIG. 6, the width P of the bonding portion between the surface of the counter electrode 20 on the transparent conductive substrate 15 side and the partition portion 31 b of the first integrated sealing portion 31 is the transparent conductive substrate 15 of the counter electrode 20. It is narrower than the width Q of the bonding portion between the side surface and the annular portion 31 a of the first integrated sealing portion 31. Furthermore, the width R of the partition part 31 b of the first integrated sealing part 31 is 100% or more and less than 200% of the width T of the annular part 31 a of the first integrated sealing part 31.

  The second integrated sealing portion 32 includes a main body portion 32 d provided on the opposite side of the counter electrode 20 from the working electrode 10, and an adhesive portion 32 e provided between the adjacent counter electrodes 20. The second integrated sealing portion 32 is bonded to the first integrated sealing portion 31 by an adhesive portion 32e.

  As shown in FIG. 1, a back sheet 80 is provided on the transparent conductive substrate 15. The backsheet 80 includes a laminate 80A including a weather resistant layer and a metal layer, and an adhesive portion that is provided on the opposite side of the laminate 80A from the metal layer and adheres to the transparent conductive substrate 15 via the connecting portion 14. 80B. Here, the bonding portion 80B is for bonding the back sheet 80 to the transparent conductive substrate 15, and as long as it is formed on the peripheral portion of the stacked body 80A as shown in FIG. However, the bonding portion 80B may be provided on the entire surface on the DSC 50 side of the stacked body 80A. The peripheral edge portion 80a of the back sheet 80 is connected to the transparent conductive films 12D, 12E, and 12F of the transparent conductive film 12 through the connecting portion 14 by the bonding portion 80B. Here, the bonding portion 80B is separated from the sealing portion 30A of the DSC 50. The connecting portion 14 is also separated from the sealing portion 30A. Furthermore, the second connection portion 12 i of the transparent conductive film 12 </ b> E is disposed inside the annular coupling portion 14. In addition, the transparent conductive film 12F connects the transparent substrate 11 and the connecting portion 14, surrounds the transparent conductive films 12A to 12D of the DSC 50, and is formed between the transparent conductive films 12A to 12D with a groove 90 (gap). Provided to form part. Here, the first groove 90 </ b> A, which is a part of the groove 90, is disposed inside the inner peripheral edge of the annular connecting portion 14, and the second groove 90 </ b> B is disposed outside the inner peripheral edge of the annular connecting portion 14. Has been. The space inside the back sheet 80 and outside the sealing portion 30A is not filled with the electrolyte 40.

  In the transparent conductive film 12D, the first current collection wiring 17 having a lower resistance than the transparent conductive film 12D extends so as to pass through the main body portion 12a, the first connection portion 12g, and the current extraction portion 12f. The first current collecting wiring 17 is arranged so as not to intersect the connecting portion 14 between the back sheet 80 and the transparent conductive substrate 15. In other words, the first current collecting wiring 17 is disposed on the inner side than the connecting portion 14.

  As shown in FIG. 2, bypass diodes 70A to 70D are connected in parallel to the DSCs 50A to 50D, respectively. Specifically, the bypass diode 70A is fixed on the partition part 32b of the second integrated sealing part 32 between the DSC 50A and the DSC 50B, and the bypass diode 70B is a second integrated between the DSC 50B and the DSC 50C. The bypass diode 70C is fixed on the partition part 32b of the second integrated sealing part 32 between the DSC 50C and the DSC 50D. The bypass diode 70D is fixed on the sealing portion 30A of the DSC 50D. A conductive material 60Q is fixed to the metal substrate 21 of the counter electrode 20 so as to pass through the bypass diodes 70A to 70D. The conductive material 60P branches from the conductive material 60Q between the bypass diodes 70A and 70B, between the bypass diodes 70B and 70C, and between the bypass diodes 70C and 70D, and the conductive material connecting portion 16A on the transparent conductive film 12A, the transparent conductive film The conductive material connecting portion 16A on 12B and the conductive material connecting portion 16A on the transparent conductive film 12C are connected to each other. A conductive material 60P is also fixed to the metal substrate 21 of the counter electrode 20 of the DSC 50A, and the conductive material 60P connects the bypass diode 70A and the conductive material connection portion 16A of the connection terminal 16 on the transparent conductive film 12E. . Further, the bypass diode 70D is connected to the transparent conductive film 12D through the conductive material 60P.

  Further, as shown in FIG. 1, a desiccant 95 is provided on the counter electrode 20 of each DSC 50.

  According to the DSC module 100, the groove 90 is formed along the edge of the transparent conductive film 12, and the groove 90 is formed on the main body portion 12a of the transparent conductive film 12 disposed inside the annular sealing portion 30A. It has the 1st groove | channel 90A formed along an edge. The insulating material 33 made of glass frit enters the first groove 90A, and the insulating material 33 also covers the edge of the main body portion 12a forming the first groove 90A. For this reason, even if a crack is formed along the groove 90 in the transparent substrate 11 and below the groove 90, and the crack is connected to the edge of the main body 12 a, the crack is sealed. Intrusion of moisture from the outside of the stop 30A is sufficiently suppressed by the insulating material 33. In particular, in the DSC module 100, since the insulating material 33 that covers the edge of the main body portion 12a that forms the first groove 90A and enters the first groove 90A is made of glass frit, the insulating material 33 is made of resin. Compared to high sealing performance. For this reason, the DSC module 100 can have excellent durability.

  In the DSC module 100, the sealing portion 30A and the insulating material 33 are arranged so as to overlap each other. For this reason, compared with the case where the insulating material 33 is arrange | positioned so that it may not overlap with 30 A of sealing parts, the area of the part which contributes to electric power generation seen from the light-receiving surface side of the DSC module 100 can be increased more. . For this reason, an aperture ratio can be improved more.

  In the DSC module 100, the first current extraction unit 12f and the second current extraction unit 12h are disposed around the DSC 50A and on the opposite side of the transparent conductive film 12B from the transparent conductive film 12A. The first current extraction portion 12f and the second current extraction portion 12h of the transparent conductive film 12E are arranged adjacent to each other via the groove 90. Therefore, in the DSC module 100, the external connection terminals 18a and 18b can be arranged adjacent to each of the first current extraction unit 12f and the second current extraction unit 12h. Therefore, the number of connectors for taking out current from the external connection terminals 18a and 18b to the outside can be reduced to one. That is, if the first current extraction part 12f is arranged on the opposite side of the transparent conductive film 12c with respect to the transparent conductive film 12D, the first current extraction part 12f and the second current extraction part 12h are arranged greatly apart from each other. Therefore, the external connection terminals 18a and 18b are also arranged far apart. In this case, in order to take out the current from the DSC module 100, two connectors are required: a connector connected to the external connection terminal 18a and a connector connected to the external connection terminal 18b. However, according to the DSC module 100, since the external connection terminals 18a and 18b can be arranged adjacent to each other, only one connector is required. For this reason, according to the DSC module 100, space saving can be achieved. Further, when the DSC module 100 is used under low illuminance, the generated current is small. Specifically, the generated current is 2 mA or less. Therefore, the second current in which a part of the transparent conductive film 12D of the DSC 50D at one end of the DSCs 50A and 50D at both ends of the DSCs 50A to 50D is electrically connected to the metal substrate 21 of the counter electrode 20 of the DSC 50A at the other end. Even if it arrange | positions as the 1st electric current extraction part 12f via the groove | channel 90 next to the extraction part 12h, the fall of the photoelectric conversion performance of the DSC module 100 can fully be suppressed.

  In the DSC module 100, the DSCs 50A to 50D are arranged in a line along the X direction, and the DSC 50A and 50D at both ends of the DSCs 50A to 50D include the transparent conductive film 12D of the DSC 50D at one end of the sealing portion 30A. It has a main body part 12a provided on the inner side, a first current extraction part 12f, and a first connection part 12g for connecting the main body part 12a and the first current extraction part 12f. Therefore, DSC 50A and DSC 50D, which are a part of DSCs 50A to 50D, are folded back halfway, and DSC 50A is used to connect two adjacent DSCs 50 to each other as compared to the case where DSC 50A and DSC 50D are arranged adjacent to each other. It becomes possible to further shorten the installation area of the connection terminals 16 provided along the arrangement direction (X direction in FIG. 2) of ˜50D, and to further reduce the space. Also, according to the DSC module 100, when the DSC module 100 is used in a low illumination environment, the generated current is usually small, so the DSC module 100 connects the main body portion 12a and the first current extraction portion 12f. Even if it has the 1st connection part 12g to perform, the fall of a photoelectric conversion characteristic can fully be suppressed.

  Further, in the DSC module 100, the first current collecting wiring 17 is disposed so as not to intersect the connecting portion 14 between the back sheet 80 and the transparent conductive substrate 15. The current collecting wiring is generally porous and has air permeability, and gas such as water vapor is permeable to the first current collecting wiring 17. The first current collecting wiring 17 is connected to the back sheet 80, the transparent conductive substrate 15, and the like. If it is arranged so as not to cross the connecting portion 14, it is possible to prevent water vapor or the like from entering the space between the back sheet 80 and the transparent conductive substrate 15 through the first current collecting wiring 17 from the outside. it can. As a result, the DSC module 100 can have excellent durability. Moreover, since the 1st current collection wiring 17 has resistance lower than transparent conductive film 12D, even if a generated current becomes large, the fall of a photoelectric conversion characteristic can fully be suppressed.

  Furthermore, when the DSC module 100 is placed in an environment where the temperature change is large, the connection terminal 16 is less likely to be peeled off from the protruding portion 12 c of the transparent conductive film 12 as the connection terminal 16 is narrower. In that respect, in the DSC module 100, the conductive material non-connecting portion 16B of the connection terminals 16 has a narrower width than the conductive material connecting portion 16A connected to the conductive material 60P. For this reason, the conductive material non-connecting portion 16 </ b> B of the connection terminal 16 is difficult to peel off from the protruding portion 12 c of the transparent conductive film 12. Therefore, even if the conductive material connecting portion 16A is peeled off from the protruding portion 12c of the transparent conductive film 12, the conductive material non-connecting portion 16B is not peeled off from the transparent conductive film 12 and can maintain the connection to the transparent conductive film 12. It becomes. Even if the conductive material connecting portion 16A is peeled off from the protruding portion 12c of the transparent conductive film 12, the DSC module 100 can operate normally. Therefore, according to the DSC module 100, connection reliability can be improved. In addition, the conductive material 60P connected to the metal substrate 21 of the counter electrode 20 in one of the two adjacent DSCs 50 is connected to the conductive material connection portion 16A on the protruding portion 12c in the other DSC 50, and the conductive material connection portion. 16A is provided outside the sealing portion 30A on the protruding portion 12c. That is, two adjacent DSCs 50 are connected to each other outside the sealing portion 30A. For this reason, according to the DSC module 100, it is possible to improve the aperture ratio.

  Further, in the DSC module 100, in the DSC 50 connected to the adjacent DSC 50 among the DSCs 50A to 50D, the projecting portion 12c extends from the main body portion 12a to the side and extends from the protruding portion 12d to the adjacent DSC 50. Of the connection terminal 16 and at least the conductive material connection portion 16A is provided on the facing portion 12e.

  In this case, since at least the conductive material connection portion 16A of the connection terminals 16 is provided on the facing portion 12e facing the main body portion 12a of the adjacent DSC 50, at least the conductive material connection portion 16A of the connection terminals 16 is Unlike the case where it is not provided on the facing portion 12e facing the main body portion 12a of the adjacent DSC 50, the conductive material 60P connected to the conductive material connecting portion 16A crosses the metal substrate 21 of the counter electrode 20 of the adjacent DSC 50. Can be sufficiently prevented. As a result, it is possible to sufficiently prevent a short circuit between adjacent DSCs 50.

  In the DSC module 100, the conductive material connecting portion 16A and the conductive material non-connecting portion 16B are both arranged along the sealing portion 30A. For this reason, compared with the case where the electrically conductive material connection part 16A and the electrically conductive material non-connection part 16B are arranged along the direction away from the sealing part 30A, the space required for the connection terminal 16 can be omitted.

  Furthermore, in the DSC module 100, the adhesive portion 80B of the back sheet 80 is separated from the sealing portion 30A of the DSC 50. For this reason, it is sufficiently suppressed that the adhesive portion 80B contracts at a low temperature to pull the sealing portion 30A and an excessive stress is applied to the interface between the sealing portion 30A and the transparent conductive substrate 15 or the counter electrode 20. Is done. In addition, even when the temperature is high, the adhesive portion 80B sufficiently expands and pushes the sealing portion 30A to apply an excessive stress to the interface between the sealing portion 30A and the transparent conductive substrate 15 or the counter electrode 20. Is done. That is, excessive stress is sufficiently suppressed from being applied to the interface between the sealing portion 30 </ b> A and the transparent conductive substrate 15 or the counter electrode 20 at both high and low temperatures. For this reason, the DSC module 100 can have excellent durability.

  Further, in the DSC module 100, the width P of the bonding portion between the surface of the counter electrode 20 on the transparent conductive substrate 15 side and the partition portion 31 b of the first integrated sealing portion 31 is the transparent conductive substrate 15 of the counter electrode 20. It is narrower than the width Q of the bonding portion between the side surface and the annular portion 31 a of the first integrated sealing portion 31. For this reason, the aperture ratio in the DSC module 100 can be improved more sufficiently. In the DSC module 100, the adjacent first sealing portions 31 </ b> A and the adjacent second sealing portions 32 </ b> A are integrated between the adjacent counter electrodes 20. Here, if the adjacent first sealing portions 31 </ b> A are not integrated, two adjacent sealing portions are exposed to the atmosphere between the adjacent DSCs 50. On the other hand, in the DSC module 100, since the adjacent first sealing portions 31A are integrated, there is one sealing portion exposed to the atmosphere between the adjacent DSCs 50. That is, since the 1st integrated sealing part 31 is comprised by the annular part 31a and the partition part 31b, the sealing part exposed with respect to air | atmosphere between adjacent DSC50 is the partition part 31b. There is only one place. Further, since the first sealing portions 31A are integrated with each other, the penetration distance of moisture and the like from the atmosphere to the electrolyte 40 is extended. For this reason, it is possible to sufficiently reduce the amount of moisture and air entering from the outside of the DSC 50 between the adjacent DSCs 50. That is, the sealing ability of the DSC module 100 can be sufficiently improved. Further, according to the DSC module 100, the adjacent first sealing portions 31A are integrated. Therefore, the width P of the bonding portion between the surface of the counter electrode 20 on the transparent conductive substrate 15 side and the partition portion 31b of the first integrated sealing portion 31 is the same as the surface of the counter electrode 20 on the transparent conductive substrate 15 side. Even if it is narrower than the width Q of the bonding portion between the first integrated sealing portion 31 and the annular portion 31a, a sufficient sealing width can be secured in the partition portion 31b. That is, according to the DSC module 100, the adhesive strength between the first sealing portion 31A and the transparent conductive substrate 15 and the adhesive strength between the first sealing portion 31A and the counter electrode 20 are sufficiently increased while improving the aperture ratio. It is possible to make it larger. As a result, the aperture ratio can be improved, and when the DSC module 100 is used at a high temperature, the electrolyte 40 expands and an excessive stress is applied from the inside to the outside of the first sealing portion 31A. In addition, peeling of the first sealing portion 31A from the transparent conductive substrate 15 and the counter electrode 20 can be sufficiently suppressed, and excellent durability can be achieved.

  Furthermore, in the DSC module 100, the width R of the counter electrode 20 and the partition portion 31b of the first integrated sealing portion 31 is 100% or more and less than 200% of the width T of the annular portion 31a of the first integrated sealing portion 31. It has become. In this case, in the partition part 31b of the first integrated sealing part 31, the width of the partition part 31b is 100% or more of the width T of the annular part 31a. In comparison with the case where the width R of the partition portion 31b is less than 100% of the width T of the annular portion 31a, the penetration distance of moisture and the like from the atmosphere to the electrolyte 40 is further extended. For this reason, it can suppress more fully that a water | moisture content penetrate | invades from the exterior through the partition part 31b between adjacent DSC50. On the other hand, compared with the case where the width R of the partition part 31b exceeds 200% of the width T of the annular part 31a, the aperture ratio can be further improved.

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

  Next, the working electrode 10, the connecting portion 14, the photosensitizing dye, the counter electrode 20, the sealing portion 30A, the electrolyte 40, the conductive materials 60P and 60Q, the back sheet 80, and the desiccant 95 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), and polyethersulfone (PES). The thickness of the transparent substrate 11 is appropriately determined according to the size of the DSC module 100 and is not particularly limited, but may be in the range of 50 to 10,000 μm, for example.

Examples of materials included in 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 containing different conductive metal oxides. When the transparent conductive film 12 is composed of a single layer, the transparent conductive film 12 preferably includes FTO because it has high heat resistance and chemical resistance. The transparent conductive film 12 may further include glass frit. The thickness of the transparent conductive film 12 may be in the range of 0.01 to 2 μm, for example.

Further, the resistance value of the first connection portion 12g of the transparent conductive film 12D among the transparent conductive film 12 is not particularly limited, but is preferably equal to or less than the resistance value represented by the following formula (1).
Resistance value = number of DSCs 50 connected in series × 120Ω (1)

  In this case, compared with the case where the resistance value of the 1st connection part 12g exceeds the resistance value represented by said Formula (1), the performance fall of the DSC module 100 can fully be suppressed. In the present embodiment, since the number of DSCs 50 is 4, the resistance value represented by the above formula (1) is 480Ω, and therefore the resistance value of the first connection portion 12g is preferably 480Ω or less.

  The thickness of the insulating material 33 is 10-30 micrometers normally, Preferably it is 15-25 micrometers.

  The connection terminal 16 includes a metal material. Examples of the metal material include silver, copper, and indium. You may use these individually or in combination of 2 or more types.

  Moreover, although the connection terminal 16 may be comprised with the material same as the electrically conductive material 60P, or may be comprised with a different material, it is preferable that it is comprised with the same material.

  In this case, since the connection terminal 16 and the conductive material 60P are made of the same material, the adhesion between the connection terminal 16 and the conductive material 60P can be more sufficiently improved. For this reason, the connection reliability in the DSC module 100 can be further improved.

  In the connection terminal 16, the width of the conductive material non-connecting portion 16B is not particularly limited as long as it is smaller than the width of the conductive material connecting portion 16A, but is preferably 1/2 or less of the width of the conductive material connecting portion 16A.

  In this case, the connection reliability in the DSC module 100 can be further improved as compared with the case where the width of the conductive material non-connecting portion 16B exceeds 1/2 of the width of the conductive material connecting portion 16A.

  The width of the conductive material connecting portion 16A is not particularly limited, but is preferably 0.5 to 5 mm, and more preferably 0.8 to 2 mm.

  The connection terminal 16 provided on the 2nd connection part 12i contained in the transparent conductive film 12E among the connection terminals 16 may have resistance lower than the transparent conductive film 12E. In this case, the connection terminal 16 provided on the second connection portion 12i functions as the second current collecting wiring. In this case, since the second current collection wiring has a lower resistance than the second connection portion 12i, it is possible to sufficiently suppress a decrease in photoelectric conversion characteristics even when the generated current is increased. Further, the connection terminals 16 are arranged so as not to intersect with the peripheral edge portion 80 a of the back sheet 80. That is, the second current collecting wiring is arranged so as not to intersect with the peripheral edge 80 a of the backsheet 80. In this case, the current collecting wiring is generally porous and has air permeability, and gas such as water vapor is permeable, and the second current collecting wiring is connected to the peripheral portion 80a of the back sheet 80. If it arrange | positions so that it may not cross | intersect, it can prevent that water vapor | steam etc. penetrate | invade from the exterior into the space inside the back seat | sheet 80 through the 2nd current collection wiring. As a result, the DSC module 100 can have excellent durability.

The oxide semiconductor layer 13 is composed of oxide semiconductor particles. Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), and 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 ) , 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 oxide semiconductor layer 13 is usually composed of an absorption layer for absorbing light, but may be composed of an absorption layer and a reflective layer that reflects light transmitted through the absorption layer and returns it to the absorption layer.

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

(Connecting part)
The material constituting the connecting portion 14 is not particularly limited as long as the back sheet 80 and the transparent conductive film 12 can be bonded. Examples of the material constituting the connecting portion 14 include a glass frit and a sealing portion. A resin material similar to the resin material used for 31A can be used. Especially, it is preferable that the connection part 14 is a glass frit. Since the glass frit has a higher sealing ability than the resin material, it is possible to effectively suppress intrusion of moisture and the like from the outside of the back sheet 80.

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

  The metal substrate 21 is made of a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, and stainless steel. The thickness of the metal substrate 21 is appropriately determined according to the size of the DSC module 100 and is not particularly limited, but may be, for example, 0.005 to 0.1 mm.

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

(Sealing part)
The sealing unit 30A includes a first sealing unit 31A and a second sealing unit 32A.

  Examples of the material constituting the first sealing portion 31A include a modified polyolefin resin containing, for example, an ionomer, an ethylene-vinyl acetic anhydride copolymer, an ethylene-methacrylic acid copolymer, an ethylene-vinyl alcohol copolymer, and ultraviolet curing. Examples thereof include resins and resins such as vinyl alcohol polymers.

  The thickness of 31A of 1st sealing parts is 40-90 micrometers normally, Preferably it is 60-80 micrometers.

  The width P of the bonded portion between the counter electrode 20 and the partition portion 31b is preferably 25% or more and less than 100% of the width Q of the bonded portion between the counter electrode 20 and the annular portion 31a of the first integrated sealing portion 31. In this case, compared with the case where the width | variety P of an adhesion part is less than 25% of the width | variety Q of an adhesion part, it becomes possible to have more outstanding durability. The width P of the bonding portion is more preferably 30% or more of the width Q of the bonding portion, and further preferably 40% or more.

  In the DSC module 100, the width R of the partition part 31b of the first integrated sealing part 31 is preferably 100% or more and less than 200% of the width T of the annular part 31a of the first integrated sealing part 31. 120 to 180% is more preferable.

  In this case, a large aperture ratio and excellent durability can be balanced.

  As the material constituting the second sealing portion 32A, for example, an ionomer, an ethylene-vinyl acetic anhydride copolymer, an ethylene-methacrylic acid copolymer, an ethylene-vinyl alcohol copolymer, as in the first sealing portion 31A. Examples thereof include resins such as modified polyolefin resins, UV curable resins, and vinyl alcohol polymers.

  The thickness of the second sealing portion 32A is usually 20 to 45 μm, preferably 30 to 40 μm.

(Electrolytes)
The electrolyte 40 contains a redox couple 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 redox pairs such as bromine / bromide ions, zinc complexes, iron complexes, and cobalt complexes. The electrolyte 40 may use 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 room temperature molten salts include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, dimethylimidazolium iodide, ethylmethylimidazolium iodide, and dimethylpropyl. Imidazolium iodide, butylmethylimidazolium iodide, or methylpropyl 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.

The electrolyte 40 includes an oxidation-reduction pair consisting of I ⁻ / I ₃ ^—, and the concentration of I ₃ ⁻ is preferably 0.006 mol / liter or less, and is 0 to 6 × 10 ⁻⁶ mol / liter. More preferably, it is more preferably 0-6 × 10 ⁻⁸ mol / liter. In this case, since the concentration of I ₃ ⁻ carrying electrons is low, the leakage current can be further reduced. For this reason, since an open circuit voltage can be increased more, a photoelectric conversion characteristic can be improved more.

(Conductive material)
For example, metal films are used as the conductive materials 60P and 60Q. As a metal material constituting the metal film, for example, silver or copper can be used.

(Back sheet)
As described above, the back sheet 80 is provided on the surface of the laminate 80A including the weather resistant layer and the metal layer, and the DSC 50 side of the laminate 80A, and bonds the laminate 80A and the connecting portion 14 together. 80B.

  The weather resistant layer may be made of, for example, polyethylene terephthalate or polybutylene terephthalate.

  The thickness of the weather resistant layer may be, for example, 50 to 300 μm.

  The metal layer should just be comprised with the metal material containing aluminum, for example. The metal material is usually composed of aluminum alone, but may be an alloy of aluminum and another metal. Examples of other metals include copper, manganese, zinc, magnesium, lead, and bismuth. Specifically, 1000 series aluminum obtained by adding a trace amount of other metals to 98% or more pure aluminum is desirable. This is because the 1000 series aluminum is cheaper and more workable than other aluminum alloys.

  Although the thickness of a metal layer is not specifically limited, For example, what is necessary is just 12-30 micrometers.

  The stacked body 80A may further include a resin layer. Examples of the material constituting the resin layer include butyl rubber, nitrile rubber, thermoplastic resin, and the like. These can be used alone or in combination of two or more. The resin layer may be formed on the entire surface of the metal layer opposite to the weather-resistant layer, or may be formed only on the peripheral edge.

  Examples of the material constituting the bonding portion 80B include butyl rubber, nitrile rubber, and thermoplastic resin. These can be used alone or in combination of two or more. The thickness of the bonding portion 80B is not particularly limited, but may be, for example, 300 to 1000 μm.

(desiccant)
The desiccant 95 may be a sheet or a granule. The desiccant 95 only needs to absorb moisture, for example, and examples of the desiccant 95 include silica gel, alumina, and zeolite.

  Next, a method for manufacturing the DSC module 100 will be described with reference to FIGS. 7 is a plan view showing a working electrode in which a connecting portion for fixing the backsheet is formed, and FIG. 8 is a first integrated sealing portion formation for forming the first integrated sealing portion of FIG. It is a top view which shows a body.

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

The transparent conductive film can be formed by sputtering, vapor deposition, or spray pyrolysis (SPD: Spray Pyrolysis).
Deposition) or a CVD method is used.

  Next, as shown in FIG. 3, grooves 90 are formed in the transparent conductive film, and transparent conductive films 12 </ b> A to 12 </ b> F that are disposed in an insulating state with the grooves 90 interposed therebetween are formed. Specifically, the four transparent conductive films 12A to 12D corresponding to the DSCs 50A to 50D are formed so as to have a rectangular main body 12a and a protrusion 12c. At this time, for the transparent conductive films 12A to 12C corresponding to the DSCs 50A to 50C, the protruding part 12c extends not only from the overhanging part 12d but also from the overhanging part 12d, and the opposing part 12e facing the main body part 12a of the adjacent DSC 50 is provided. It is formed so that it also has. Regarding the transparent conductive film 12D, not only the rectangular main body 12a and the overhanging portion 12d, but also the first current extraction portion 12f, the first connection portion 12g that connects the first current extraction portion 12f and the main body portion 12a, and It forms so that it may have. At this time, the first current extraction portion 12f is formed to be disposed on the opposite side of the transparent conductive film 12B with respect to the transparent conductive film 12A. Further, the transparent conductive film 12E is formed so that the second current extraction portion 12h and the second connection portion 12i are formed. At this time, the second current extraction portion 12h is disposed on the opposite side of the transparent conductive film 12A with respect to the transparent conductive film 12A, and is disposed adjacent to the first current extraction portion 12f via the groove 90. Form.

The groove 90 can be formed by a laser scribing method using, for example, a YAG laser or a CO ₂ laser as a light source.

  Thus, a transparent conductive substrate 15 formed by forming the transparent conductive film 12 on the transparent substrate 11 is obtained.

  Next, a precursor of the connection terminal 16 composed of the conductive material connection portion 16A and the conductive material non-connection portion 16B is formed on the protruding portion 12c of the transparent conductive films 12A to 12C. Specifically, the precursor of the connection terminal 16 is formed so that the conductive material connection portion 16A is provided on the facing portion 12e. Also, the precursor of the connection terminal 16 is formed on the transparent conductive film 12E. The precursor of the conductive material non-connecting portion 16B is formed to be narrower than the width of the conductive material connecting portion 16A. The precursor of the connection terminal 16 can be formed, for example, by applying a silver paste and drying it.

  Furthermore, the precursor of the 1st current collection wiring 17 is formed on the 1st connection part 12g of transparent conductive film 12D. The precursor of the 1st current collection wiring 17 can be formed by apply | coating a silver paste and drying, for example.

  Also, precursors for external connection terminals 18a and 18b for taking out current to the outside are formed on the first current extraction part 12f and the second current extraction part 12h of the transparent conductive film 12A, respectively. The precursor of the terminal for external connection can be formed, for example, by applying a silver paste and drying it.

  Further, the precursor of the insulating material 33 made of glass frit so as to enter the first groove 90A formed along the edge of the main body 12a in the first groove 90A and also cover the edge of the main body 12a. Form the body. The insulating material 33 can be formed, for example, by applying and drying a paste containing glass frit.

  Further, in order to fix the back sheet 80, the annular connecting portion 14 is surrounded by the annular conductive portion 14 so as to surround the insulating material 33 and pass through the transparent conductive film 12D, the transparent conductive film 12E, and the transparent conductive film 12F. A precursor is formed.

  Furthermore, the precursor of the oxide semiconductor layer 13 is formed on each main body part 12a of the transparent conductive films 12A to 12D. The precursor of the oxide semiconductor layer 13 can be formed by printing a porous oxide semiconductor layer forming paste containing oxide semiconductor particles and then drying the paste.

  The oxide semiconductor layer forming paste contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles.

  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.

  Then, the precursor of the connection terminal 16, the precursor of the insulating material 33, the precursor of the connecting portion 14, and the precursor of the oxide semiconductor layer 13 are baked together, and the connecting terminal 16, the insulating material 33, the connecting portion 14, Then, the oxide semiconductor layer 13 is formed.

  At this time, the firing temperature varies depending on the types of oxide semiconductor particles and glass frit, but is usually 350 to 600 ° C., and the firing time also varies depending on the types of oxide semiconductor particles and glass frit, but usually 1 to 5 It's time.

  In this way, as shown in FIG. 7, the working electrode 10 in which the connecting portion 14 for fixing the back sheet 80 is formed is obtained.

  Next, a photosensitizing dye is supported on the oxide semiconductor layer 13 of the working electrode 10. For this purpose, the working electrode 10 is immersed in a solution containing a photosensitizing dye, the 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 layer 13.

  Next, as shown in FIG. 8, a first integrated sealing portion forming body 131 for forming the first integrated sealing portion 31 is prepared. The first integrated sealing portion forming body 131 prepares one sealing resin film made of the material constituting the first integrated sealing portion 31, and the sealing resin film according to the number of DSCs 50. It can be obtained by forming a rectangular opening 131a. The first integrated sealing portion forming body 131 has a structure in which a plurality of first sealing portion forming bodies 131A are integrated.

  Then, the first integrated sealing portion forming body 131 is adhered on the working electrode 10. At this time, the first integrated sealing portion forming body 131 is bonded to the working electrode 10 so as to overlap the insulating material 33. The first integrated sealing portion forming body 131 can be adhered to the working electrode 10 by heating and melting the first integrated sealing portion forming body 131. The first integrated sealing portion forming body 131 is adhered to the working electrode 10 so that the main body portion 12 a of the transparent conductive film 12 is disposed inside the first integrated sealing portion forming body 131.

  On the other hand, the same number of counter electrodes 20 as the number of DSCs 50 are prepared.

  The counter electrode 20 can be obtained by forming a conductive catalyst layer 22 that promotes the reduction reaction on the surface of the counter electrode 20 on the metal substrate 21.

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

  Next, the first integrated sealing portion forming body 131 bonded to the counter electrode 20 and the first integrated sealing portion forming body 131 bonded to the working electrode 10 are superposed to form a first integrated sealing portion forming body. 131 is heated and melted under pressure. Thus, the first integrated sealing portion 31 is formed between the working electrode 10 and the counter electrode 20. At this time, the width P of the bonding portion between the surface of the counter electrode 20 on the transparent conductive substrate 15 side and the partition portion 31b of the first integrated sealing portion 31 is equal to the surface of the counter electrode 20 on the transparent conductive substrate 15 side. The first integrated sealing portion 31 is formed so as to be narrower than the width Q of the bonding portion between the first integrated sealing portion 31 and the annular portion 31a. Further, the first integrated sealing is performed such that the width R of the partition portion 31b of the first integrated sealing portion 31 is not less than 100% and less than 200% of the width T of the annular portion 31a of the first integrated sealing portion 31. A portion 31 is formed. The formation of the first integrated sealing portion 31 may be performed under atmospheric pressure or under reduced pressure, but is preferably performed under reduced pressure.

  Next, the 2nd integrated sealing part 32 is prepared (refer FIG. 5). The second integrated sealing portion 32 has a structure formed by integrating a plurality of first sealing portions 32A. The second integrated sealing portion 32 can be obtained by preparing a single sealing resin film and forming the rectangular openings 32c corresponding to the number of DSCs 50 in the sealing resin film. The second integrated sealing portion 32 is bonded to the counter electrode 20 so as to sandwich the edge portion 20 a of the counter electrode 20 together with the first integrated sealing portion 31. The adhesion of the second integrated sealing portion 32 to the counter electrode 20 can be performed by heating and melting the second integrated sealing portion 32.

  Examples of the sealing resin film include ionomers, ethylene-vinyl acetic anhydride copolymers, modified polyolefin resins containing ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, ultraviolet curable resins, and vinyls. Examples thereof include resins such as alcohol polymers. The constituent material of the sealing resin film for forming the second integrated sealing portion 32 has a higher melting point than the constituent material of the sealing resin film for forming the first integrated sealing portion 31. It is preferable. In this case, since the second sealing portion 32A is harder than the first sealing portion 31A, it is possible to effectively prevent contact between the counter electrodes 20 of the adjacent DSCs 50. In addition, since the first sealing portion 31A is softer than the second sealing portion 32A, the stress applied to the sealing portion 30A can be effectively relieved.

  Next, the bypass diodes 70 </ b> A, 70 </ b> B, and 70 </ b> C are fixed to the partition part 32 b of the second sealing part 32. The bypass diode 70D is also fixed on the sealing portion 30A of the DSC 50D.

  Then, the conductive material 60Q is fixed to the metal substrate 21 of the counter electrode 20 of the DSCs 50B to 50C so as to pass through the bypass diodes 70A to 70D. Furthermore, each conductive material 60Q between the bypass diodes 70A and 70B, between the bypass diodes 70B and 70C, between the bypass diodes 70C and 70D, the conductive material connection portion 16A on the transparent conductive film 12A, and the conductive material connection portion on the transparent conductive film 12B. A conductive material 60P is formed so as to connect 16A and the conductive material connecting portion 16A on the transparent conductive film 12C. Further, the conductive material 60P is fixed to the metal substrate 21 of the counter electrode 20 of the DSC 50A so as to connect the conductive material connection portion 16A on the second connection portion 12i of the transparent conductive film 12E and the bypass diode 70A. Further, the transparent conductive film 12D and the bypass diode 70A are connected by the conductive material 60P.

  At this time, as the conductive material 60P, a paste containing a metal material constituting the conductive material 60P is prepared, and this paste is applied from the counter electrode 20 to the conductive material connection portion 16A of the connection terminal 16 of the adjacent DSC 50 and cured. . For the conductive material 60Q, a paste containing a metal material constituting the conductive material 60Q is prepared, and this paste is applied on each counter electrode 20 so as to connect adjacent bypass diodes, and is cured. At this time, as the paste, it is preferable to use a low-temperature curable paste that can be cured at a temperature of 90 ° C. or less from the viewpoint of avoiding an adverse effect on the photosensitizing dye.

  Finally, a back sheet 80 is prepared, and the peripheral edge 80 a of the back sheet 80 is bonded to the connecting portion 14. At this time, the back sheet 80 is disposed so that the adhesive portion 80B of the back sheet 80 and the sealing portion 30A of the DSC 50 are separated from each other.

  The DSC module 100 is obtained as described above.

  In the above description, in order to form the connection terminal 16, the insulating material 33, the connecting portion 14, and the oxide semiconductor layer 13, the precursor of the connecting terminal 16, the precursor of the insulating material 33, and the precursor of the connecting portion 14. Body, the precursor of the oxide semiconductor layer 13 is baked in a lump, but the connection terminal 16, the insulating material 33, the connecting portion 14, and the oxide semiconductor layer 13 are separately fired. May be formed.

  The present invention is not limited to the above embodiment. For example, in the above-described embodiment, the DSCs 50A to 50D are arranged in a line along the X direction in FIG. 2, but like the DSC module 200 shown in FIG. The DSC 50A and the DSC 50D may be arranged so that they are adjacent to each other. In FIG. 9, the back sheet 80 is omitted. In this case, unlike the DSC module 100, the transparent conductive film 12D does not need to provide the first connection part 12g between the main body part 12a and the first current extraction part 12f. For this reason, it is not necessary to provide the 1st current collection wiring 17 either.

  Moreover, in the said embodiment, the groove | channel formed along the edge part of the part except the main-body part 12a of the transparent conductive film 12 among 90 A of 1st groove | channels, and the adhesion part of the back sheet 80 and the transparent conductive substrate 15 14 is not covered with an insulating material 33 made of glass frit, but at least the second groove 90B is made of an insulating material made of glass frit as in the DSC module 300 shown in FIG. 33 is preferably covered. In FIG. 10, the back sheet 80 is omitted. As shown in FIG. 10, when at least the second groove 90 </ b> B intersects the bonding portion 14, moisture enters the space between the back sheet 80 and the transparent conductive substrate 15 through the second groove 90 </ b> B. It becomes possible. In this case, since the insulating material 33 enters at least the second groove 90B and covers the edge of the transparent conductive film 12 that forms the second groove 90B, moisture from the outside to the inside of the back sheet 80 is absorbed. Intrusion is sufficiently suppressed. For this reason, the moisture that has entered the space between the back sheet 80 and the transparent conductive substrate 15 is sufficiently suppressed from entering the electrolyte 40 through the sealing portion 30A. For this reason, it is possible to sufficiently suppress a decrease in durability of the DSC module 300.

Furthermore, in the said embodiment, although the 1st electric current extraction part 12f and the 2nd electric current extraction part 12h are arrange | positioned around the DSC50A side, from a viewpoint of achieving the said 2nd objective, the DSC module shown in FIG. As indicated by 400, the first current extraction portion 12f and the second current extraction portion 12h may be disposed around the DSC 50D side. In this case, the 1st electric current extraction part 12f is provided so that it may protrude to the outer side of 30 A of sealing parts on the opposite side to DSC50C with respect to the main-body part 12a of transparent conductive film 12D. On the other hand, the second current extraction portion 12h is provided on the opposite side of the DSC 50C with respect to the main body portion 12a of the transparent conductive film 12D. The second connection portion 12i extends along the transparent conductive films 12A to 12D, and the second connection portion 12i connects the second current extraction portion 12h and the metal substrate 21 of the counter electrode 20 of the DSC 50A. Specifically, a second current collecting wiring 417 is provided on the second connecting portion 12i along the second connecting portion 12i, and the second current collecting wiring 417 and a conductive material 60P extending from the bypass diode 70A are provided. It is connected. The DSC module 400 can also save space while having excellent photoelectric conversion characteristics. In this case, the resistance value of the second connection part 12i is preferably equal to or less than the resistance value represented by the following formula (1), as in the above embodiment.
Resistance value = number of DSCs 50 connected in series × 120Ω (1)

  Moreover, in the said embodiment, although the width | variety of the conductive material connection part 16A and the conductive material connection part 16B of the connection terminal 16 is made constant, the width | variety of the conductive material connection part 16A and the conductive material connection part 16B is respectively the connection terminal 16. It may change along the extending direction. For example, the width of the conductive material non-connecting portion 16B monotonically increases from the end farthest from the conductive material connecting portion 16A toward the end closest to the conductive material connecting portion 16A. The width may monotonously increase from the end portion on the 16B side toward the end portion farthest from the conductive member non-connecting portion 16B. However, when the widths of the conductive material non-connecting portion 16B and the conductive material connecting portion 16A are constant, the width of the connection terminal 16 changes abruptly at the boundary between the conductive material non-connecting portion 16B and the conductive material connecting portion 16A. Therefore, the conductive material non-connecting portion 16B becomes more difficult to peel off.

  In the above embodiment, the conductive material connecting portion 16A and the conductive material connecting portion 16B are provided along the sealing portion 30A, respectively, but these are formed to extend in a direction away from the sealing portion 30A. Also good. However, in this case, it is preferable that the conductive material connecting portion 16A is disposed at a position closer to the sealing portion 30A than the conductive material non-connecting portion 16B. In this case, the conductive material 60P can be made shorter.

  Alternatively, in the connection terminals 16 formed on the transparent conductive films 12A to 12C, the conductive material non-connecting portion 16B may be disposed so as to be orthogonal to the conductive material connecting portion 16A.

  In the above embodiment, the second sealing portion 32A is bonded to the first sealing portion 31A. However, the second sealing portion 32A may not be bonded to the first sealing portion 31A.

  Furthermore, in the said embodiment, although 30 A of sealing parts are comprised by 31 A of 1st sealing parts and 32 A of 2nd sealing parts, 32 A of 2nd sealing parts may be abbreviate | omitted.

  Moreover, in the said embodiment, the width P of the adhesion part of the counter electrode 20 and the partition part 31b of the 1st integrated sealing part 31 is the adhesion part of the counter electrode 20 and the annular part 31a of the 1st integrated sealing part 31. Although it is narrower than the width Q, from the viewpoint of achieving the first object, the width P of the bonded portion may be equal to or greater than the width Q of the bonded portion.

  Furthermore, in the said embodiment, the width | variety R of the partition part 31b of the 1st integrated sealing part 31 is 100% or more of the width | variety T of the annular part 31a of the 1st integrated sealing part 31, and less than 200%. However, the width R of the partition part 31b may be less than 100% of the width T of the annular part 31a of the first integrated sealing part 31, or 200% or more.

  Furthermore, in the said embodiment, although cyclic | annular 1st sealing part 31A of adjacent DSC50 is integrated, cyclic | annular 1st sealing part 31A of adjacent DSC50 is not necessarily integrated. Good. That is, the annular first sealing portions 31A may be separated from each other.

  Furthermore, in the said embodiment, although the back sheet 80 is provided, the back sheet 80 does not necessarily need to be provided. In this case, the connecting portion 14 is not provided.

  Moreover, in the said embodiment, although the back sheet 80 and the transparent conductive film 12 are adhere | attached via the connection part 14, the back sheet 80 and the transparent conductive film 12 are not necessarily adhere | attached via the connection part 14. There is no need to be.

  Furthermore, in the said embodiment, it forms along the edge of the part except the main-body part 12a of the transparent conductive film 12 among 1st groove | channel 90A as a clearance gap between a isolation | separation part and transparent conductive films 12A-12D. Although the groove and the second groove 90B are used, the gap does not necessarily need to be formed by a groove.

  Moreover, in the said embodiment, although the groove | channel 90 has the 2nd groove | channel 90B, the 2nd groove | channel 90B does not necessarily need to be formed. In other words, the entire gap between the transparent conductive film 12 </ b> F as the separation part and the transparent conductive films 12 </ b> A to 12 </ b> D may be disposed inside the inner peripheral edge of the coupling part 14.

  Furthermore, in the said embodiment, although the transparent conductive film 12F is used as a isolation | separation part which surrounds the transparent conductive films 12A-12D, the isolation | separation part does not need to be comprised with a conductor like the transparent conductive film 12F. In addition, it may be made of an insulator.

  Further, in the above-described embodiment, the separation portion such as the transparent conductive film 12F is not necessarily required and can be omitted.

  Furthermore, in the said embodiment, although the connection part 14 and 30 A of sealing parts are mutually spaced apart, these may be adhere | attached mutually.

  Furthermore, in the said embodiment, although the transparent conductive substrate 15 has the transparent substrate 11 and the transparent conductive film 12, and the counter electrode 20 has the metal substrate 21, from a viewpoint of achieving the 2nd objective, it is a counter electrode. 20 may include the transparent substrate 11 and the transparent conductive film 12 instead of the metal substrate 21, and the transparent conductive substrate 15 may be formed of the metal substrate 21. Alternatively, the counter electrode 20 may include the transparent substrate 11 and the transparent conductive film 12 instead of the metal substrate 21, and the transparent conductive substrate 15 may include the transparent substrate 11 and the transparent conductive film 12.

  Furthermore, in the said embodiment, although the connection part 14 and the insulating material 33 are spaced apart, it is preferable that these are all comprised and integrated with the glass frit. In this case, even if moisture enters in the space between the back sheet 80 and the transparent conductive substrate 15, the interface between the connecting portion 14 and the transparent conductive substrate 15, the sealing portion 30 </ b> A and the transparent conductive substrate 15. The interface between and no longer exists. Further, both the insulating material 33 and the connecting portion 14 are made of glass frit, and have a higher sealing ability than resin. For this reason, it is possible to sufficiently suppress the intrusion of moisture through the interface between the connecting portion 14 and the transparent conductive substrate 15 or through the interface between the insulating material 33 and the transparent conductive substrate 15.

  Moreover, in the said embodiment, although the insulating material 33 consists of glass frit, the material which comprises the insulating material 33 should just have melting | fusing point higher than the material which comprises 30 A of 1st sealing parts. For this reason, examples of such a material include glass frit, thermosetting resins such as polyimide resins, and thermoplastic resins. Among these, it is preferable to use a thermosetting resin. In this case, even if the sealing portion 30A becomes fluid at high temperatures, the insulating material 33 is less likely to be fluidized at high temperatures than when it is made of a thermoplastic resin, as in the case of glass frit. For this reason, the contact between the transparent conductive substrate 15 and the counter electrode 20 is sufficiently suppressed, and a short circuit between the transparent conductive substrate 15 and the counter electrode 20 can be sufficiently suppressed.

  Moreover, in the said embodiment, although the transparent conductive substrate 15 has the insulating material 33, it does not need to have the insulating material 33. FIG.

  Furthermore, in the said embodiment, although several DSC50 is connected in series, you may connect in parallel.

  Further, in the above embodiment, a plurality of DSCs 50 are used. However, from the viewpoint of achieving the first object described above, only one DSC 50 is used as in the dye-sensitized solar cell element 500 shown in FIG. May be. In the dye-sensitized solar cell element 500 shown in FIG. 12, the DSC 50A to DSC 50C are omitted, and the connection terminal 16 provided on the second connection part 12i and the metal substrate 21 of the counter electrode 20 of the DSC 50D are electrically conductive material 60P. It is electrically connected via. Further, in the dye-sensitized solar cell element 500, the connection terminal 16 includes only the conductive material connection portion 16A, and the conductive material connection portion 16A is disposed between the sealing portion 30A and the coupling portion 14. That is, the conductive material connecting portion 16A is not disposed at a position facing the side edge portion 12b of the main body portion 12a in the transparent conductive film 12D of the DSC 50D. For this reason, in the DSC module 100 of the first embodiment, the oxide semiconductor layer 13 can be expanded to the space where the conductive material connecting portion 16A is disposed. In this case, a useless space is effectively used and the power generation area can be expanded.

  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 laminate was prepared by forming a transparent conductive film made of FTO having a thickness of 1 μm on a transparent substrate made of glass having a thickness of 1 mm. Next, as shown in FIG. 3, CO ₂ to form a groove 90 on the transparent conductive film 12 by a laser (Universal System Co. V-460), to form a transparent conductive film 12A-12F. At this time, the width of the groove 90 was 1 mm. Each of the transparent conductive films 12A to 12C was formed so as to have a rectangular main body portion of 4.6 cm × 2.0 cm and a protruding portion protruding from one side edge portion of the main body portion. The transparent conductive film 12D was formed to have a 4.6 cm × 2.1 cm rectangular main body portion and a protruding portion protruding from one side edge of the main body portion. Further, of the transparent conductive films 12A to 12D, the projecting portions 12c of the three transparent conductive films 12A to 12C extend from the one side edge portion 12b of the main body portion 12a and the projecting portion 12d, and are adjacent to each other. The conductive film 12 is constituted by a facing portion 12e facing the main body portion 12a. Further, the projecting portion 12c of the transparent conductive film 12D is configured only by the overhanging portion 12d protruding from the one side edge portion 12b of the main body portion 12a. At this time, the length of the overhang portion 12d in the overhang direction (direction orthogonal to the X direction in FIG. 2) was 2.1 mm, and the width of the overhang portion 12d was 9.8 mm. The width of the facing portion 12e was 2.1 mm, and the length of the facing portion 12e in the extending direction was 9.8 mm.

  The transparent conductive film 12D has not only the main body portion 12a and the protruding portion 12c but also a first current extraction portion 12f and a first connection portion 12g that connects the first current extraction portion 12f and the main body portion 12a. Formed. The transparent conductive film 12E was formed to have the second current extraction part 12h and the second connection part 12i. At this time, the width of the first connection portion 12g was 1.3 mm, and the length was 59 mm. Moreover, it was 100 (ohm) when the resistance value of the 1st connection part 12g was measured by the four-terminal method.

  Next, the precursor of the connection terminal 16 composed of the conductive material connection portion 16A and the conductive material non-connection portion 16B was formed on the protruding portion 12c of the transparent conductive films 12A to 12C. Specifically, the precursor of the connection terminal 16 is provided such that the precursor of the conductive material non-connecting portion 16B is provided on the overhanging portion 12d so that the precursor of the conductive material connecting portion 16A is provided on the facing portion 12e. Formed. At this time, the precursor of the conductive material non-connecting portion 16B was formed to be narrower than the width of the conductive material connecting portion 16A. The precursor of the connection terminal 16 was formed by applying and drying a silver paste (“GL-6000X16” manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) by screen printing.

  Furthermore, the precursor of the 1st current collection wiring 17 was formed on the 1st connection part 12g of transparent conductive film 12D. The precursor of the first current collector wiring 17 was formed by applying a silver paste by screen printing and drying.

  In addition, precursors of external connection terminals 18a and 18b for taking out current to the outside were formed on the first current extraction portion 12f and the second current extraction portion 12h of the transparent conductive film 12D, respectively. The precursor of the terminal for external connection was formed by applying a silver paste by screen printing and drying.

  Furthermore, the precursor of the insulating material 33 made of glass frit was formed so as to enter the first groove 90A and cover the edge of the main body part 12a forming the first groove 90A. The insulating material 33 was formed by applying and drying a paste containing glass frit by screen printing. At this time, the edge of the transparent conductive film covered with the insulating material 33 was a portion 0.2 mm from the groove 90.

  Further, in order to fix the back sheet 80, in the same manner as the insulating material 33, an annular ring made of glass frit is formed so as to surround the insulating material 33 and pass through the transparent conductive film 12D, the transparent conductive film 12E, and the transparent conductive film 12F. The precursor of the connection part 14 was formed. Moreover, at this time, the precursor of the connection part 14 was formed so that the precursor of the 1st current collection wiring 17 might be arrange | positioned inside. Moreover, the connection part 14 was formed so that the 1st electric current extraction part and the 2nd electric current extraction part may be arrange | positioned on the outer side. The connecting part 14 was formed by applying and drying a paste containing glass frit by screen printing.

  Furthermore, the precursor of the oxide semiconductor layer 13 was formed on each main body part 12a of the transparent conductive films 12A to 12D. The precursor of the oxide semiconductor layer 13 is a porous oxide semiconductor layer forming paste containing titania (“PST-21NR” manufactured by JGC Catalysts & Chemicals Co., Ltd.) three times by screen printing, dried, and further titania. It was formed by applying a porous oxide semiconductor layer forming paste (“PST-400C” manufactured by JGC Catalysts & Chemicals Co., Ltd.) by screen printing, followed by drying.

Next, a precursor of the connection terminal 16, a precursor of the first current collector wiring 17, a precursor of the external connection terminals 18a and 18b, a precursor of the insulating material 33, a precursor of the connecting portion 14, and a precursor of the insulating material 33 Body, the precursor of the oxide semiconductor layer 13 is baked at 500 ° C. for 15 minutes, and the connection terminal 16, the first current collector wiring 17, the external connection terminals 18 a and 18 b, the connecting portion 14, the insulating material 33, and the oxide semiconductor layer 13 was formed. At this time, the width of the conductive material connection portion of the connection terminal 16 was 1.0 mm, and the width of the conductive material non-connection portion was 0.3 mm. Further, the length along the extending direction of the conductive material connecting portion was 7.0 mm, and the length along the extending direction of the conductive material non-connecting portion was 7.0 mm. The dimensions of the first current collector wiring 17, the external connection terminals 18 a and 18 b, the connecting portion 14, and the oxide semiconductor layer 13 were as follows.

First current collecting wiring 17: thickness 4 μm, width 200 μm, length 79 mm along the X direction in FIG. 2, length 21 mm along the direction orthogonal to the X direction in FIG.
External connection terminals 18a and 18b: thickness 20 μm, width 2 mm, length 7 mm
Connection part 14: thickness 50 μm, width 3 mm
Oxide semiconductor layer 13: 13 μm thick, 17 mm length in the X direction in FIG. 2, 42.1 mm length in the direction orthogonal to the X direction in FIG.

  Next, the working electrode is immersed overnight in a dye solution containing 0.2 mM of a photosensitizing dye composed of N719 and a solvent in which acetonitrile and tert-butanol are mixed at a volume ratio of 1: 1. Then, it was taken out and dried, and a photosensitizing dye was supported on the oxide semiconductor layer.

  Next, on the oxide semiconductor layer, in a solvent composed of 3-methoxypropionitrile, hexylmethylimidazolium iodide 2M, n-methylbenzimidazole 0.3M, and guanidinium thiocyanate 0.1M are formed. The electrolyte was applied and dried to place the electrolyte.

  Next, a first integrated sealing portion forming body for forming the first sealing portion was prepared. The first integrated sealing portion forming body is a single sealing made of an ethylene-methacrylic acid copolymer (trade name: Nucrel, manufactured by Mitsui DuPont Polychemical Co., Ltd.) of 8.0 cm × 4.6 cm × 50 μm. A resin film was prepared and obtained by forming four rectangular openings in the sealing resin film. At this time, each opening has a size of 1.7 cm × 4.4 cm × 50 μm, the width of the annular portion is 2 mm, and the width of the partition portion that partitions the inner opening of the annular portion is 2.6 mm. The 1st integrated sealing part formation body was produced.

  Then, after the first integrated sealing portion forming body is overlaid on the insulating material 33 of the working electrode, the first integrated sealing portion forming body is bonded to the insulating material 33 of the working electrode by heating and melting. It was.

  Next, four counter electrodes were prepared. Of the four counter electrodes, two counter electrodes were prepared by forming a catalyst layer of platinum having a thickness of 5 nm on a 4.6 cm × 1.9 cm × 40 μm titanium foil by sputtering. The remaining two counter electrodes among the four counter electrodes were prepared by forming a catalyst layer made of platinum having a thickness of 5 nm on a 4.61 cm × 2.0 cm × 40 μm titanium foil by sputtering. In addition, another first integrated sealing portion forming body was prepared, and this first integrated sealing portion forming body was adhered to the surface of the counter electrode facing the working electrode in the same manner as described above. .

Then, the first integrated sealing portion forming body bonded to the working electrode and the first integrated sealing portion forming body bonded to the counter electrode are opposed to each other, and the first integrated sealing portion forming bodies are overlapped with each other. Combined. In this state, the first integrated sealing portion forming body was heated and melted while pressurizing the first integrated sealing portion forming body. Thus, the first sealing portion was formed between the working electrode and the counter electrode. At this time, the width P of the bonded portion between the partition portion of the first integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode, and the transparent conductive portion of the annular portion and the counter electrode of the first integrated sealing portion. The width Q of the bonded portion with the surface on the conductive substrate side, the width R of the partition portion of the first integrated sealing portion, and the width T of the annular portion were as follows.

P = 1.0mm
Q = 2.0mm
R = 2.6mm
T = 2.2mm

  Next, a second integrated sealing part was prepared. The second integrated sealing portion is prepared by preparing a sealing resin film made of maleic anhydride-modified polyethylene (trade name: Binnel, manufactured by DuPont) of 8.0 cm × 4.6 cm × 50 μm. It was obtained by forming four rectangular openings in the stopping resin film. At this time, each opening has a size of 1.7 cm × 4.4 cm × 50 μm, the width of the annular portion is 2 mm, and the width of the partition portion that partitions the inner opening of the annular portion is 2.6 mm. A second integrated sealing portion was prepared. The second integrated sealing portion was bonded to the counter electrode so as to sandwich the edge of the counter electrode together with the first integrated sealing portion. At this time, the first integrated sealing portion and the second integrated sealing portion were bonded to the counter electrode and the first integrated sealing portion by heating and melting while pressing the second integrated sealing portion against the counter electrode.

  Next, the desiccant sheet was affixed with the double-sided tape on the metal substrate of each counter electrode. The dimensions of the desiccant sheet were 1 mm thick × 3 cm long × 1 cm wide, and a zeo sheet (trade name, manufactured by Shinagawa Kasei Co., Ltd.) was used as the desiccant sheet.

  Next, as shown in FIG. 2, bypass diodes 70 </ b> A to 70 </ b> C are respectively provided in the three partition portions of the second integrated sealing portion, and a low-temperature curing type silver paste (Dotite D500 manufactured by Fujikura Kasei Co., Ltd.) is used. It fixed by apply | coating so that it might connect with the metal substrate 21 of the counter electrode 20 from the terminal of both ends. Further, among the four DSCs 50A to 50D, the bypass diode 70D is connected to the annular part of the second integrated sealing part of the DSC 50D, and the low-temperature curing type silver paste is connected to the counter electrode from one of the terminals at both ends of the diode. It was fixed by applying as follows. Thus, the conductive material 60Q was formed so as to connect the two adjacent bypass diodes to the four bypass diodes 70A to 70D. At this time, the conductive material 60Q was formed by curing the low temperature curable silver paste at 30 ° C. for 12 hours. As the bypass diode, RB751V-40 manufactured by ROHM was used.

  Further, a low temperature curing type silver paste (Dotite D-500, manufactured by Fujikura Kasei Co., Ltd.) is used so as to connect each conductive material 60Q between the bypass diodes and the conductive material connecting portions on the three transparent conductive films 12A to 12C. The conductive material 60P was formed by applying and curing. Further, for the bypass diode 70A, the conductive material 60P was formed by applying and curing the above-mentioned low-temperature curable silver paste so as to be connected to the conductive material connecting portion on the second connecting portion 12i of the transparent conductive film 12E. At this time, the conductive material 60P was formed by curing the low temperature curable silver paste at 30 ° C. for 12 hours.

  Next, butyl rubber (“Aikamelt” manufactured by Aika Kogyo Co., Ltd.) was applied onto the connecting portion 14 with a dispenser while heating at 200 ° C. to form a precursor of the bonded portion. On the other hand, a laminate is prepared by laminating a film (thickness 50 μm) made of polybutylene terephthalate (PBT) resin film (thickness 50 μm), aluminum foil (thickness 25 μm) and binel (trade name, manufactured by DuPont) in this order. did. And it piled up on the peripheral part of this laminated body 80A, and the precursor of the adhesion part 80B, and pressurized for 10 seconds. In this way, a back sheet 80 composed of the bonding portion 80B and the laminated body 80A was obtained at the connecting portion 14. A DSC module was obtained as described above.

(Example 2)
A DSC module was produced in the same manner as in Example 1 except that the first current collecting wiring 17 was not formed.

Example 3
A DSC module was produced in the same manner as in Example 1 except that the connecting portion 14 was not formed.

Example 4
The first current collecting wiring 17 is connected to the external connection terminal 18a from the main body portion 12a of the transparent conductive film 12D through the first connection portion 12g and the first current extraction portion 12f before the connection portion 14 is formed. A DSC module was produced in the same manner as in Example 1 except that the connecting portion 14 was formed so that the first current collecting wiring 17 and the connecting portion 14 intersected.

(Example 5)
When forming the first integrated sealing portion between the working electrode and the counter electrode, the width P of the adhesive portion between the partition portion of the first integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode, The width Q of the adhesive portion between the annular portion of the integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode, the width R of the partition portion of the first integrated sealing portion, and the first integrated sealing portion A DSC module was produced in the same manner as in Example 1 except that the width T of each annular portion was as follows.

P = 1.4mm
Q = 2.0mm
R = 0.4mm
T = 3.2mm

Example 6
When forming the first integrated sealing portion between the working electrode and the counter electrode, the width P of the adhesive portion between the partition portion of the first integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode, The width Q of the adhesive portion between the annular portion of the integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode, the width R of the partition portion of the first integrated sealing portion, and the first integrated sealing portion A DSC module was produced in the same manner as in Example 1 except that the width T of each annular portion was as follows.

P = 0.8mm
Q = 1.5mm
R = 0.8mm
T = 2.4mm

(Example 7)
A DSC module was produced in the same manner as in Example 1 except that the second integrated sealing portion was not bonded to the counter electrode and the first integrated sealing portion.

(Example 8)
When forming the first integrated sealing portion between the working electrode and the counter electrode, the width P of the adhesive portion between the partition portion of the first integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode, Except that the width Q of the bonded portion between the annular portion of the one integrated sealing portion and the surface on the transparent conductive substrate side of the counter electrode and the width R of the partition portion of the first integrated sealing portion are as follows. Produced a DSC module in the same manner as in Example 1.

P = 0.5mm
Q = 0.5mm
R = 0.6mm
T = 1.6mm

Example 9
A DSC module was produced in the same manner as in Example 1 except that the width of the conductive material non-connection portion was set to 1/3 times the width of the conductive material connection portion.

(Example 10)
A DSC module was produced in the same manner as in Example 1 except that the width of the conductive member non-connecting portion 16 was the same as the width of the conductive member connecting portion 16.

(Characteristic evaluation)
(Photoelectric conversion characteristics)
About the DSC module obtained in Examples 1-4, photoelectric conversion efficiency (eta) (%) was measured under the illumination intensity of 200 lux. Moreover, about the DSC module obtained in Examples 1-4, photoelectric conversion efficiency (eta) (%) was measured like the above also under the illumination intensity of 20000 lux. The results are shown in Table 1.

(Aperture ratio)
About the DSC module obtained in Example 1 and Examples 5-8, the aperture ratio was measured. The results are shown in Table 2.

(durability)
About the DSC module obtained in Example 1 and Examples 5-8, the photoelectric conversion efficiency ((eta) ₀ ) was measured. Subsequently, the photoelectric conversion efficiency (η) of the DSC modules obtained in Example 1 and Examples 5 to 8 after being left for 1000 hours in a high-temperature and high-humidity environment at 85 ° C. and 85% RH was also measured. did. And the following formula:
Retention rate of photoelectric conversion efficiency (%) = η / η ₀ × 100
Based on the above, the retention rate of photoelectric conversion efficiency (photoelectric conversion retention rate) was calculated. The results are shown in Table 2.

(Connection reliability)
The connection reliability is evaluated by conducting a heat cycle test according to JIS C 8938 on the DSC modules obtained in Example 1 and Examples 9 to 10 and examining the presence or absence of peeling of the connection terminals from the transparent conductive film. did. The results are shown in Table 3. In addition, the heat cycle test 1 was performed 200 cycles when the cycle which raises or falls environmental temperature from -40 degreeC to 90 degreeC was made into 1 cycle.

  As shown in Table 1, the DSC modules of Examples 1 to 4 showed large photoelectric conversion efficiency under a low illuminance of 200 lux, but the photoelectric conversion efficiency was decreased under a high illuminance of 20000 lux. I understood. Moreover, since the DSC modules of Examples 1 to 4 are arranged so that the first current extraction unit and the second current extraction unit are adjacent to each other, space saving can be achieved.

  As shown in Table 2, the DSC modules of Example 1 and Examples 5 to 7 can further improve the aperture ratio, and have a higher photoelectric conversion retention rate than the DSC module of Example 8. I found out that

  As shown in Table 3, in the DSC module obtained in Example 1 and Example 9, it was found that in the heat cycle test 1, the connection terminal did not peel from the transparent conductive film. In contrast, the DSC module obtained in Example 10 was found to peel from the transparent conductive film by the heat cycle test.

  From the above, it was confirmed that the DSC element for low illuminance of the present invention can save space while having excellent photoelectric conversion characteristics.

DESCRIPTION OF SYMBOLS 11 ... Transparent substrate 12 ... Transparent conductive film 12F ... Transparent conductive film (separation part)
12a ... Main body part 12c ... Projection part 12e ... Opposite part 12f ... 1st current extraction part 12h ... 2nd current extraction part 12g ... 1st connection part 12i ... 2nd connection part 13 ... Oxide semiconductor layer 14 ... Connection part 15 ... Transparent conductive substrate (first electrode)
DESCRIPTION OF SYMBOLS 16 ... Connection terminal 16A ... Conductive material connection part 16B ... Conductive material non-connection part 17,417 ... Current collection wiring 20 ... Counter electrode (2nd electrode)
DESCRIPTION OF SYMBOLS 21 ... Metal substrate 30A ... Sealing part 31a, 32a ... Annular part 31b, 32b ... Partition part 31 ... 1st integrated sealing part 32 ... 2nd integrated sealing part 33 ... Insulating material 50, 50A-50D ... Dye Sensitized solar cell 60P, 60Q ... Conductive material 80 ... Back sheet 80a ... Back sheet peripheral edge 90A ... First groove (gap)
90B ... Second groove (gap)
100, 200, 300, 400 ... Dye-sensitized solar cell module (dye-sensitized solar cell element)
500 ... Dye-sensitized solar cell element

That is, the present invention provides at least one dye-sensitized solar cell, a first current extraction unit for extracting current from the at least one dye-sensitized solar cell, and extracts current from the at least one dye-sensitized solar cell. A first electrode having a transparent substrate, a transparent conductive film provided on one surface of the transparent substrate, and a first electrode having a second current extraction portion for opposing the first electrode. A second electrode having a metal substrate, an oxide semiconductor layer provided on the first electrode or the second electrode, and an annular sealing portion for joining the first electrode and the second electrode. The first current extraction unit is included in the transparent conductive film of one of the at least one dye-sensitized solar cell, and the second current extraction unit is the at least One color One of the sensitized solar cells is electrically connected to the metal substrate of the second electrode of the dye-sensitized solar cell, and is disposed so that the first current extraction portion and the second current extraction portion are adjacent to each other. A low-illuminance dye-sensitized solar cell element , further comprising a back sheet that covers the at least one dye-sensitized solar cell on the one surface side of the transparent substrate, and the second current extraction unit and the It is a low-illuminance dye-sensitized solar cell element in which a metal substrate is connected to the outside of the sealing portion and the inside of the back sheet .

The present invention also provides at least one dye-sensitized solar cell, a first current extraction unit for taking out current from the at least one dye-sensitized solar cell, and taking out current from the at least one dye-sensitized solar cell. A first electrode having a transparent substrate, a transparent conductive film provided on one surface of the transparent substrate, and a first electrode having a second current extraction portion for opposing the first electrode. A second electrode having a metal substrate, an oxide semiconductor layer provided on the first electrode or the second electrode, and an annular sealing portion for joining the first electrode and the second electrode. The first current extraction unit is included in the transparent conductive film of one of the at least one dye-sensitized solar cell, and the second current extraction unit is the at least 1 dye increase One of the solar cells is electrically connected to the metal substrate of the second electrode of the dye-sensitized solar cell, and the first current extraction unit and the second current extraction unit are disposed adjacent to each other. A low-illuminance dye-sensitized solar cell element, further comprising a back sheet that covers the at least one dye-sensitized solar cell on the one surface side of the transparent substrate, and is insulated on the entire periphery of the peripheral edge of the back sheet A connecting portion is provided, the transparent substrate and the connecting portion are connected, and a gap is formed between the transparent conductive film and the transparent conductive film so as to surround the transparent conductive film of at least one dye-sensitized solar cell. And a separation portion provided so as to form an annular structure together with the first current extraction portion and the second current extraction portion. on the inside It is location, a dye-sensitized solar cell element for low illuminance.

The present invention also provides at least one dye-sensitized solar cell, a first current extraction unit for taking out current from the at least one dye-sensitized solar cell, and taking out current from the at least one dye-sensitized solar cell. A first electrode having a transparent substrate, a transparent conductive film provided on one surface of the transparent substrate, and a first electrode having a second current extraction portion for opposing the first electrode. A second electrode having a metal substrate, an oxide semiconductor layer provided on the first electrode or the second electrode, and an annular sealing portion for joining the first electrode and the second electrode. The first current extraction unit is included in the transparent conductive film of one of the at least one dye-sensitized solar cell, and the second current extraction unit is the at least 1 dye increase One of the solar cells is electrically connected to the metal substrate of the second electrode of the dye-sensitized solar cell, and the first current extraction unit and the second current extraction unit are disposed adjacent to each other. A dye-sensitized solar cell element for low illuminance , comprising a plurality of the dye-sensitized solar cells, wherein the transparent substrate is composed of a common transparent substrate of the plurality of dye-sensitized solar cells and is adjacent to each other The second electrodes of two dye-sensitized solar cells are spaced apart from each other, and the sealing portion has an annular first sealing portion provided between the first electrode and the second electrode. The first sealing portions of two adjacent dye-sensitized solar cells are integrated to form a first integrated sealing portion, and the first integrated sealing portion includes an annular portion, A partition portion for partitioning the opening in the annular portion, and the partition portion of the first integrated sealing portion; The width of the bonding portion between the second electrode and the surface on the first electrode side is the bonding between the annular portion of the first integrated sealing portion and the surface on the first electrode side of the second electrode. This is a dye-sensitized solar cell element for low illuminance, which is narrower than the width of the portion.

The present invention also provides at least one dye-sensitized solar cell, a first current extraction unit for taking out current from the at least one dye-sensitized solar cell, and taking out current from the at least one dye-sensitized solar cell. A first electrode having a transparent substrate, a transparent conductive film provided on one surface of the transparent substrate, and a first electrode having a second current extraction portion for opposing the first electrode. A second electrode having a metal substrate, an oxide semiconductor layer provided on the first electrode or the second electrode, and an annular sealing portion for joining the first electrode and the second electrode. The first current extraction unit is included in the transparent conductive film of one of the at least one dye-sensitized solar cell, and the second current extraction unit is the at least 1 dye increase One of the solar cells is electrically connected to the metal substrate of the second electrode of the dye-sensitized solar cell, and the first current extraction unit and the second current extraction unit are disposed adjacent to each other. A plurality of dye-sensitized solar cells, wherein the plurality of dye-sensitized solar cells are connected in series and electrically, and the plurality of dye-sensitized solar cells Among the batteries, the dye-sensitized solar cell connected to the adjacent dye-sensitized solar cell further includes a connection terminal provided on the transparent conductive film, and the transparent conductive film is the annular sealing One of the two adjacent dye-sensitized solar cells, which has a main body provided on the inner side of the unit, and a protruding part protruding from the main body to the outer side of the sealing part and provided with the connection terminal The connection terminal in the sensitized solar cell In the other dye-sensitized solar cell, the metal substrate of the second electrode is connected via a conductive material, the connection terminal is connected to the conductive material, and along a certain direction outside the sealing portion. A conductive material connecting portion extending; and a conductive material non-connecting portion extending along a certain direction from the conductive material connecting portion outside the sealing portion, wherein the width of the conductive material non-connecting portion is the conductive material connecting portion. This is a low-illuminance dye-sensitized solar cell element narrower than the width of the portion.

Claims (14)

At least one dye-sensitized solar cell;
A first current extraction portion for extracting current from the at least one dye-sensitized solar cell;
A second current extraction portion for extracting current from the at least one dye-sensitized solar cell,
The dye-sensitized solar cell is
A first electrode having a transparent substrate and a transparent conductive film provided on one surface of the transparent substrate;
A second electrode facing the first electrode and having a metal substrate;
An oxide semiconductor layer provided on the first electrode or the second electrode;
An annular sealing portion for joining the first electrode and the second electrode,
The first current extraction portion is included in the transparent conductive film of one of the at least one dye-sensitized solar cell;
The second current extraction unit is electrically connected to the metal substrate of the second electrode of one of the at least one dye-sensitized solar cell;
The low-illuminance dye-sensitized solar cell element, wherein the first current extraction unit and the second current extraction unit are disposed adjacent to each other.   The dye-sensitized solar cell element for low illuminance according to claim 1, further comprising a back sheet that covers the at least one dye-sensitized solar cell on the one surface side of the transparent substrate. An insulating connecting portion is provided on the entire periphery of the backsheet.
A separation portion provided to connect the transparent substrate and the connecting portion, surround the transparent conductive film of at least one dye-sensitized solar cell, and form a gap between the transparent conductive film; Have
The separation part is provided so as to form an annular structure together with the first current extraction part and the second current extraction part;
The dye-sensitized solar cell element for low illuminance according to claim 2, wherein a part of the gap is disposed inside the connecting portion. The first current extraction part and the second current extraction part are arranged around one dye-sensitized solar cell of the at least one dye-sensitized solar cell,
3. The metal substrate of the second electrode of the dye-sensitized solar cell of the at least one dye-sensitized solar cell and the second current extraction unit are connected by a second connection unit. Or the dye-sensitized solar cell element for low illumination intensity of 3.   The dye-sensitized solar cell element for low illuminance according to claim 4, further comprising a second current collector wiring provided on the second connection part and having a lower resistance than the second connection part.   The dye-sensitized solar cell element for low illuminance according to claim 5, wherein the second current collecting wiring is disposed so as not to intersect with a peripheral edge portion of the back sheet.   The dye-sensitized solar cell element for low illuminance according to any one of claims 4 to 6, wherein the second connection portion is disposed on an inner side than a peripheral edge portion of the back sheet. The first current extraction part and the second current extraction part are arranged around one dye-sensitized solar cell of the at least one dye-sensitized solar cell,
The transparent conductive film of one dye-sensitized solar cell of the at least one dye-sensitized solar cell,
A main body provided inside the annular sealing portion;
The dye-sensitized solar cell element for low illuminance according to any one of claims 2 to 7, further comprising a first connection portion that connects the main body portion and the first current extraction portion.   The dye-sensitized solar cell of the at least one dye-sensitized solar cell is provided along at least the first connection portion on the first connection portion, and has a lower resistance than the first connection portion. The dye-sensitized solar cell element for low illuminance according to claim 8, further comprising a first current collector wiring.   The low-illuminance dye-sensitized solar cell element according to claim 9, wherein the first current collector wiring is disposed so as not to intersect with a peripheral edge portion of the back sheet. Having a plurality of the dye-sensitized solar cells,
The transparent substrate is composed of a common transparent substrate of the plurality of dye-sensitized solar cells,
The second electrodes of two adjacent dye-sensitized solar cells are separated from each other,
The sealing part has an annular first sealing part provided between the first electrode and the second electrode;
The first sealing portions of two adjacent dye-sensitized solar cells are integrated to form a first integrated sealing portion,
The first integrated sealing part has an annular part and a partition part that partitions an opening in the annular part,
The width of the bonding portion between the partition portion of the first integrated sealing portion and the surface of the second electrode on the first electrode side is set so that the annular portion of the first integrated sealing portion and the second portion The dye-sensitized solar cell element for low illuminance according to any one of claims 1 to 10, which is narrower than a width of an adhesive portion between the electrode and a surface on the first electrode side.   The low-illuminance dye-sensitized solar cell element according to claim 11, wherein, in the first integrated sealing portion, a width of the partition portion is 100% or more and less than 200% of a width of the annular portion. The sealing part of the plurality of dye-sensitized solar cells is provided so as to overlap the first sealing part, and an annular second seal that sandwiches the edge of the second electrode together with the first sealing part. Further having a stop,
The dye-sensitized solar cell element for low illuminance according to claim 11 or 12, wherein the second sealing portion is integrated to form a second integrated sealing portion. Having a plurality of the dye-sensitized solar cells, the plurality of dye-sensitized solar cells are connected in series and electrically,
Among the plurality of dye-sensitized solar cells, the dye-sensitized solar cell connected to an adjacent dye-sensitized solar cell is
It further comprises a connection terminal provided on the transparent conductive film,
The transparent conductive film is
A main body provided inside the annular sealing portion;
Projecting from the main body part to the outside of the sealing part, and having a projecting part provided with the connection terminal,
Of the two adjacent dye-sensitized solar cells, the connection terminal in one dye-sensitized solar cell and the metal substrate of the second electrode in the other dye-sensitized solar cell are connected via a conductive material,
The connection terminal is
A conductive material connecting portion connected to the conductive material and extending along a certain direction outside the sealing portion;
A conductive material non-connecting portion extending along a certain direction from the conductive material connecting portion outside the sealing portion;
The low-illuminance dye-sensitized solar cell element according to any one of claims 1 to 13, wherein a width of the conductive material non-connecting portion is narrower than a width of the conductive material connecting portion.

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