WO2017154493A1

WO2017154493A1 - Dye-sensitized solar cell module

Info

Publication number: WO2017154493A1
Application number: PCT/JP2017/005554
Authority: WO
Inventors: 明彦吉原; 清茂児島; 和志池上; 孝介青山
Original assignee: 日本ゼオン株式会社
Priority date: 2016-03-10
Filing date: 2017-02-15
Publication date: 2017-09-14
Also published as: TW201735379A

Abstract

This dye-sensitized solar cell module is provided with a photoelectrode substrate 3, a counterelectrode substrate 7 forming multiple cells together with the photoelectrode substrate 3, electrolyte layers 4, cell connecting units 9 connecting mutually adjacent cells in series, and separating walls 8 arranged between the photoelectrode substrate 3 and the counterelectrode substrate 7 and surrounding the electrolyte layers 4 and cell connecting units 9. Further, the cell connecting units 9 contain a conductive resin composition in which the average particle diameter of the conductive particles is 0.5-30 μm, and the content ratio of the conductive particles is 0.1-10 vol%.

Description

Dye-sensitized solar cell module

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

In recent years, solar cells have attracted attention as photoelectric conversion elements that convert light energy into electric power. In particular, dye-sensitized solar cells can be expected to be lighter than silicon solar cells, etc., can generate power stably over a wide illuminance range, and do not require large-scale equipment. It attracts attention because it can be manufactured using inexpensive materials.

Here, the dye-sensitized solar cell usually has a structure in which a photoelectrode including a porous semiconductor fine particle layer on which a sensitizing dye is adsorbed, an electrolyte layer, and a counter electrode including a catalyst layer are arranged in this order. It is used in the form of a solar cell module formed by connecting a plurality of cells, or a solar cell array formed by connecting a plurality of solar cell modules in series or in parallel.

And as a dye-sensitized solar cell module formed by connecting cells of a dye-sensitized solar cell in series, for example, a photoelectrode substrate in which a plurality of photoelectrodes are arranged in parallel on a base material, and a base material A counter electrode substrate having a plurality of counter electrodes arranged side by side so that the photoelectrodes forming each cell and the counter electrode face each other, and between the adjacent cells, the photoelectrode of one cell and the other There has been proposed a module formed by bonding so that the counter electrode of each cell is electrically connected (see, for example, Patent Document 1).

In the conventional dye-sensitized solar cell module, the cell connection portion that electrically connects the photoelectrode of one cell and the counter electrode of the other cell between adjacent cells may be, for example, metal or conductive The wiring etc. which were formed using the resin composition are used.

JP 2007-220608 A

Here, in the dye-sensitized solar cell module, as the conductive resin composition used for connection between adjacent cells, for example, a composition containing a resin and conductive particles is used. However, the dye-sensitized solar cell module having a cell connection portion formed using a conductive resin composition containing a resin and conductive particles is improved in terms of further improving photoelectric conversion efficiency and reliability. There was room.

Therefore, the present invention provides a dye-sensitized solar cell module having a cell connection portion formed using a conductive resin composition, which is excellent in reliability and has high photoelectric conversion efficiency. The purpose is to provide.

An object of the present invention is to advantageously solve the above problems, and a dye-sensitized solar cell module of the present invention includes a photoelectrode, a counter electrode facing the photoelectrode, and the photoelectrode. A dye-sensitized solar cell module comprising a plurality of cells connected in series with an electrolyte layer provided between the counter electrodes, wherein a plurality of photoelectrodes are spaced apart from each other on a substrate. A plurality of counter electrodes spaced apart from each other on a base material, which are arranged to face the photoelectrode substrate so as to form the cells, and to each other An electrolyte layer disposed between the opposing photoelectrode and the opposing electrode, a cell connecting portion for connecting cells adjacent to each other in series, and the photoelectrode substrate and the opposing electrode substrate. The electrolyte layer and the cell connection part Each of the cell connection portions includes a conductive resin composition containing a resin and conductive particles, and the conductive resin composition has an average particle diameter of 0 for the conductive particles. 0.5 to 30 μm, and the content ratio of the conductive particles is 0.1 to 10% by volume. Thus, if a cell connection part is formed using the conductive resin composition which contains the electroconductive particle whose average particle diameter is 0.5 micrometer or more and 30 micrometers or less in the ratio of 0.1 volume% or more and 10 volume% or less. Thus, a dye-sensitized solar cell module with high photoelectric conversion efficiency and reliability can be obtained.
In the present invention, the “average particle diameter of conductive particles” refers to the median diameter of conductive particles.

Here, in the dye-sensitized solar cell module of the present invention, the photoelectrode includes a conductive layer, and a porous semiconductor fine particle layer formed on the conductive layer and carrying a sensitizing dye, and the cell connection The unit electrically connects the conductive layer of the photoelectrode of one cell and the counter electrode of the other cell, and is connected to each other via the cell connection unit, the photoelectrodes of adjacent cells The conductive resin composition is preferably present between the conductive layers. When the photoelectrodes arranged apart from each other have a conductive layer, the long-term reliability of the dye-sensitized solar cell module can be obtained if the conductive resin composition is present between the conductive layers of the photoelectrodes of adjacent cells. Can increase the sex.

In the dye-sensitized solar cell module of the present invention, it is preferable that the distance between the conductive layers of the photoelectrodes of the cells adjacent to each other is 3 to 30 times the average particle diameter of the conductive particles. When the distance between the conductive layers is 3 to 30 times the average particle size of the conductive particles, the reliability can be further improved while increasing the photoelectric conversion efficiency of the dye-sensitized solar cell module.

Furthermore, in the dye-sensitized solar cell module of the present invention, the counter electrode includes a conductive layer and a catalyst layer formed on the conductive layer, and the cell connection portion includes the counter electrode of one cell. The conductive resin composition is electrically connected to the photoelectrode of the other cell, and is connected to each other via the cell connection portion, and the conductive resin composition is disposed between the conductive layers of the counter electrodes of adjacent cells. Is preferably present. When the counter electrodes arranged apart from each other have a conductive layer, the long-term reliability of the dye-sensitized solar cell module can be obtained if a conductive resin composition exists between the conductive layers of the counter electrodes of adjacent cells. Can increase the sex.

In the dye-sensitized solar cell module of the present invention, it is preferable that the distance between the conductive layers of the counter electrodes of the cells adjacent to each other is 3 to 30 times the average particle diameter of the conductive particles. When the distance between the conductive layers is 3 to 30 times the average particle size of the conductive particles, the reliability can be further improved while increasing the photoelectric conversion efficiency of the dye-sensitized solar cell module.

Furthermore, in the dye-sensitized solar cell module of the present invention, it is preferable that the cell connection portion further includes a metal wiring. If the cell connection part is formed using the metal wiring and the conductive resin composition, the electric resistance of the cell connection part is reduced as compared with the case where the cell connection part is formed using only the conductive resin composition, The photoelectric conversion efficiency of the dye-sensitized solar cell module can be further increased.

The dye-sensitized solar cell module according to the present invention includes the electrolyte layer from a surface including a shortest distance A from the metal wiring to the partition and a position where the distance from the metal wiring is the shortest from the metal wiring. It is preferable that the shortest distance B to the surface including the position where the distance from the shortest distance satisfies the following relational expression: 4.0 ≧ (A + B) / A> 1.0. If the shortest distance A and the shortest distance B satisfy the above relational expression, the long-term reliability can be further enhanced while increasing the photoelectric conversion efficiency of the dye-sensitized solar cell module.

According to the present invention, a dye-sensitized solar cell module with high photoelectric conversion efficiency and high reliability can be provided.

It is sectional drawing which shows schematic structure of an example of a dye-sensitized solar cell module. (A)-(d) is a perspective view which shows the first half part of an example of the manufacturing process of a dye-sensitized solar cell module. (A)-(d) is an end view showing the latter half of an example of the manufacturing process of the dye-sensitized solar cell module. (A)-(d) is an end view which shows the first half part of the other example of the manufacturing process of a dye-sensitized solar cell module. (A)-(d) is an end view showing the latter half of another example of the manufacturing process of the dye-sensitized solar cell module.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, in each figure, what attached | subjected the same code | symbol shall show the same component.

Here, the dye-sensitized solar cell module of the present invention is a dye-sensitized solar cell module formed by connecting a plurality of cells in series, particularly a dye-sensitized solar cell module having a Z-type integrated structure. .

And as an example of the dye-sensitized solar cell module of the present invention, the dye-sensitized solar cell module having a Z-type integrated structure is not particularly limited. For example, FIG. 1 is a sectional view in the thickness direction. And a dye-sensitized solar cell module 10 as shown in FIG.

Here, the dye-sensitized solar cell module 10 shown in FIG. 1 is a so-called dye-sensitized solar cell module in which a plurality of (four in the illustrated example) cells partitioned by the partition walls 8 are connected in series. It has a Z-type integrated structure. The dye-sensitized solar cell module 10 includes a photoelectrode substrate including a photoelectrode substrate 1 and a plurality of (four in the illustrated example) photoelectrodes 2 provided on the photoelectrode substrate 1 so as to be separated from each other. 3 and a counter electrode substrate 7 including a counter electrode substrate 5 and a plurality of (four in the illustrated example) counter electrodes 6 provided on the counter electrode substrate 5 so as to be spaced apart from each other. With the partition wall 8 interposed between the counter electrode substrate 7 and the counter electrode substrate 7, the photoelectrode 2 and the counter electrode 6 forming each cell face each other with the electrolyte layer 4 interposed therebetween (that is, so as to form a cell). And a structure in which the photoelectrode 2 of one cell and the counter electrode 6 of the other cell are bonded so as to be electrically connected via the cell connection portion 9 between adjacent cells. Yes. Each cell of the dye-sensitized solar cell module 10 includes a photoelectrode 2, a counter electrode 6 facing the photoelectrode 2, and an electrolyte layer 4 provided between the photoelectrode 2 and the counter electrode 6. I have.

In addition, the structure of the dye-sensitized solar cell module of the present invention is not limited to the structure shown in FIG. Specifically, the dye-sensitized solar cell module 10 shown in FIG. 1 is provided on the photoelectrode conductive layer 21 provided on the photoelectrode substrate 1 and on a part of the photoelectrode conductive layer 21. The photoelectrode 2 is provided with the porous semiconductor fine particle layer 22 carrying (adsorbing) the sensitizing dye. The photoelectrode of the dye-sensitized solar cell module of the present invention is dye-sensitized. It can be set as the arbitrary photoelectrode which can form a type solar cell. The dye-sensitized solar cell module 10 includes a counter electrode conductive layer 61 provided on the counter electrode substrate 5 and a catalyst layer 62 provided on a part of the counter electrode conductive layer 61. Although the counter electrode 6 is provided, the counter electrode of the dye-sensitized solar cell module of the present invention can be any counter electrode that can form a dye-sensitized solar cell. Further, in the dye-sensitized solar cell module 10, a part of the surface of the counter electrode conductive layer 61 wider than the catalyst layer 62 and light wider than the porous semiconductor fine particle layer 22 on which the sensitizing dye is adsorbed. Although a part of the electrode conductive layer 21 is electrically connected via the cell connection portion 9, the structure and position where the cells are connected in series are not limited to the structure and position shown in FIG. .

Here, the photoelectrode substrate 3 of the dye-sensitized solar cell module 10 shown in FIG. 1 includes a photoelectrode substrate 1 and a plurality of photoelectrodes 2 provided on the photoelectrode substrate 1 so as to be separated from each other. And. The photoelectrode 2 includes a photoelectrode conductive layer 21 provided on the photoelectrode substrate 1 and a porous semiconductor fine particle layer 22 provided on a part of the photoelectrode conductive layer 21. Yes. The photoelectrode conductive layer 21 is provided with a gap 23 therebetween. The adjacent photoelectrodes 2 are provided so as to be electrically insulated from each other. This insulation is not particularly limited, for example, by forming the cell connection portion 9 present in the gap 23 between the adjacent photoelectrode conductive layers 21 using a specific conductive resin composition described later, Can be achieved.

And as the base material 1 for photoelectrodes, there is no particular limitation, and a known base material having transparency in the visible region such as a glass plate or a plastic film can be used. Among them, from the viewpoint of obtaining a dye-sensitized solar cell module that is thin and excellent in flexibility, it is preferable to use a flexible plastic film as the substrate 1 for photoelectrodes. In addition, as a plastic film which has flexibility, it is not specifically limited, For example, polyester resins, such as a polyethylene terephthalate (PET) and a polyethylene naphthalate (PEN), an acrylic resin, an epoxy resin, a fluororesin, a silicone resin, Examples include films made of polycarbonate resin, diacetate resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, and the like.

The photoelectrode conductive layer 21 is not particularly limited, and a known conductive layer such as a conductive layer made of a conductive material such as metal, metal oxide, or conductive carbon material is used. Can do. Among these, a transparent conductive layer is preferably used as the photoelectrode conductive layer 21, and a transparent conductive layer made of a metal oxide such as fluorine-doped tin oxide (FTO) or indium tin oxide (ITO), or carbon. It is more preferable to use a transparent conductive layer composed of a fibrous carbon nanomaterial having conductivity such as a nanotube. In addition, the transparent conductive layer comprised from the fibrous carbon nanomaterial which has electroconductivity, such as a carbon nanotube, may further contain the binder for binding this material. Moreover, as a method of forming the photoelectrode conductive layer 21 on the photoelectrode substrate 1, a known forming method such as a method combining sputtering and etching or screen printing can be used.

Further, the porous semiconductor fine particle layer 22 carrying (adsorbing) a sensitizing dye is not particularly limited, and an organic dye or a porous semiconductor fine particle layer containing particles of an oxide semiconductor such as titanium oxide can be used. A porous semiconductor fine particle layer formed by adsorbing a sensitizing dye such as a metal complex dye can be used. In addition, as a method for forming the porous semiconductor fine particle layer on the photoelectrode conductive layer 21, a known forming method such as screen printing or coating can be used. Further, as a method for adsorbing the sensitizing dye to the porous semiconductor fine particle layer, a known method such as immersion of the porous semiconductor fine particle layer in a solution containing the sensitizing dye can be used.

The counter electrode substrate 7 of the dye-sensitized solar cell module 10 includes a counter electrode substrate 5 and a plurality of counter electrodes 6 provided on the counter electrode substrate 5 so as to be separated from each other. . The counter electrode 6 includes a counter electrode conductive layer 61 provided on the counter electrode substrate 5 and a catalyst layer 62 provided on a part of the counter electrode conductive layer 61. The catalyst layer 62 faces the porous semiconductor fine particle layer 22 of the photoelectrode 2.
The counter electrodes 6 adjacent to each other are provided so as to be electrically insulated from each other. This insulation is not particularly limited, and can be achieved, for example, by interposing the partition wall 8 in the gap between the opposing electrodes 6 adjacent to each other.

Further, as the counter electrode substrate 5, the same substrate as the photoelectrode substrate 1 can be used.

As the counter electrode conductive layer 61, a conductive layer similar to the photoelectrode conductive layer 21 can be used.

Furthermore, as the catalyst layer 62, any catalyst layer containing a component that can function as a catalyst such as platinum or a carbon material can be used.

Moreover, the partition wall 8 of the dye-sensitized solar cell module 10 is provided between the photoelectrode substrate 3 and the counter electrode substrate 7 and surrounds each of the electrolyte layer 4 and the cell connection portion 9. In other words, the space in which the electrolyte layer 4 is provided and the space in which the cell connection portion 9 is provided are partitioned by the photoelectrode substrate 3, the counter electrode substrate 7, and the partition walls 8.

Specifically, in FIG. 1, the partition wall 8 is a photoelectrode conductive layer 21 (porous semiconductor fine particle layer 22 of the photoelectrode 2 of the photoelectrode substrate 3 on one side in the width direction of each cell (left side in FIG. 1). 1 is provided between the counter electrode substrate 7 and the counter electrode substrate 5, and the other side in the width direction of each cell (in FIG. 1). (Right side), the photoelectrode conductive layer 21 of the photoelectrode 2 of the photoelectrode substrate 3 (the portion located on the other side in the width direction from the portion where the porous semiconductor fine particle layer 22 is formed) or the light of the photoelectrode substrate 3 Provided between the electrode substrate 1 and the counter electrode conductive layer 61 of the counter electrode 6 of the counter electrode substrate 7 (the portion located on the other side in the width direction from the portion where the catalyst layer 62 is formed). Yes. The electrolyte layers 4 and the cell connection portions 9 are alternately provided between the partition walls 8.

The partition wall 8 is not particularly limited, and the electrolyte layer hole formed at a position corresponding to the position where the electrolyte layer 4 is provided and the connection part hole formed at a position corresponding to the cell connection part 9. Or a partition formed by applying a thermosetting or photocurable resin and curing the applied resin, or the like. Among these, from the viewpoint of manufacturability, the partition wall 8 is preferably formed using an adhesive sheet. From the viewpoint of improving the bonding strength and bonding accuracy between the photoelectrode substrate 3 and the counter electrode substrate 7. It is preferable to use an adhesive sheet having thermoplasticity.
The adhesive sheet is not particularly limited, and examples thereof include resins such as acrylic resins, epoxy resins, fluorine resins, olefin resins, silicone resins, polyisobutylene resins, polyamide resins, and ionomer resins. The sheet | seat (for example, Surlyn film etc.) formed using can be used.

Also, the electrolyte layer 4 of the dye-sensitized solar cell module 10 is provided in a space surrounded by the porous semiconductor fine particle layer 22 of the photoelectrode 2, the catalyst layer 62 of the counter electrode 6, and the partition walls 8. The electrolyte layer 4 is not particularly limited, and can be formed using any electrolytic solution, gel electrolyte, or solid electrolyte that can be used in the dye-sensitized solar cell.

Furthermore, the cell connection portion 9 of the dye-sensitized solar cell module 10 electrically connects cells adjacent to each other in series. Specifically, the cell connection portion 9 includes the photoelectrode conductive layer 21 of the photoelectrode 2 of the cell located on the right side in FIG. 1 and the counterelectrode conductive layer of the counter electrode 6 of the cell located on the left side in FIG. 61 is electrically connected.

The cell connection portion 9 of the dye-sensitized solar cell module 10 includes a wiring 91 formed on the photoelectrode conductive layer 21 of the photoelectrode 2 so as to be separated from the porous semiconductor fine particle layer 22, and the photoelectrode substrate 3. The conductive resin composition 93 is filled in a space surrounded by the counter electrode substrate 7 and the partition walls 8. In addition, in the dye-sensitized solar cell module 10 shown in FIG. 1, although the cell connection part 9 is formed using the wiring 91 and the conductive resin composition 93, in the dye-sensitized solar cell module of this invention, The cell connection portion may be formed using only the conductive resin composition. The wiring may be formed on the counter electrode conductive layer 61 of the counter electrode 6.

Here, the wiring 91 is not particularly limited, and wiring made of a conductive material such as metal and metal oxide can be used. Among these, from the viewpoint of increasing the photoelectric conversion efficiency of the dye-sensitized solar cell module by reducing the resistance of the cell connection portion 9, the wiring 91 is a metal wiring such as a copper wiring, a gold wiring, a silver wiring, or an aluminum wiring. It is preferable to use it. As a method for forming the wiring 91 on the photoelectrode conductive layer 21, a known forming method such as sputtering or screen printing can be used.

The conductive resin composition 93 contains a resin and conductive particles, the average particle diameter of the conductive particles is 0.5 μm or more and 30 μm or less, and the content ratio of the conductive particles is 0.1. It is necessary to use a composition that is at least 10% by volume. This is because when the average particle size and / or content ratio of the conductive particles is outside the above range, the photoelectric conversion efficiency of the dye-sensitized solar cell module is lowered.
In the dye-sensitized solar cell module 10, the conductive resin composition 93 is also filled in the gaps 23 between the adjacent photoelectrode conductive layers 21, but the conductive resin composition 93 is conductive. Since the average particle diameter of the particles is 0.5 μm or more and 30 μm or less and the content ratio of the conductive particles is 0.1% by volume or more and 10% by volume or less, a conductive network is formed by the conductive particles in the gap 23. This can prevent the conductive layers 21 for photoelectrodes adjacent to each other from conducting (that is, insulation between the photoelectrodes 2 adjacent to each other can be ensured).
The median diameter of the conductive particles contained in the solar cell module is, for example, the conductive particles contained in the resulting melt by dissolving the conductive resin contained in the solar cell module using an appropriate solvent. Can be obtained by measuring using a laser diffraction method based on JIS Z8825.

Here, the resin of the conductive resin composition 93 is not particularly limited, and examples thereof include a resin cured by irradiation with actinic radiation or ultraviolet rays, or a resin cured by heating. Specific examples of the resin of the conductive resin composition 93 include (meth) acrylic resins; bisphenol type epoxy resins, novolac type epoxy resins, cyclic epoxy resins, alicyclic epoxy resins, and other epoxy resins; silicone resins; It is done. Arbitrary hardening agents, such as a radical initiator, a cationic hardening agent, and an anionic hardening agent, can be used for the said resin, and a polymerization form is not specifically limited, such as addition polymerization and ring-opening polymerization.

In addition, the conductive particles of the conductive resin composition 93 are not particularly limited, and for example, metal particles, metal oxide particles, conductive carbon particles, and the like can be used.
And the average particle diameter of electroconductive particle needs to be 0.5 micrometer or more, it is preferable that it is 5 micrometers or more, it is necessary to be 30 micrometers or less, and it is preferable that it is 10 micrometers or less. When the average particle diameter of the conductive particles is equal to or larger than the lower limit, it is possible to reliably prevent the conductive layers 21 for photoelectrodes adjacent to each other from conducting. Moreover, if the average particle diameter of electroconductive particle is below the said upper limit, the resistance of the cell connection part 9 can be reduced and the photoelectric conversion efficiency of a dye-sensitized solar cell module can be improved.
Furthermore, the content ratio of the conductive particles needs to be 0.1% by volume or more, preferably 1% by volume or more, needs to be 10% by volume or less, and is 6% by volume or less. More preferred. If the content rate of electroconductive particle is more than the said lower limit, the resistance of the cell connection part 9 can be reduced and the photoelectric conversion efficiency of a dye-sensitized solar cell module can further be improved. Further, if the content ratio of the conductive particles is not more than the above upper limit value, the viscosity of the composition forming the conductive resin composition 93 can be appropriately lowered, and the composition can be easily filled. It is possible to more reliably prevent the conductive layers 21 for photoelectrodes adjacent to each other from conducting.

In addition, the cell connection part 9 using the conductive resin composition 93 described above is not particularly limited. For example, the cell connection part 9 includes an uncured resin and conductive particles in a position where the cell connection part 9 is formed. It can be formed by filling a cured conductive resin composition and curing the filled uncured conductive resin composition.

And according to the dye-sensitized solar cell module 10 having the above-described configuration, the cell connection portion 9 is formed using the conductive resin composition 93 containing conductive particles having a predetermined average particle diameter in a predetermined ratio. Since it forms, the resistance of the cell connection part 9 can be reduced and the photoelectric conversion efficiency and reliability can be improved, preventing the adjacent photoelectrodes 2 from conducting.

Further, according to the dye-sensitized solar cell module 10, since the conductive resin composition 93 is also disposed in the gap 23 between the adjacent photoelectrode conductive layers 21, for example, a metal wiring as the wiring 91. Even when the electrolyte is used, components such as the electrolyte solution and the gel electrolyte constituting the electrolyte layer 4 leak to the cell connection portion 9 side, and the leaked components come into contact with the wiring 91 to corrode the wiring 91. It can be prevented well. Therefore, a dye-sensitized solar cell module excellent in long-term reliability can be obtained.

In the dye-sensitized solar cell module 10, when the gap 23 is provided between the photoelectrode conductive layers 21 adjacent to each other, the width of the gap 23 (that is, the distance between the photoelectrode conductive layers 21) is set to be conductive. The average particle diameter of the conductive particles contained in the resin composition is preferably 3 times or more, more preferably 5 times or more, more preferably 30 times or less, and preferably 10 times or less. Is more preferable. If the distance between the photoelectrode conductive layers 21 is equal to or greater than the lower limit, insulation between the photoelectrodes 2 adjacent to each other can be more reliably ensured, and the reliability of the dye-sensitized solar cell module 10 can be further increased. This is because it can be improved. Moreover, if the distance between the conductive layers 21 is set to the upper limit value or less, the increase in the resin amount suppresses the resistance of the cell connection portion 9 from increasing, and the photoelectric conversion efficiency of the dye-sensitized solar cell module 10 is sufficient. This is because it can be improved. In addition, in addition to making the average particle diameter and the content ratio of the conductive particles of the conductive resin composition 93 within the specific numerical range described above, the distance between the photoelectrode conductive layers 21 is set to the specific numerical range described above. By making it inside, the insulation between the photoelectrodes 2 adjacent to each other can be more reliably ensured.

The gaps 23 between the photoelectrode conductive layers 21 can be formed by laser processing such as CO ₂ laser, excimer laser, YAG laser, etching processing, or the like. The gap 23 of the photoelectrode conductive layer 21 is usually 1 μm or more and 1000 μm or less, preferably 30 μm or more and 500 μm or less, more preferably 40 μm or more and 300 μm or less, and particularly preferably 50 μm or more and 250 μm or less. If the width of the gap 23 of the photoelectrode conductive layer 21 is within such a range, the insulation between the photoelectrodes 2 adjacent to each other is more reliably ensured, and the reliability of the dye-sensitized solar cell module 10 is further increased. And the photoelectric conversion efficiency of the dye-sensitized solar cell module 10 can be further improved.
FIG. 1 illustrates a structure in which the photoelectrode conductive layer 21 is disposed with a gap 23 as an example of the structure of the dye-sensitized solar cell module 10 of the present invention. The gap 23 between the photoelectrode conductive layers 21 has been described as an example. However, as described above, the structure shown in FIG. 1 is merely an example, and for example, a gap between adjacent counter electrode conductive layers 61 may correspond to the gap 23. Also in this case, it is preferable to be within a specific numerical range similar to the gap 23 between the photoelectrode conductive layers 21.

In addition, when the wiring 91 such as a metal wiring is provided in the dye-sensitized solar cell module 10 as shown in FIG. 1 in an enlarged manner, the region surrounded by the two-dot chain line in the dye-sensitized solar cell module 10 is shown. The shortest distance A from the wiring 91 to the partition wall 8 and the shortest distance B from the surface including the position on the partition wall 8 where the distance from the wiring 91 is shortest to the surface including the position where the distance from the electrolyte layer 4 is shortest. Preferably satisfies the following relational expression: 4.0 ≧ (A + B) / A> 1.0, (A + B) / A is more preferably 1.5 or more, and 2.0 or more. More preferably, it is more preferably 3.0 or less. If (A + B) / A is equal to or greater than the above lower limit value, it is more reliable that components such as the electrolyte and gel electrolyte constituting the electrolyte layer 4 leak to the cell connection portion 9 side and come into contact with the wiring 91. This is because the long-term reliability of the dye-sensitized solar cell module 10 can be further improved. If (A + B) / A is equal to or less than the above upper limit, the partition wall 8 is thinned to sufficiently secure an area such as the porous semiconductor fine particle layer 22 and the photoelectric conversion efficiency of the dye-sensitized solar cell module 10. It is because it can fully improve. In the enlarged view of FIG. 1, the partition wall 8 and the electrolyte layer 4 are illustrated as being adjacent to each other, but a gap may exist between the partition wall 8 and the electrolyte layer 4. Further, the shortest distance B described above is the partition wall 8 (that is, the figure) separating the electrolyte layer 4 disposed on the porous semiconductor fine particle layer 22 provided on the same photoelectrode conductive layer 21 as the wiring 91. 1 substantially corresponds to the thickness of the partition wall 8) located on the right side of the wiring 91.

Furthermore, in the dye-sensitized solar cell module 10, when the wiring 91 such as a metal wiring is provided, the width of the cell connection portion 9 is preferably more than 1.1 times the width of the wiring 91, and 1.3 times. More preferably, it is 1.7 times or more, further preferably 3.0 times or less, and more preferably 2.5 times or less. If the width of the cell connection portion 9 is more than 1.1 times the width of the wiring 91, a gap is provided between the wiring 91 and the wall surface of the partition wall 8, and a conductive resin is provided between the wiring 91 and the wall surface of the partition wall 8. Composition 93 can be entrained. Therefore, even when a component such as an electrolytic solution that forms the electrolyte layer 4 oozes out between the partition wall 8 and the photoelectrode substrate 3 during use of the dye-sensitized solar cell module 10, It is because it can suppress that the wiring 91 corrodes with a component. On the other hand, if the width of the cell connection portion 9 is 3.0 times or less the width of the wiring 91, the amount of the conductive resin composition 93 used for forming the cell connection portion 9 increases and the resistance of the cell connection portion 9 is increased. It is because it can suppress that this increases. Therefore, when the width of the cell connection portion 9 is within the above range, a dye-sensitized solar cell module having excellent long-term reliability and photoelectric conversion efficiency can be obtained.

The dye-sensitized solar cell module 10 having the above-described configuration is not particularly limited and can be manufactured, for example, as shown in FIGS. Specifically, first, as shown in the first half of the manufacturing process in FIG. 2, after producing the photoelectrode substrate 3 including the photoelectrode 2 (photoelectrode substrate production process), on the produced photoelectrode substrate 3, An adhesive sheet having an electrolyte layer hole 81 formed at a position corresponding to the position where the electrolyte layer 4 is provided, and a connection portion hole 82 formed at a position corresponding to the cell connection portion 9 for connecting cells in series. (Partition wall) 8 is arranged (sheet arrangement process). Next, as shown in FIG. 3, an uncured conductive resin composition 92 is filled in the connection portion hole 82 of the adhesive sheet 8 disposed on the photoelectrode substrate 3 (resin composition filling step). Furthermore, the components constituting the electrolyte layer 4 such as an electrolyte solution are filled in the electrolyte layer holes 81 of the adhesive sheet 8 (electrolyte layer filling step). Thereafter, as shown in FIG. 3, the counter electrode substrate 7 including the counter electrode 6 is bonded to the photoelectrode substrate 3 via the adhesive sheet 8 (bonding step), and further, an uncured conductive resin composition. The cell connection portion 9 is formed by curing 92, and the photoelectrode substrate 3 and the counter electrode substrate 7 are firmly bonded (bonding step).

Here, in the photoelectrode substrate manufacturing step, first, as shown in FIG. 2A, a plurality of (four in the illustrated example) photoelectrode conductive layers 21 corresponding to the number of cells to be formed are separated from each other. It forms on the base material 1 for photoelectrodes. Next, as shown in FIG. 2B, the wiring 91 is formed on the photoelectrode conductive layer 21 formed on the photoelectrode substrate 1. Thereafter, as shown in FIG. 2C, a porous semiconductor fine particle layer 22 having adsorbed a sensitizing dye is formed on a part of each photoelectrode conductive layer 21 to obtain a photoelectrode substrate 3. Here, the wiring 91 and the porous semiconductor fine particle layer 22 are formed on the photoelectrode conductive layer 21 while being separated from each other.
In the example shown in FIG. 2, the wiring 91 is formed after the photoelectrode conductive layer 21 is formed and before the porous semiconductor fine particle layer 22 is formed. You may form on the conductive layer 21 for photoelectrodes before forming. Further, the formation of the wiring 91 may be performed after the sheet placement process is performed.

Next, in the sheet arranging step, as shown in FIG. 2D, the electrolyte layer hole 81 formed at the position corresponding to the position where the electrolyte layer 4 is provided and the position corresponding to the position where the cell connecting portion 9 is provided. The adhesive sheet 8 having the formed connection part hole 82 is positioned so that the electrolyte layer hole 81 is located on the place where the electrolyte layer 4 is provided, and the connection part hole 82 is provided with the cell connection part 9. It arrange | positions on the photoelectrode board | substrate 3 so that it may be located on a place. More specifically, as shown in FIG. 3A, for example, the adhesive sheet 8 includes a porous semiconductor fine particle layer 22 having adsorbed a sensitizing dye accommodated in an electrolyte layer hole 81 and a wiring 91. Is accommodated in the connection portion hole 82, and the photoelectrode 2 and the counter electrode 6 can be electrically connected via the cell connection portion 9 provided in the connection portion hole 82. 3 is arranged.

In the resin composition filling step, as shown in FIG. 3A, the uncured conductive resin composition 92 is filled in the connection portion holes 82 of the adhesive sheet 8 disposed on the photoelectrode substrate 3. . Here, the filling of the uncured conductive resin composition 92 into the connection portion hole 82 is not particularly limited, and can be performed using a screen printing apparatus, a dispenser, or the like. In this example, the uncured conductive resin composition 92 is also filled in the gaps between the photoelectrode conductive layers 21.
In addition, you may implement a resin composition filling process after the electrolyte layer filling process mentioned later.

Here, when a thermoplastic sheet is used as the adhesive sheet 8 described above, it is preferable to use a composition containing a thermosetting resin that is cured by heating as the uncured conductive resin composition 92. When the adhesive sheet 8 has thermoplasticity, if a composition containing a thermosetting resin is used as the conductive resin composition 92, the conductive resin composition 92 can be cured and lighted by heating once in the bonding step described later. This is because adhesion between the electrode substrate 3 and the counter electrode substrate 7 can be achieved.

In the electrolyte layer filling step, as shown in FIG. 3B, the components constituting the electrolyte layer 4 such as the electrolyte solution are filled in the electrolyte layer holes 81 of the adhesive sheet 8 disposed on the photoelectrode substrate 3. Thus, the electrolyte layer 4 is formed. In FIG. 3B, the components constituting the electrolyte layer 4 such as the electrolytic solution are filled up to the upper end of the electrolyte layer hole 81, but the filling amount of the electrolytic solution or the like is the air in the formed cell. Any adjustment can be made as long as it is within the range not mixed.
Moreover, the filling of the components constituting the electrolyte layer 4 such as the electrolytic solution into the electrolyte layer holes 81 is not particularly limited, and can be performed using a screen printing apparatus or a dispenser.

In the bonding step, as shown in FIG. 3C, the counter electrode substrate 7 including the counter electrodes 6 (four in the illustrated example) corresponding to the number of cells is attached to the photoelectrode via the adhesive sheet 8. The substrate 3 is bonded. Specifically, in the bonding step, the counter electrode substrate 7 and the photoelectrode substrate 3 are opposed to each other with at least a part of the counter electrode 6 and at least a part of the photoelectrode 2 sandwiching the electrolyte layer 4 (that is, To form a cell). Note that, from the viewpoint of preventing air from being mixed into the cell, the bonding is preferably performed in a reduced pressure environment.

In the illustrated example, the counter electrode substrate 7 and the photoelectrode substrate 3 are bonded so that the catalyst layer 62 of the counter electrode 6 and the porous semiconductor fine particle layer 22 of the photoelectrode 2 face each other with the electrolyte layer 4 interposed therebetween. ing. After bonding, the adhesive sheet 8 becomes a partition wall that surrounds the electrolyte layer 4 and the cell connection portion 9.

In the bonding step, as shown in FIG. 3 (d), the uncured conductive resin composition 92 is cured to form a conductive resin composition 93 to form the cell connection portion 9, and the photoelectrode substrate 3 And the counter electrode substrate 7 are firmly bonded.

Here, the method for curing the conductive resin composition 92 may be appropriately selected according to the type of the curable resin contained in the conductive resin composition 92. As described above, when a thermoplastic sheet is used as the adhesive sheet 8 and a composition containing a thermosetting resin is used as the conductive resin composition 92, the conductive resin composition can be obtained by a single heating. Since the curing of 92 and the adhesion of the photoelectrode substrate 3 and the counter electrode substrate 7 can be achieved, the dye-sensitized solar cell module can be efficiently manufactured. Furthermore, if a thermoplastic sheet is used as the adhesive sheet 8, the adhesive sheet 8 can be made to follow the shapes of the photoelectrode substrate 3 and the counter electrode substrate 7 by heating. Therefore, the partition wall 8 can be formed satisfactorily. However, when a thermoplastic sheet is used as the adhesive sheet 8, the temperature at which the adhesive sheet 8 and the uncured conductive resin composition 92 are heated is the curing contained in the uncured conductive resin composition 92. It is preferable that the temperature is not less than the curing temperature of the adhesive resin and not more than 10 ° C. higher than the softening point of the adhesive sheet 8. In other words, the curing temperature of the curable resin used in combination with the thermoplastic adhesive sheet 8 is preferably 10 ° C. or lower than the softening point of the adhesive sheet 8. When the adhesive sheet 8 is heated at an excessively high temperature, the adhesive sheet 8 may be excessively softened and the adhesiveness may be lowered, or a component constituting the electrolyte layer 4 such as an electrolytic solution may be leaked. Because. The softening point and curing temperature can be measured by differential scanning calorimetry and viscoelasticity measurement. In addition, the temperature at which the adhesive sheet 8 and the uncured conductive resin composition 92 are heated is determined from the viewpoint of suppressing the generation of bubbles in the electrolyte layer 4 of components such as an electrolyte solution that forms the electrolyte layer 4. It is preferably less than the boiling point.

And according to an example of the manufacturing method of the dye-sensitized solar cell module mentioned above, after filling the component which comprises electrolyte layer 4, such as electrolyte solution, in the hole 81 for electrolyte layers of the adhesive sheet 8, a photoelectrode substrate 3 and the counter electrode substrate 7 are bonded together, so that a step of forming a hole in the substrate after the bonding and filling with an electrolytic solution or the like is unnecessary, and the dye-sensitized solar cell module can be efficiently manufactured. it can.

Further, since the adhesive sheet 8 is used instead of the liquid sealing material that is easily deformed when an external force is applied, the positional accuracy and height when the photoelectrode substrate 3 and the counter electrode substrate 7 are bonded together. The accuracy can be sufficiently increased. Further, the strength of the laminate obtained by bonding the photoelectrode substrate 3 and the counter electrode substrate 7 and the dye-sensitized solar cell module is moderately increased, and the handling properties of the laminate and the dye-sensitized solar cell module are improved. Can be improved. In addition, since the electrolyte layer hole 81 of the adhesive sheet 8 is filled with a component constituting the electrolyte layer 4 such as an electrolytic solution, an electrolyte such as an electrolytic solution is used compared to the case where a liquid sealing material is used. It is possible to suppress the dissolution and deformation of the adhesive sheet 8 at the contact surface with the component constituting the layer 4 and increase the bonding strength between the photoelectrode substrate 3 and the counter electrode substrate 7.

In the dye-sensitized solar cell module 10 of the above example, the conductive resin composition 93 is present in the gap 23 between the adjacent photoelectrode conductive layers 21, and the wiring 91 is provided on the photoelectrode conductive layer 21. In the dye-sensitized solar cell module of the present invention, the conductive resin composition may be present in the gap between the opposing electrode conductive layers adjacent to each other, and the wiring is provided on the opposing electrode conductive layer. It may be formed. Here, the dye-sensitized solar cell module in which the conductive resin composition is present in the gap between the conductive layers for the counter electrode and the wiring is formed on the conductive layer for the counter electrode is electrically conductive in the gap between the conductive layers for the counter electrode. A configuration similar to that of the dye-sensitized solar cell module 10 of the above example can be adopted except that the resin composition is present and wiring is formed on the conductive layer for the counter electrode.

The dye-sensitized solar cell module in which a gap is provided between the counter electrode conductive layers and the wiring is formed on the counter electrode conductive layer is not particularly limited. For example, as shown in FIGS. Can be manufactured. Specifically, first, as shown in FIG. 4 showing the first half of the manufacturing process, after manufacturing the counter electrode substrate 7 including the counter electrode 6 (counter electrode substrate manufacturing process), on the counter electrode substrate 7 thus manufactured. Adhesiveness having an electrolyte layer hole 81 formed at a position corresponding to the position where the electrolyte layer 4 is provided, and a connection portion hole 82 formed at a position corresponding to the cell connection portion 9 connecting the cells in series. A sheet (partition wall) 8 is arranged (sheet arrangement process). Next, as shown in FIG. 5, the components constituting the electrolyte layer 4 such as the electrolyte solution are filled in the electrolyte layer holes 81 of the adhesive sheet 8 (electrolyte layer filling step), and further on the counter electrode substrate 7. The uncured conductive resin composition 92 is filled in the connection portion hole 82 of the adhesive sheet 8 disposed in the resin sheet (resin composition filling step). Thereafter, as shown in FIG. 5, the counter electrode substrate 7 including the counter electrode 6 is bonded to the photoelectrode substrate 3 via the adhesive sheet 8 (bonding step), and further, an uncured conductive resin composition. The cell connection portion 9 is formed by curing 92, and the photoelectrode substrate 3 and the counter electrode substrate 7 are firmly bonded (bonding step).

Here, in the counter electrode substrate manufacturing step, first, as shown in FIG. 4A, a plurality of (four in the illustrated example) counter electrode conductive layers 61 corresponding to the number of cells to be formed are separated from each other. It forms on the base material 5 for counter electrodes. Next, as shown in FIG. 4B, the catalyst layer 62 is formed on a part of each counter electrode conductive layer 61. Thereafter, as shown in FIG. 4C, a wiring 91 is formed on the counter electrode conductive layer 61 formed on the counter electrode substrate 5 to obtain the counter electrode substrate 7. The wiring 91 and the catalyst layer 62 are formed on the counter electrode conductive layer 61 so as to be separated from each other.
In the example shown in FIG. 4, the wiring 91 is formed after the catalyst layer 62 is formed. However, the wiring 91 may be formed on the counter electrode conductive layer 61 before the catalyst layer 62 is formed. Good. Further, the formation of the wiring 91 may be performed after the sheet placement process is performed.

In the sheet arranging step, as shown in FIG. 4D, the electrolyte layer hole 81 is formed at a position corresponding to the position where the electrolyte layer 4 is provided, and the position corresponding to the position where the cell connection portion 9 is provided. The adhesive sheet 8 having the connection portion hole 82 is positioned on the place where the electrolyte layer hole 81 is provided on the electrolyte layer 4 and the connection portion hole 82 is provided on the place where the cell connection portion 9 is provided. It arrange | positions on the counter electrode board | substrate 7 so that it may be located in FIG. More specifically, in the adhesive sheet 8, for example, as shown in FIG. 4 (d), the catalyst layer 62 is accommodated in the electrolyte layer hole 81 and the wiring 91 is accommodated in the connection portion hole 82. Furthermore, the counter electrode 6 and the photoelectrode 2 are arranged on the counter electrode substrate 7 so that they can be electrically connected via the cell connection portion 9 provided in the connection hole 82.

In the electrolyte layer filling step, as shown in FIG. 5A, the components constituting the electrolyte layer 4 such as the electrolyte solution are filled in the electrolyte layer holes 81 of the adhesive sheet 8 disposed on the counter electrode substrate 7. Thus, the electrolyte layer 4 is formed. In addition, filling with electrolyte solution etc. can be performed like the electrolyte layer filling process of the dye-sensitized solar cell module of the previous example. Moreover, you may implement an electrolyte layer filling process after the resin composition filling process mentioned later.

Further, in the resin composition filling step, as shown in FIG. 5B, an uncured conductive resin composition 92 is placed in the connection portion hole 82 of the adhesive sheet 8 disposed on the counter electrode substrate 7. Fill. The conductive resin composition can be filled in the same manner as in the resin composition filling step of the dye-sensitized solar cell module of the previous example. In the resin composition filling step, the uncured conductive resin composition 92 is also filled in the gaps between the counter electrode conductive layers 61.

As shown in FIGS. 5C and 5D, the bonding step and the bonding step are other than bonding the photoelectrode substrate 3 including the photoelectrode 2 to the counter electrode substrate 7 on which the adhesive sheet 8 is disposed. Can be carried out in the same manner as in the pasting step and bonding step of the dye-sensitized solar cell module of the previous example.

The dye-sensitized solar cell module of the present invention and the manufacturing method thereof have been described above using an example. However, the dye-sensitized solar cell module of the present invention and the manufacturing method thereof are limited to the above-described examples. However, the dye-sensitized solar cell module of the present invention and the manufacturing method thereof can be modified as appropriate.

Specifically, a part of the configuration of the example described above may be replaced with another configuration or may be omitted. For example, the partition may be formed by applying and curing a curable resin instead of the adhesive sheet.
Moreover, the dye-sensitized solar cell module of this invention may further surround the outer peripheral side of a partition with a sealing material. Specifically, in the dye-sensitized solar cell module of the present invention, the partition walls on the photoelectrode substrate or the counter electrode substrate are arranged before the photoelectrode substrate and the counter electrode substrate are bonded together. You may arrange | position a sealing material in the outer peripheral side of a position. If a sealing material is arrange | positioned, the long-term reliability of the dye-sensitized solar cell module obtained can be improved further. In addition, as a sealing material, although the known sealing material which can be used for manufacture of a dye-sensitized solar cell module can be used, it is preferable to use the sealing material which has thermoplasticity especially.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
In the examples and comparative examples, the bonding state, photoelectric conversion efficiency, and reliability of the dye-sensitized solar cell module were evaluated using the following methods, respectively.

<Lamination state after bonding process>
The sealing state of the electrolyte solution after the bonding step was observed visually and with a digital microscope (magnification: 50 times), and judged according to the following criteria. If there is no portion that is swollen, dissolved or penetrated by the electrolytic solution, it can be said that the sealing property is excellent.
A: There is no portion that is swollen, dissolved or penetrated by the electrolyte solution around the electrolyte layer.
B: There is a portion that swells, dissolves, or penetrates with the electrolytic solution around the electrolyte layer.
<Photoelectric conversion efficiency>
As a light source, a pseudo-sunlight irradiation device (PEC-L11 type, manufactured by Pexel Technologies, Inc.) in which an AM1.5G filter is attached to a 150 W xenon lamp light source was used. The amount of light was adjusted to 1 sun (AM1.5G, 100 mW / cm ² (JIS C8912 class A)). The produced dye-sensitized solar cell module was connected to a source meter (type 2400 source meter, manufactured by Keithley), and the following current-voltage characteristics were measured.
The output current was measured while changing the bias voltage from 0 V to 0.8 V in units of 0.01 V under 1 sun light irradiation. The output current was measured by integrating the values from 0.05 seconds to 0.15 seconds after changing the voltage in each voltage step. Measurement was also performed by changing the bias voltage from 0.8 V to 0 V in the reverse direction, and the average value of the measurements in the forward direction and the reverse direction was taken as the photocurrent.
The photoelectric conversion efficiency (%) was calculated from the measurement results of the current-voltage characteristics and evaluated according to the following criteria.
A: Photoelectric conversion efficiency is 3.0% or more B: Photoelectric conversion efficiency is 2.5% or more and less than 3.0% C: Photoelectric conversion efficiency is less than 2.5% <Reliability>
The produced dye-sensitized solar cell module was left in a constant temperature and humidity chamber (60 ° C., 60 RH%) for 2 days. Then, the photoelectric conversion efficiency (%) was calculated for the dye-sensitized solar cell module after being left in the same manner as described above, and evaluated according to the following criteria.
A: Photoelectric conversion efficiency is 3.0% or more B: Photoelectric conversion efficiency is 2.5% or more and less than 3.0% C: Photoelectric conversion efficiency is less than 2.5% <average particle diameter (median diameter) of conductive particles >
The median diameter of the conductive particles used for producing the dye-sensitized solar cell module was measured according to JIS Z8825.

Example 1
A dye-sensitized solar cell module in which five cells of a dye-sensitized solar cell were connected in series was produced as follows. And the bonding state, photoelectric conversion efficiency, and long-term reliability of a dye-sensitized solar cell module were evaluated. The results are shown in Table 1.
<Preparation of dye-sensitized solar cell module>
[Photoelectrode substrate manufacturing process]
An ITO-PEN film (size: 10 cm × 10 cm) having a thickness of 125 μm having a conductive layer made of indium tin oxide (ITO) on a photoelectrode substrate made of polyethylene naphthalate (PEN) film was prepared. Then, an ITO etching paste is screen printed at a width of 0.13 mm and a length of 6 cm on the 6 cm × 6 cm area in the center of the ITO-PEN film from the left side so that the intervals are 16 mm, 11 mm, 11 mm, and 11 mm. did. Then, a part of the ITO layer on the PEN film was etched by removing the dried etching paste, and five photoelectrode conductive layers made of ITO were formed on the photoelectrode substrate made of the PEN film. Further, after surface-treating the PEN film provided with the photoelectrode conductive layer with a high-pressure mercury lamp, an isopropyl alcohol solution of titanium isopropoxide having a concentration of 5 mM is applied onto the photoelectrode conductive layer by a bar coating method and dried. It was. Thereafter, the buffer layer was formed by drying for 15 minutes on a hot plate at 150 degrees.
Next, a silver wiring having a width of 5 mm and a length of 60 mm is screen-printed on a 5 mm portion from the left side in a 6 cm × 6 cm region in the center of the PEN film provided with the photoelectrode conductive layer, and further etched in each region. Silver wiring (current collection wiring) having a width of 0.7 mm and a length of 6 cm was screen-printed on a portion 0.2 mm from the left side. Pernox K3105 was used as the silver paste for screen printing. After printing the silver, the silver was fixed by heat treatment at 150 degrees for 30 minutes. The thickness of the silver wiring after drying was 8 μm.
Thereafter, the surface of the PEN film provided with the photoelectrode conductive layer and the silver wiring was irradiated with light from a high-pressure mercury lamp, and the surface was subjected to a hydrophilic treatment. Then, on each photoelectrode conductive layer, a titanium oxide layer (width 7 mm × length 55 mm) as a porous semiconductor fine particle layer was screen-printed at the center of the region where ITO was etched and the region where silver wiring was formed. . As the screen printing paste, a water-based titanium oxide paste (PECC-AW1-01, manufactured by Pexel Technologies, Inc.) was used. The thickness of the titanium oxide layer was 8 μm. Thereafter, heat treatment was performed at 150 degrees for 30 minutes.
A 6 cm × 6 cm region in the center of the PEN film provided with the photoelectrode conductive layer, silver wiring and titanium oxide layer was cut out with a cutter knife to obtain a 6 cm × 6 cm substrate. Then, the substrate was immersed in an ethanol solution of N719 dye (manufactured by Tateyama Kasei Co., Ltd.) having a concentration of 0.3 mM, and allowed to stand in a constant temperature bath at 40 degrees for 2 hours, and then the substrate was taken out. Next, it was washed with ethanol and dried under a nitrogen atmosphere, thereby adsorbing N719 dye as a sensitizing dye on the titanium oxide layer to obtain a photoelectrode substrate.
[Counter electrode substrate manufacturing process]
A 125 μm thick ITO-PEN film (size: 10 cm × 10 cm) having a conductive layer made of indium tin oxide (ITO) on a counter electrode substrate made of polyethylene naphthalate (PEN) film was prepared. Then, an ITO etching paste is screen printed at a width of 0.13 mm and a length of 6 cm on the 6 cm × 6 cm area in the center of the ITO-PEN film from the left side so that the intervals are 16 mm, 11 mm, 11 mm, and 11 mm. did. Thereafter, a part of the ITO layer on the PEN film was etched by removing the dried etching paste, and five counter electrode conductive layers made of ITO were formed on the counter electrode substrate made of the PEN film.
Next, a 5 mm portion from the left side, a 5 mm portion from the upper side, a 5 mm portion from the lower side, and a 10 mm portion from the right side of the PEN film provided with the conductive layer for the counter electrode were masked with a scotch tape. A platinum nano colloid solution (manufactured by Tanaka Kikinzoku) was applied thereto by bar coating and dried. Thereafter, the scotch tape was peeled off and treated with heated steam to fix the platinum catalyst and form a catalyst layer.
A 6 cm × 6 cm region in the center of the PEN film provided with the conductive layer for the counter electrode, the catalyst layer, and the silver wiring was cut out with a cutter knife to obtain a 6 cm × 6 cm counter electrode substrate.
[Sheet placement process]
For the formation of the partition wall, a Surlyn film (thickness 25 μm, softening point 120 ° C.) having an outer shape of 55 mm × 60 mm was prepared as a thermoplastic sheet. Then, the Surlyn film is cut out by a commercially available cutting machine, and the hole for the electrolyte is made so that the titanium oxide layer and the Surlyn film are not in direct contact with each titanium oxide layer provided on the conductive layer for each photoelectrode. Formed. Similarly, holes for connecting portions having a width S2 shown in Table 1 were formed at positions corresponding to the respective silver wirings provided on the respective conductive layers for photoelectrodes to obtain an adhesive sheet.
Then, an adhesive sheet was pressure-bonded (120 ° C., 15 seconds) on the photoelectrode substrate.
[Electrolyte filling process]
An electrolyte solution (PECE-G3, manufactured by Pexel Technologies Co., Ltd.) was filled in the electrolyte holes with a dispenser.
[Resin composition filling step]
3% by volume of epoxy resin (manufactured by 3M, Scotchweld EW2050, curing temperature 120 ° C.), thermosetting resin, and micropearl AU (manufactured by Sekisui Jushi, average particle diameter (median diameter) 8 μm) as conductive particles The resin composition obtained by adding and uniformly mixing with the rotation and revolution mixer was filled in the hole for the connection part with a dispenser.
[Lamination process]
The photoelectrode substrate was placed on the lower substrate of the aluminum bonding jig, and the counter electrode substrate was stacked thereon.
[Adhesion process]
Then, after combining the upper part of a jig | tool, it put on the hotplate heated at 120 degreeC, put a 500-g weight, and thermocompression bonded for 15 minutes. Thereafter, the jig was removed from the hot plate and allowed to cool with pressure applied. Thereafter, the obtained dye-sensitized solar cell module was taken out from the jig.

(Example 2)
In the sheet placement step, the width S2 of the connection hole formed in the Surlyn film is changed as shown in Table 1, and the screen printing position of the silver wiring is changed to maintain the shortest distance A as in Example 1. In the resin composition filling step, the same procedure as in Example 1 was conducted except that the addition amount of micropearl AU (made by Sekisui Resin, average particle diameter of 8 μm) as conductive particles was changed to 6% by volume. A sensitized solar cell module was produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
In the sheet placement step, the width S2 of the connection hole formed in the Surlyn film is changed as shown in Table 1, and the screen printing position of the silver wiring is changed so that the shortest distance A is the same distance as in Example 1. A dye-sensitized solar cell module was produced in the same manner as in Example 1 except that this was maintained. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Examples 4 to 5)
In the sheet arranging step, the width S2 of the connection hole formed in the Surlyn film and the shortest distance B are changed as shown in Table 1, and an epoxy resin (manufactured by 3M) which is a thermosetting resin in the resin composition filling step. Dye sensitization in the same manner as in Example 1 except that a polyisobutylene-based photocurable resin was used instead of Scotchweld EW2050) and ultraviolet rays of 4000 mJ / cm ² were irradiated with a UV lamp after heating in the bonding step. Type solar cell module was produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In the resin composition filling step, the dye increase was carried out in the same manner as in Example 1 except that the addition amount of micropearl AU (made by Sekisui Plastics, average particle diameter (median diameter) 8 μm) as conductive particles was changed to 30% by volume. A sensitive solar cell module was produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 2 and 3)
In the resin composition filling step, gold nanoparticles NP-AU-05 (manufactured by Tanaka Kikinzoku, average particle diameter (median diameter) 0.1 μm) instead of Micropearl AU as conductive particles were each 3% by volume (Comparative Example 2). ) And 20% by volume (Comparative Example 3) A dye-sensitized solar cell module was produced in the same manner as in Example 1 except that it was added. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
In the resin composition filling step, the example is except that micropearl AU (manufactured by Sekisui Resin) having an average particle diameter (median diameter) of 50 μm is added as conductive particles instead of micropearl AU (manufactured by Sekisui Resin) having an average particle diameter of 8 μm. In the same manner as in Example 1, a dye-sensitized solar cell module was produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 5)
In the resin composition filling step, the coloring matter was the same as in Example 1 except that the content of micropearl AU (made by Sekisui Resin, average particle diameter (median diameter) 8 μm) was changed to 0.05 vol% as the conductive particles. A sensitized solar cell module was produced. About the pasted state after the adhesion process of the created module, it was evaluated in the same manner as in Example 1. As a result, there was no portion that was swollen, dissolved or penetrated by the electrolyte solution around the electrolyte layer, and the pasted state after the adhesion process Was excellent. However, the created module did not exhibit photoelectric conversion ability at all, and the photoelectric conversion efficiency and reliability could not be evaluated. This is presumably because there were few conductive particles, the connection between the photoelectrode and the counter electrode was insufficient, and sufficient conductivity was not obtained for measuring the photoelectric conversion efficiency. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Base material for photoelectrodes 2 Photoelectrode 3 Photoelectrode substrate 4 Electrolyte layer 5 Base material for counter electrodes 6 Counter electrode 7 Counter electrode substrate 8 Partition (adhesive sheet)
9 Cell connection 10 Dye-sensitized solar cell module 21 Photoelectrode conductive layer 22 Porous semiconductor fine particle layer 23 carrying sensitizing dye 23 Gap 61 Counter electrode conductive layer 62 Catalyst layer 81 Electrolyte layer hole 82 Connection Hole 91 Wiring 92 Uncured conductive resin composition 93 Conductive resin composition

Claims

A dye-sensitized solar cell module in which a plurality of cells each including a photoelectrode, a counter electrode facing the photoelectrode, and an electrolyte layer provided between the photoelectrode and the counter electrode are connected in series. And
A photoelectrode substrate in which a plurality of photoelectrodes are spaced apart from each other on a substrate;
A counter electrode substrate that is disposed to face the photoelectrode substrate so as to form the cell, and is formed by disposing a plurality of counter electrodes on a base material apart from each other;
An electrolyte layer disposed between the photoelectrode and the counter electrode facing each other;
A cell connection part for connecting cells adjacent to each other in series;
A partition wall disposed between the photoelectrode substrate and the counter electrode substrate, and surrounding each of the electrolyte layer and the cell connection portion,
The cell connection portion includes a conductive resin composition containing a resin and conductive particles,
In the conductive resin composition, the conductive particles have an average particle diameter of 0.5 μm or more and 30 μm or less, and a content ratio of the conductive particles is 0.1 volume% or more and 10 volume% or less. Sensitized solar cell module.
The photoelectrode comprises a conductive layer, and a porous semiconductor fine particle layer formed on the conductive layer and carrying a sensitizing dye,
The cell connection portion electrically connects the conductive layer of the photoelectrode of one cell and the counter electrode of the other cell,
The dye-sensitized solar cell module according to claim 1, wherein the conductive resin composition is present between conductive layers of photoelectrodes of adjacent cells connected to each other via the cell connection portion.
The dye-sensitized solar cell module according to claim 2, wherein the distance between the conductive layers of the photoelectrodes of the cells adjacent to each other is 3 to 30 times the average particle diameter of the conductive particles.
The counter electrode includes a conductive layer and a catalyst layer formed on the conductive layer,
The cell connection portion electrically connects the conductive layer of the counter electrode of one cell and the photoelectrode of the other cell,
The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the conductive resin composition is present between conductive layers of counter electrodes of adjacent cells connected to each other via the cell connection portion. module.
The dye-sensitized solar cell module according to claim 4, wherein the distance between the conductive layers of the counter electrodes of the cells adjacent to each other is 3 to 30 times the average particle diameter of the conductive particles.
The dye-sensitized solar cell module according to any one of claims 1 to 5, wherein the cell connection portion further includes a metal wiring.
The shortest distance A from the metal wiring to the partition, and the shortest distance from the surface including the position where the distance from the metal wiring is the shortest to the surface including the position where the distance from the electrolyte layer is the shortest. The distance B is the following relational expression:
4.0 ≧ (A + B) / A> 1.0
The dye-sensitized solar cell module according to claim 6, wherein