WO2014157060A1

WO2014157060A1 - Solar cell and manufacturing method for dye-sensitized solar cell

Info

Publication number: WO2014157060A1
Application number: PCT/JP2014/058027
Authority: WO
Inventors: 佐々木　健了; 俊久藤高; 河野　充; 健二肆矢
Original assignee: 新日鉄住金化学株式会社
Priority date: 2013-03-29
Filing date: 2014-03-24
Publication date: 2014-10-02
Also published as: JPWO2014157060A1; TW201507183A

Abstract

Provided is a solar cell whereby it is possible to solve the problem of effective planar area of the cell, which is a power-generating area, being constrained as a result of a non-power-generating area occupied by an electrode structure. A solar cell (10) has: a photovoltaic conversion unit (12); a porous anode (14); and a cathode (16), in which a non-porous cathode, or non-porous material and porous material, are stacked. The anode (14) is provided on the opposite side of a light-incident side of the photovoltaic conversion unit (12), and the cathode (16) is provided so as to face the anode (14). A non-porous conductor unit (24) is provided on the opposite side of the light-incident side of a portion of the electrode of the anode (14), and a portion of the non-porous conductor unit (24) is exposed from a first aperture (26) formed on a sealing portion (20) at a position not overlapping the cathode (16) in plan view so as to form a first external connection terminal (28). Meanwhile, a portion of the electrode of the cathode (16) is exposed from a second aperture (30) formed at a position different from the first aperture (26) of the sealing portion (20) at the opposite side from the light-incident portion and forms a second external connection terminal (32).

Description

Solar cell and method for producing dye-sensitized solar cell

The present invention relates to an electrode structure of a solar cell.

The solar cell refers to all photoelectric conversion elements that convert light into electric power in a broad sense. Generally, a solar cell is a semiconductor element using a pn junction of p-type and n-type semiconductors. Examples of solar cells made of such semiconductor elements include silicon-based solar cells using silicon semiconductors, compound thin-film solar cells using compound semiconductors, and organic thin-film solar cells using organic semiconductors. On the other hand, there is also a dye-sensitized solar cell that uses the principle that a dye absorbs light and generates electrons without using a semiconductor.
In order to put all types of solar cells into practical use, it is a common big problem to achieve long-term reliability of an electrode structure that can extract power without impairing power generation efficiency. It is also an object to achieve long-term reliability of a sealing structure for shielding the solar cell from the atmospheric atmosphere, and in particular, the dye-sensitized solar cell has an electrolyte solution as described below for the battery structure. Since it is used, a reliable sealing structure is required.

The latter dye-sensitized solar cell is called a wet solar cell or a Gretzel battery, and is characterized by having an electrochemical cell structure typified by an iodine solution. Dye-sensitized solar cells are porous, such as a titania layer formed by baking titanium dioxide powder or the like on a transparent conductive glass plate (transparent conductive substrate anode electrode laminated with a transparent conductive film) and adsorbing the dye to this. It has a simple structure in which an iodine solution or the like is disposed as an electrolytic solution (electrolyte) between a counter electrode composed of a semiconductor layer and a conductive glass plate (conductive substrate cathode electrode). The dye adsorbed on the surface of the porous titanium oxide electrode absorbs light and causes excitation of electrons. The dye that has lost the electrons receives and regenerates electrons from iodine ions.
Dye-sensitized solar cells are attracting attention as low-cost solar cells because they are inexpensive and do not require large-scale equipment for production.
However, since dye-sensitized solar cells have lower power generation efficiency than other solar cells, further improvement in power generation efficiency is required.

As with other solar cells, conventional dye-sensitized solar cells have extraction electrodes that are electrically connected to the anode electrode and the cathode electrode, respectively, extending around the cell, such as opposite ends of the cell in plan view. To do. A conductor wiring is connected to the external connection terminal of each extraction electrode, and a load is provided between the two conductor wirings to generate power (see, for example, Patent Document 1).
The extension part of the extraction electrode provided in the periphery of the battery can be said to be a non-power generation area, in which the battery cannot be arranged with respect to the battery as the power generation area.

As a method for improving this problem, there is a method in which the direction of light incident toward the wiring portion (non-power generation region) provided between adjacent cells is changed to the power generation region by the incident light direction changing unit. It is disclosed (see Patent Document 2).
However, in this case, the incident light direction changing unit is arranged so as to cover a part of the power generation amount region, which causes a decrease in light transmittance. Further, the cost of providing the incident light direction changing unit is high.

In addition, the present inventors have a laminated structure part composed of a porous semiconductor layer adsorbing a dye, a conductor layer serving as a cathode electrode, and a conductive metal layer serving as an anode electrode. One end portion of each of the layer and the conductor layer extends to be provided with an extending portion, in other words, an extraction electrode, and the laminated structure portion and the extending portion are sealed together with the encapsulated electrolyte by a sealing material, and conductive metal A dye-sensitized solar cell is proposed in which a part of each layer and the extended portion of each conductor layer is exposed from a sealing material to serve as an external connection terminal (see Patent Document 3). Thereby, it can prevent reliably that electrolyte solution leaks from the extraction location of the extension part electrically connected to a conductive metal layer and a conductor layer.

WO / 2011/013581 WO / 2009/098857 WO / 2011/13581

The problem to be solved is that in the conventional solar cell, the effective planar area of the battery cell which is the power generation region is restricted by the non-power generation region occupied by the electrode structure.

A solar cell according to the present invention includes a photoelectric conversion unit, a porous anode electrode provided on the opposite side of the photoelectric conversion unit from the light incident side, and a nonporous cathode electrode or nonporous material provided to face the anode electrode. In a solar cell having a cathode electrode formed by laminating a material and a porous material and sealing the whole, a non-porous conductor portion is laminated on the side opposite to the light incident side of a part of the electrode of the anode electrode And a part of the non-porous conductor part is exposed from the first opening formed in the sealing part at a position not overlapping the cathode electrode in plan view on the side opposite to the light incident side. And a part of the cathode electrode is exposed from a second opening formed on a side opposite to the light incident side at a position different from the first opening of the sealing portion, It is a connection terminal.

In the above solar cell, preferably, the photoelectric conversion part is disposed on the light incident side, and is a porous semiconductor layer that adsorbs a dye, and the anode electrode is light incident on the porous semiconductor layer that adsorbs the dye. A non-porous conductor layer or a non-porous conductor layer provided on a surface opposite to the side, the cathode electrode being provided to face the porous conductor layer via the sealed electrolyte layer It is a conductor layer formed by laminating a porous material and a porous material.

In addition, the method for producing a dye-sensitized solar cell according to the present invention includes applying a slurry-like raw material of a porous anode electrode onto a base material that can be dissolved by chemical treatment, and sintering the slurry-like raw material to obtain a sintered body. Then, the substrate is separated from the sintered body by chemical treatment, and a dye-adsorbing porous semiconductor layer is formed on the sintered body to obtain a porous anode electrode with a dye-adsorbing porous semiconductor layer. A step of laminating a non-porous conductor portion at one corner on the anode side of a porous anode electrode with a porous semiconductor layer, and a substantially same plane dimension as a porous anode electrode with a dye-adsorbing porous semiconductor layer A non-porous cathode electrode or a non-porous material and a porous material laminated with a non-porous cathode electrode formed by notching a portion corresponding to the non-porous conductor portion when overlapped with the anode electrode. Process with a dye adsorbing porous semiconductor layer A step of laminating a porous anode electrode and a cathode electrode while aligning a non-porous conductor part of a porous anode electrode with a dye-adsorbing porous semiconductor layer and a notch part of the cathode electrode, and a resin sheet and an outer side of the cathode electrode Sealing with at least one of the sealing materials, and further forming an opening that exposes at least a part of the non-porous conductor part and a part of the cathode electrode to the outside of the cathode electrode. Features.

The solar cell according to the present invention includes a photoelectric conversion unit, a nonporous transparent anode electrode provided on the light incident side of the photoelectric conversion unit, and a nonporous material provided to face the anode electrode with the photoelectric conversion unit interposed therebetween. In a solar cell having a cathode electrode or a cathode electrode in which a non-porous material and a porous material are laminated, and the whole is sealed, a part of the electrode of the anode electrode is a flat surface on the side opposite to the light incident side. It is exposed from the third opening formed in the sealing part at a position where it does not overlap with the cathode electrode as viewed to be the third external connection terminal, and a part of the cathode electrode is sealed on the side opposite to the incident side. A fourth external connection terminal is exposed from a fourth opening formed at a position different from the third opening of the stopper.

In the solar cell according to the present invention, a nonporous conductor portion is laminated on the side opposite to the light incident side of a part of the electrode of the porous anode, and a part of the nonporous conductor portion is formed on the light incident side. Is exposed from a first opening formed in the sealing portion on the opposite side to serve as a first external connection terminal, and a non-porous cathode electrode or a cathode electrode in which a non-porous material and a porous material are laminated A part of the electrode is exposed from a second opening formed at a position different from the first opening of the sealing portion on the side opposite to the light incident side to serve as a second external connection terminal.
For this reason, since the extraction electrode does not extend to the end portions of the anode and cathode electrodes in plan view, the planar area of the battery cell as the power generation region is restricted by the non-power generation region occupied by the electrode structure. In addition, since a part of the electrode of the porous anode electrode is not directly exposed, an internal structure component such as a photoelectric conversion part in contact with the porous anode electrode is interposed through the porous anode electrode. Since it does not substantially communicate with the outside, it is possible to reduce contamination of internal structural components due to the external atmosphere.

At this time, the solar cell is a porous semiconductor layer that adsorbs the dye, the photoelectric conversion part is disposed on the light incident side, and the anode electrode is opposite to the light incident side of the porous semiconductor layer that adsorbs the dye A porous conductor layer provided on the side surface, and the cathode electrode is porous with a non-porous conductor layer or a non-porous material provided opposite to the porous conductor layer via an electrolyte layer to be sealed When the conductive layer is formed by laminating a porous material, there is little possibility that the electrolyte will leak to the outside through the porous anode electrode.

In addition, the method for producing a dye-sensitized solar cell according to the present invention can suitably obtain the above-described dye-sensitized solar cell.

Further, the solar cell according to the present invention is a third portion formed in a sealing portion at a position where a part of the electrode of the nonporous transparent anode electrode does not overlap the cathode electrode in a plan view on the side opposite to the light incident side. A fourth opening that is exposed from the opening to serve as a third external connection terminal, and a part of the cathode electrode is formed at a position opposite to the incident side at a position different from the third opening of the sealing portion. To be a fourth external connection terminal.
For this reason, since the extraction electrode does not extend to the end portions of the anode and cathode electrodes in plan view, the planar area of the battery cell as the power generation region is restricted by the non-power generation region occupied by the electrode structure. In addition, the internal structure components such as the photoelectric conversion part that is in contact with the porous anode electrode are passed through the porous anode electrode with a simple configuration that directly exposes a part of the electrode of the anode electrode. Therefore, the internal structural components can be prevented from being contaminated by the external atmosphere.

FIG. 1 is a plan view of a solar cell according to a first example of the present embodiment as viewed from the light incident side. FIG. 2 is a partial cross-sectional view as seen from the direction AA in FIG. FIG. 3 is a partial cross-sectional view as seen from the direction BB in FIG. FIG. 4 is an example showing an overlapping state of the anode electrode and the cathode electrode in the solar cell according to the first example of the present embodiment. FIG. 5 is an example different from FIG. 4 showing the overlapping state of the anode and cathode in the solar cell according to the first example of the present embodiment. FIG. 6 is a plan view of the solar cell according to the second example of the present embodiment as viewed from the light incident side. FIG. 7 is a partial cross-sectional view as seen from the direction AA in FIG. FIG. 8 is a partial cross-sectional view seen from the BB direction in FIG.

DETAILED DESCRIPTION Embodiments of the present invention (hereinafter referred to as “examples of the present embodiment”) will be described below with reference to the drawings.

First, a solar cell according to a first example of the present embodiment will be described with reference to FIGS.
A solar cell 10 according to the first example of the present embodiment shown in FIGS. 1 to 3 includes a photoelectric conversion unit 12, a porous anode electrode 14, and a non-porous cathode electrode 16. The anode 14 is provided on the side opposite to the light incident side of the photoelectric conversion unit 12. The cathode electrode 16 is provided to face the anode electrode 14. The solar cell 10 is provided with a transparent substrate 18 on the outside of the photoelectric conversion unit 12 and a transparent substrate 19 on the outside of the cathode electrode 16, and is entirely sealed with an appropriate sealing material or sealing member. 2 and 3 show an example of sealing with a sealing material (sealing portion) 20. It is sufficient to seal the outside of the cathode electrode 16, in other words, the back surface with either the substrate 19 or the sealing portion 20, and it is not essential to provide both the substrate 19 and the sealing portion 20. The cathode electrode 16 may be a laminate of a non-porous material and a porous material.
It is sufficient that the sealing material or the sealing member can seal the photoelectric conversion unit 12. As shown in FIGS. 2 and 3, a transparent substrate 18 is provided on the outer surface of the photoelectric conversion unit 12, while the cathode electrode 16 itself is formed of a non-porous metal layer. It can be said that the photoelectric conversion part 12 is sealed by 18 and the cathode electrode 16, and eventually the entire solar cell 10 is sealed. In order to securely seal by a simple method, it is preferable to omit the transparent substrate 18 and the substrate 19 and seal the entire solar cell 10 with the sealing material 20.

The solar cell 10 is preferably a dye-sensitized solar cell, the photoelectric conversion unit 12 is a porous semiconductor layer that adsorbs a dye and is disposed on the light incident side, and the anode electrode 14 is a porous that adsorbs the dye. A porous conductor layer provided on the surface opposite to the light incident side of the porous semiconductor layer, the cathode 16 being an anode via an electrolyte layer (not shown in FIGS. 1 to 3) enclosed It is a non-porous conductor layer provided opposite to the electrode 14 or a conductor layer in which a non-porous material and a porous material are laminated. The reason why the anode 14 is porous is to obtain good liquid permeability of the electrolyte between the cathode 16 side and the porous semiconductor layer, or hole or electron conductivity.
An insulating layer 22 is preferably provided between the anode 14 and the cathode 16. Thereby, even when the bending force is applied to the solar cell 10, the anode 14 and the cathode 16 can be reliably insulated.
A specific configuration of the dye-sensitized solar cell can be applied as it is, and is not essence of the present invention. Note that these configurations can also be applied to a solar cell according to a second example of the present embodiment described later.
The anode 14 may be a metal mesh, a metal layer in which numerous holes are formed in advance, or a porous metal layer formed by thermal spraying or thin film formation. The material of the anode electrode 14 is not particularly limited, but Ti, W, Ni, Pt, Ta, Nb, Zr, Au, and the like can be suitably used. The thickness of the anode 14 is not particularly limited, but is preferably 0.2 μm-600 μm.
The cathode 16 is a catalyst film or a non-porous conductive film laminated on a catalyst film. As the catalyst film, a noble metal such as platinum, high surface area carbon, or the like can be used. When a platinum film is formed by, for example, a sputtering method, a non-porous film is formed, and when high surface area carbon is formed by, for example, a carbon particle printing method, a porous film is formed. In either case, the electrolyte does not leak to the outside due to the presence of the nonporous conductive film. The thickness of the cathode electrode 16 is not particularly limited, but is preferably, for example, about several tens of nm or more from the viewpoint of obtaining good conductivity.
In the porous semiconductor layer that has adsorbed the dye, an appropriate metal oxide such as TiO 2, ZnO, or SnO 2 can be used as a semiconductor material. The thickness of the porous semiconductor layer is not particularly limited, but is preferably 10 μm or more. The dye adsorbed on the porous semiconductor layer has absorption at a wavelength of 400 nm to 1200 nm. For example, ruthenium dye, phthalocyanine dye, osmium-based, iron-based and platinum-based metal complexes, cyanine dye, methine-based , Organic dyes such as mercurochrome, xanthene, porphyrin, phthalocyanine, subphthalocyanine, azo, and coumarin.
The electrolyte layer can use a known electrolyte solution or solid electrolyte, and includes, for example, iodine, lithium ion, ionic liquid, t-butylpyridine, etc. For example, in the case of iodine, it consists of a combination of iodide ions and iodine. A redox form can be used. The electrolyte layer contains an appropriate solvent capable of dissolving these redox substances.
The transparent substrate 18 and the substrate 19 may be glass or a transparent resin sheet. The material of the transparent resin sheet is, for example, PP, PE, PS, ABS, PS, PC, PMMA, PVC, PA, POM, PET, PEN, PIB, PVB, PA6, polyimide, polyamide, polyolefin, polyester, polyether, Examples thereof include a cured acrylic resin, a cured epoxy resin, a cured silicone resin, various engineering plastics, and a cyclic polymer obtained by metathesis polymerization. The substrate 19 provided in contact with the cathode electrode 16 does not have to be transparent. The thickness of the substrate 19 is not particularly limited, and can be, for example, 1 μm to 3 mm.
As the material of the sealing portion 20, for example, an acrylic resin, an epoxy resin, an ionomer resin, a silicone resin, or the like can be used. The thickness of the sealing portion 20 that seals the substrate 19 is not particularly limited, and can be, for example, 1 μm to 10 μm.

A non-porous conductor 24 is provided on the side opposite to the light incident side of a part of the electrode of the anode 14, and a first opening formed in the sealing part 20 at a position not overlapping the cathode 16 in plan view. A part of the non-porous conductor portion 24 is exposed from 26 to form the first external connection terminal 28. On the other hand, a part of the electrode of the cathode electrode 16 is exposed from the second opening 30 formed at a position different from the first opening 26 of the sealing portion 20 on the side opposite to the light incident side, and the second external connection. Terminal 32 is used. As a result, the anode 14 and the first external connection terminal 28 are reliably electrically insulated from the cathode 16 and the second external connection terminal 32.
2 and 3, the

external connection terminals

28 and 32 seem to be largely retracted from the

openings

26 and 30, but in reality, the substrate 19 and the sealing portion 20 are thin, and thus the

external connection terminals

28 and 28 are thin. , 32 are exposed to a degree sufficient to connect the conductor wiring.
If the

external connection terminals

28 and 32 are arranged close to each other as shown in FIG. 1, it is preferable in terms of the layout of the conductor wiring connected thereto.
The material of the non-porous conductor portion 24 is not particularly limited, but is a metal material such as Ti, W, Ni, Pt, Ta, Nb, Zr and Au, or a compound thereof, or is covered with these. A material is preferred.

In order to prevent the non-porous conductor portion 24 and the cathode electrode 16 from overlapping each other in plan view, in other words, in order to ensure insulation between the non-porous conductor portion 24 and the cathode electrode 16, the following electrodes are used. It can be a structure.
For example, as shown in FIG. 4, a notch is formed at a position of the cathode electrode 16 corresponding to a region overlapping with the nonporous conductor portion 24, in other words, a region where the first opening 26 appears (indicated by an arrow A in FIG. 4). ). As a result, the area of the cathode electrode 16 that does not overlap the anode electrode 14 in plan view can be made only a cut-out portion, and the overlapping area of the anode electrode 14 and the cathode electrode 16, that is, an effective power generation area can be increased. it can.
Further, for example, as shown in FIG. 5, a region where the length dimension L2 of the cathode electrode 16 overlaps with the porous conductor portion 24 rather than the length dimension L1 of the anode electrode 14, in other words, a region where the first opening 26 appears. If it is shortened by this amount, the step of notching the cathode electrode 16 can be omitted.

In the solar cell 10 according to the first example of the present embodiment described above, the extraction electrodes that are electrically connected to the anode electrode and the cathode electrode in the conventional solar cell have opposite ends of the cell in plan view, etc. The non-power generation region generated by extending around the battery is eliminated, and the plane area of the battery cell that is the power generation region can be increased accordingly.
For example, in a battery cell in which a conventional extraction electrode is extended in a planar manner, when a planar area of a battery cell that is a power generation region can be secured by 6.56 cm ² , a part of the cathode electrode is notched in the solar battery 10. By exposing the porous conductor portion, the planar area of the battery cell that is the power generation region can be expanded to, for example, 8.38 cm ² . In consideration of the fact that the anode electrode with a dye-adsorbing titania layer in which notches are not formed functions independently of the dimensions of the cathode electrode, the planar area of the battery cell as the power generation region is the same as the anode electrode without notches. The area can be as large as, for example, 8.8 cm ² .
In addition, in the solar cell 10 according to the first example of the present embodiment, since a part of the electrode of the porous anode electrode is not directly exposed, the internal structure components such as the photoelectric conversion unit in contact with the porous anode electrode are porous. Since it does not substantially communicate with the outside via the quality anode electrode, the contamination of the internal structural components due to the external atmosphere can be reduced. When the solar cell 10 is a dye-sensitized solar cell, it can prevent that electrolyte solution leaks outside via a porous anode electrode.
In addition, since the solar cell 10 does not have an extraction electrode in the appearance seen from the light incident side, it is excellent in design.

Next, a method for manufacturing a dye-sensitized solar cell according to this embodiment will be described. According to the method for manufacturing a dye-sensitized solar cell according to this embodiment, the dye-sensitized solar cell according to the first example of this embodiment can be suitably obtained.

The method for manufacturing a dye-sensitized solar cell according to the present embodiment includes a step (first step) of obtaining a porous anode electrode with a dye-adsorbing porous semiconductor layer provided with a nonporous conductor portion, and a notch A step of obtaining a cathode electrode formed with a cathode (second step), a step of laminating a porous anode electrode with a dye-adsorbing porous semiconductor layer and a cathode electrode (third step), A step of providing at least one of the substrate having the opening formed therein or the sealing resin sheet having the sixth opening formed therein and the seventh opening formed at a position corresponding to the notch (fourth step) ).

In the first step, the slurry-like raw material of the porous anode electrode is coated on a dissolvable substrate by chemical treatment, and the slurry-like raw material is sintered to form a sintered body, and then the substrate is formed by chemical treatment. Separated from the sintered body, a dye-adsorbing porous semiconductor layer is formed on the sintered body to obtain a porous anode electrode with a dye-adsorbing porous semiconductor layer, and an anode of a porous anode electrode with a dye-adsorbing porous semiconductor layer A non-porous conductor is laminated at one corner on the pole side.
As the slurry-like raw material for the porous anode, for example, a slurry-like composition in which titanium powder having a particle size of 3 to 40 μm and an average particle size of 10 μm is mixed with, for example, an ethylcellulose binder can be used. This slurry-like composition is applied onto a base material, such as iron foil, that can be dissolved by chemical treatment using a metal mask, for example, by a squeegee method (screen printing method), and dried under reduced pressure to obtain a pre-fired shaped body. Thereafter, the molded body before firing is pressed. And this sintered compact is heated together with the iron foil and degreased. Further, firing is performed to obtain a sintered body. The sintered body is immersed in, for example, an aqueous sulfuric acid solution, and the iron foil portion in contact with the sintered body is dissolved to peel the iron foil from the sintered body. The obtained sintered body is repeatedly washed with distilled water or the like to remove sulfuric acid and then dried by heating. Further, for example, a titania paste is printed, dried and fired, and the operation of printing and firing the titania base is repeated a plurality of times to obtain a porous Ti sheet substrate with a titania layer. Furthermore, the non-film-formed portions on the four sides of the porous Ti sheet substrate with a titania layer are removed. Next, for example, a porous Ti sheet substrate with a titania layer prepared is impregnated with a mixed solvent solution of N719 dye acetonitrile and t-butyl alcohol, the dye is adsorbed on the titania surface, and the adsorbed substrate is acetonitrile and t-butyl. Wash with a mixed solvent of alcohol and dry. Further, for example, a titanium foil as a non-porous conductor portion is laminated at one corner on the back side of the porous Ti sheet substrate with the dye-adsorbing titania layer, which is not attached with the non-porous conductor portion. The provided porous anode with a dye adsorbing porous semiconductor layer is obtained.

In the second step, substantially the same plane dimensions as the porous anode electrode with a dye-adsorbing porous semiconductor layer are formed, and the portion corresponding to the nonporous conductor portion is notched when the anode electrode is overlapped with the notched portion. The formed cathode is obtained.
For example, platinum is sputtered on one surface of a titanium foil to obtain a Ti substrate with a Pt catalyst layer. Further, a hole for inserting an electrolytic solution is formed in the central portion of the Ti substrate with the Pt catalyst layer, and a portion corresponding to the non-porous conductor portion is cut out when overlapped with the anode electrode to obtain a cathode electrode. For the cathode electrode, for example, instead of platinum, a Ti substrate with a carbon catalyst layer in which carbon particles are deposited on one side of a titanium foil may be used.

In the third step, the porous anode electrode and cathode electrode with a dye-adsorbing porous semiconductor layer are aligned with the nonporous conductor portion of the porous anode electrode with the dye-adsorbing porous semiconductor layer and the notch portion of the cathode electrode. Laminate while.

In the fourth step, a substrate or a sealing resin sheet is provided outside the cathode electrode. At this time, you may provide both a board | substrate and the resin sheet for sealing. The substrate forms a fifth opening at an arbitrary position. When the sealing resin sheet is provided together with the substrate, the sealing resin sheet is formed at a position corresponding to the fifth opening. When the sealing resin sheet is provided alone, the sealing resin sheet is formed at a position corresponding to the notch while forming the sixth opening at an arbitrary position. Forming a seventh opening;
At this time, the surface of the anode electrode is also sealed with a resin sheet, or the whole battery is sealed with a sealing material.
For example, when a resin sheet is used as the substrate, for example, a PEN sheet is used, and the substrate is laminated by, for example, a roll press method. In the substrate, a notch is formed at a position corresponding to the notch of the cathode electrode, or a portion that overlaps at least a part of the non-porous conductor in plan view of the PEN sheet is opened by, for example, a drill, and the like A part of the cathode electrode is opened.
For example, a thermoplastic adhesive sheet is used as the sealing material. Similarly to the case of the PEN sheet, an opening that exposes at least a part of the non-porous conductor part and a part of the cathode electrode to the outside of the cathode electrode is formed.
Further, for example, an electrolytic solution of a tetraglyme solvent containing iodine and LiI is injected under reduced pressure from the electrolytic solution insertion hole, and then the electrolytic solution insertion hole is sealed with a UV curable resin to obtain a dye-sensitized solar cell.

Next, a solar cell according to a second example of the present embodiment will be described with reference to FIGS.
A solar cell 10a according to a second example of the present embodiment shown in FIGS. 6 to 8 includes a photoelectric conversion unit 12, a nonporous transparent anode electrode 14a, and a nonporous cathode electrode 16. The anode 14 a is provided on the light incident side of the photoelectric conversion unit 12. The cathode electrode 16 is provided to face the anode electrode 14a with the photoelectric conversion unit 12 interposed therebetween. The cathode electrode 16 may be a laminate of a non-porous material and a porous material.
The solar cell 10a can be suitably applied to a dye-sensitized solar cell and can also be suitably applied to other thin film solar cells having a transparent conductive film.
The solar cell 10 a is provided with a transparent substrate 18 outside the photoelectric conversion unit 12, and is entirely sealed with an appropriate sealing material or sealing member. 7 and 8 show an example of sealing with a sealing material (sealing portion) 20.
As with the solar cell 10, the solar cell 10 a is sufficient if the sealing material or the sealing member can seal the photoelectric conversion unit 12. As shown in FIGS. 7 and 8, a transparent substrate 18 is provided on the outer surface of the nonporous transparent anode electrode 14a, while the cathode electrode 16 itself is formed of a nonporous metal layer. It can be said that the photoelectric conversion unit 12 is sealed by the transparent substrate 18 and the cathode electrode 16, and eventually the entire solar cell 10 is sealed. In order to securely seal by a simple method, it is preferable to seal the entire solar cell 10 with the sealing material 20.
As with the solar cell 10, the solar cell 10 a may be provided with an insulating layer.
As the specific configuration of the solar cell, a well-known one of a dye-sensitized solar cell and other thin film solar cells having a transparent conductive film can be applied as it is, and since it is not the essence of the present invention, a detailed description is omitted. .

A part of the anode 14 is exposed from the third opening 26a formed in the sealing part 20 at a position not overlapping the cathode 16 in plan view on the side opposite to the light incident side of a part of the electrode of the anode 14. The third external connection terminal 28a. On the other hand, a part of the electrode of the cathode electrode 18 is exposed from a fourth opening 30a formed at a position different from the third opening 26a of the sealing portion 20 on the side opposite to the light incident side, and the fourth external connection. Terminal 32a.
In FIGS. 7 and 8, the external connection terminals 28a and 32a appear to be largely retracted from the openings 26a and 30a. However, since the sealing portion 20 is actually thin, it is necessary to connect the conductor wiring. Expose to a sufficient extent.
If the external connection terminals 28a and 32a are arranged close to each other as shown in FIG. 6, it is preferable in terms of the layout of the conductor wiring connected to them.
The material of the nonporous transparent anode electrode 14a is not particularly limited, and may be, for example, a commonly used ITO (tin doped indium film), FTO (fluorine doped tin oxide film), or SnO ₂ film. May be. In addition, a metal mesh using an inexpensive metal, a metal layer in which an infinite number of holes are formed in advance, or a metal layer formed by thermal spraying or a thin film forming method can be used.
In addition, it is a preferred embodiment to laminate a non-porous conductor portion on a part of the exposed anode electrode 14 similarly to the solar cell 10.

In order to prevent the nonporous transparent anode electrode 14a and the cathode electrode 16 of the solar cell 10a from overlapping each other in plan view, the electrode structure similar to that of the solar cell 10 described above can be used.
Moreover, the manufacturing method of the solar cell 10a can be performed according to the manufacturing method of the dye-sensitized solar cell which concerns on this Example.

In the solar cell 10a according to the second example of the present embodiment described above, in the same manner as the solar cell 10, in the conventional solar cell, the extraction electrode electrically connected to each of the anode electrode and the cathode electrode has a plan view. Thus, the non-power generation region generated by extending around the battery, such as the opposite ends of the battery, is eliminated, and the plane area of the battery cell that is the power generation region can be increased accordingly.
In addition, the solar cell 10a is substantially free from the outside through the anode electrode, and the internal structure components such as the photoelectric conversion unit in contact with the anode electrode are provided without providing the nonporous conductor 24 that is essential in the solar cell 10. Therefore, the contamination of the internal structural components due to the external atmosphere can be reduced. When the solar cell 10a is a dye-sensitized solar cell, it can prevent that electrolyte solution leaks outside via a porous anode electrode.
In addition, the solar cell 10a is excellent in the design property since there is no extraction electrode in the appearance seen from the light incident side, like the solar cell 10.

DESCRIPTION OF SYMBOLS 10, 10a Solar cell 12 Photoelectric conversion part 14, 14a Anode pole 16 Cathode pole 18 Transparent substrate 19 Substrate 20 Sealing part 22 Insulating layer 24 Nonporous conductor part 26 First opening 26a Third opening 28 First External connection terminal 28a Third external connection terminal 30 Second opening 30a Fourth opening 32 Second external connection terminal 32a Fourth external connection terminal

Claims

A photoelectric conversion unit, a porous anode electrode provided on the side opposite to the light incident side of the photoelectric conversion unit, and a non-porous cathode electrode or a non-porous material and a porous material provided to face the anode electrode. In a solar cell having a laminated cathode electrode and entirely sealed,
A non-porous conductor part is laminated on the opposite side of the anode electrode to the light incident side, and a part of the non-porous conductor part is opposite to the light incident side in plan view. Exposed from the first opening formed in the sealing portion at a position not overlapping with the cathode electrode to be a first external connection terminal, and a part of the electrode of the cathode electrode is on the side opposite to the light incident side A solar cell, wherein the solar cell is exposed from a second opening formed at a position different from the first opening of the sealing portion to serve as a second external connection terminal.
The photoelectric conversion unit is a porous semiconductor layer that is disposed on the light incident side and adsorbs a dye, and the anode electrode is on a surface opposite to the light incident side of the porous semiconductor layer that adsorbs the dye. A non-porous conductor layer or a non-porous material and a porous material, wherein the non-porous conductor layer or the non-porous material is provided so that the cathode electrode is opposed to the porous conductor layer via an electrolyte layer to be sealed The solar cell according to claim 1, wherein the solar cell is a laminated conductor layer.
A photoelectric conversion unit, a nonporous transparent anode electrode provided on the light incident side of the photoelectric conversion unit or a cathode electrode in which a nonporous material and a porous material are laminated, and the anode electrode across the photoelectric conversion unit In a solar cell having a nonporous cathode electrode provided oppositely and sealed entirely,
A part of the electrode of the anode electrode is exposed from a third opening formed in the sealing portion at a position not overlapping the cathode electrode in a plan view on the side opposite to the light incident side, and a third external connection terminal And a part of the electrode of the cathode electrode is exposed from a fourth opening formed on a side opposite to the light incident side at a position different from the third opening of the sealing portion. A solar cell characterized by being an external connection terminal.
The slurry-like raw material of the porous anode electrode is coated on a dissolvable base material by chemical treatment, and the slurry-like raw material is sintered to form a sintered body, and then the base material is subjected to chemical treatment. And forming a dye-adsorbing porous semiconductor layer on the sintered body to obtain a porous anode electrode with a dye-adsorbing porous semiconductor layer. Laminating a non-porous conductor portion at one corner on the side;
A non-porous portion having substantially the same planar dimensions as the porous anode electrode with the dye-adsorbing porous semiconductor layer and notched with a portion corresponding to the non-porous conductor portion when overlapped with the anode electrode, Obtaining a porous cathode or a cathode formed by laminating a non-porous material and a porous material;
The porous anode electrode with the dye-adsorbing porous semiconductor layer and the cathode electrode are aligned with the non-porous conductor portion of the porous anode electrode with the dye-adsorbing porous semiconductor layer and the notch portion of the cathode electrode. Laminating steps;
At least one of a substrate in which a fifth opening is formed outside the cathode electrode, or a sealing resin sheet in which a sixth opening is formed and a seventh opening is formed at a position corresponding to the notch Providing one,
The manufacturing method of the dye-sensitized solar cell characterized by having.