JP2007048674A - Dye-sensitized solar cell and its sealing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell and a method of sealing it involving less deterioration of a sensitizing dye at the time of manufacture and capable of sealing electrodes and electrolytic solution. <P>SOLUTION: The dye-sensitized solar cell is equipped with a counter-electrode base board 11, a transparent base board 12 made of glass installed confronting one surface of the counter-electrode base board, a catalyst electrode 13 installed on the mentioned surface of the counter-electrode base board, a semiconductor electrode 14 having the sensitizing dye installed on the surface confronting the counter-electrode base board of the transparent base board, the electrolytic solution 17 contained at least in the semiconductor electrode and put fully between the catalyst electrode and the semiconductor electrode, and walls 18 provided between the counter-electrode base board and the transparent base board and around the catalyst electrode and the semiconductor electrode. Each wall is formed in the part where the wall part of a glass base board to become transparent base board is formed, from a substance generated by melting and solidifying the mentioned part of formation with a laser beam cast from the vertical direction on the transparent base board side. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a dye-sensitized solar cell capable of sealing an electrode and an electrolyte while suppressing detachment of a sensitizing dye due to heat during production and a sealing method thereof.

  At present, in solar power generation, solar cells using single crystal silicon, polycrystalline silicon, amorphous silicon, a combination of these with HIT (Heterojunction with Intrinsic Thin-layer), etc. have been put into practical use and have become the main technology. These solar cells are excellent with photoelectric conversion efficiency of nearly 20%. However, silicon-based solar cells are expensive in terms of energy production, have many problems in terms of environmental impact, and have limitations in price and material supply. On the other hand, a dye-sensitized solar cell proposed by Gratzel et al. Has attracted attention as an inexpensive solar cell (see, for example, Non-Patent Document 1 and Patent Document 1). This solar cell has a structure in which an electrolytic solution is interposed between a semiconductor electrode using a porous titania carrying a sensitizing dye and a counter electrode, and the photoelectric conversion efficiency is higher than that of current silicon-based solar cells. Although it is low, the cost can be significantly reduced in terms of materials and manufacturing method.

In addition, the porous electrode, the counter electrode, and the electrolytic solution are accommodated in a space between the translucent substrate and the counter electrode substrate and surrounded by a wall portion. When this wall is heated to melt the translucent substrate or heated to accelerate curing using an adhesive resin, the sensitizing dye is removed from the semiconductor electrode when exposed to a high temperature of about 100 ° C. or higher. Due to desorption, the performance of the battery was low compared to unheated.
As described above, in order to form the wall portion without increasing the temperature of the sensitizing dye, a method of heating only the necessary portion by irradiating the laser beam toward the end surfaces of the translucent substrate and the counter electrode substrate. Has been proposed (see, for example, Patent Document 2).

Nature (Vol. 353, pp. 737-740, 1991) Japanese Patent Laid-Open No. 1-220380 JP 2003-170290 A

However, in the case of heating by irradiating from the side surface as in Patent Document 2, unless the side surfaces of the light-transmitting substrate and the counter electrode substrate are aligned, it becomes difficult for the laser light to reach the boundary surface between the two substrates and sufficient heating is not performed. . Further, the formation of the wall portion other than the end portion, for example, the central portion of the substrate was difficult to reach even when the laser beam was irradiated from the side surface and could not be heated.
The present invention has been made in view of the above situation, and a dye-sensitized solar cell capable of suppressing detachment of a sensitizing dye due to heat during production and sealing an electrode and an electrolytic solution, and It aims at providing the sealing method.

The dye-sensitized solar cell and the sealing method thereof of the present invention are as follows.
1. A counter electrode substrate 11, a glass-made translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, a catalyst electrode 13 disposed on the one surface side of the counter electrode substrate 11, and the light-transmitting substrate A semiconductor electrode 14 having a sensitizing dye disposed on one side of the conductive substrate 12 facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and the catalyst electrode 13 and the semiconductor electrode 14 An electrolyte solution 17 filled between and a wall portion 18 provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14;
The wall portion 18 is formed by a laser beam irradiated from a vertical direction on the translucent substrate 12 side to a formation site where the wall portion 18 of the glass substrate to be the translucent substrate 12 is formed. A dye-sensitized solar cell, which is formed by a melted and solidified product obtained by melting and solidifying a formation site.
2. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. And a wall portion 18A provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14, and the wall portion 18A. Is a method of melting and solidifying the formation site by the laser beam irradiated from the vertical direction on the side of the light-transmitting substrate 12 to the formation site where the wall portion 18A of the substrate to be the counter electrode substrate 11 is formed. Formed by the molten coagulum obtained Dye-sensitized solar cells, characterized.
3. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. A wall portion 18B provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14; Is filled between the bonded surface to be bonded to the wall portion 18B of the counter electrode substrate 11 and the bonded surface to be bonded to the wall portion 18B of the translucent substrate 12. The applied adhesive resin was irradiated from the vertical direction on the translucent substrate 12 side. Dye-sensitized solar cell characterized by being formed by curing the laser light.
4). 1. The above-described 1., further comprising a current collecting electrode 161 that is electrically connected to the semiconductor electrode 14 and that absorbs laser light at a joint surface of the translucent substrate 12 with the wall portions 18, 18A, 18B. To 3. The dye-sensitized solar cell according to any one of the above.
5. 1. The above-mentioned 1., further comprising a current collecting electrode 151 that is electrically connected to the catalyst electrode 13 and absorbs laser light at a joint surface between the counter electrode substrate 11 and the wall portions 18, 18B. Or 3. The dye-sensitized solar cell described.
6). The counter substrate 11 is made of ceramics. To 5. The dye-sensitized solar cell according to any one of the above.

7). A counter electrode substrate 11, a glass-made translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, a catalyst electrode 13 disposed on the one surface side of the counter electrode substrate 11, and the light-transmitting substrate A semiconductor electrode 14 having a sensitizing dye disposed on one side of the conductive substrate 12 facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and the catalyst electrode 13 and the semiconductor electrode 14 And a wall portion 18 provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14. A method for sealing a photosensitive solar cell, wherein a light absorbing material and a glass flux are attached to a formation site where the wall portion 18 of the glass substrate to be the translucent substrate 12 is to be formed, From the vertical direction of the light transmissive substrate 12 side to the light absorbing material The glass substrate is melted by irradiating with the user's light, and then the melt is allowed to reach the counter electrode substrate 11 and then solidified to form the wall portion 18 to form the counter electrode substrate 11 and the light transmitting material. A method for sealing a dye-sensitized solar cell, comprising bonding a substrate 12.
8). Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. A dye-sensitized solar comprising: a filled electrolyte solution 17; and a wall portion 18A provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14. In the battery sealing method, a light absorbing material and a glass flux are attached to a formation site where the wall portion 18A of the substrate to be the counter electrode substrate 11 is formed, and then the light absorbing material is subjected to the transparent material. Laser light irradiation from the vertical direction on the optical substrate 12 side The substrate is melted, and then the melt is allowed to reach the light transmitting substrate 12 and then solidified to form the wall portion 18A to join the counter electrode substrate 11 and the light transmitting substrate 12 together. A method for sealing a dye-sensitized solar cell, comprising:
9. The light absorbing material is contained in the glass flux. Or 8. A method for sealing a dye-sensitized solar cell as described.
10. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. A dye-sensitized solar comprising: a filled electrolyte solution 17; and a wall portion 18B provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14. In a method for sealing a battery, a light absorbing material is attached to a formation site where the translucent substrate 12 and / or the wall portion 18B of the counter electrode substrate 11 is formed, and the counter electrode substrate 11 and The wall 18B of the translucent substrate 12 is formed; Adhesive resin is filled between the forming portions to be formed, and then the light absorbing material is irradiated with laser light from the vertical direction on the light transmitting substrate 12 side to cure the adhesive resin to form the wall portion 18B. A method for sealing a dye-sensitized solar cell, comprising joining the counter electrode substrate 11 and the translucent substrate 12 through the wall portion 18B.
11. The light absorbing material is contained in the adhesive resin. A method for sealing a dye-sensitized solar cell as described.
12 6. The above described 7. further comprising a current collecting electrode 161 that is electrically connected to the semiconductor electrode 14 at the formation site of the translucent substrate 12 and functions as the light absorbing material. To 11. A method for sealing a dye-sensitized solar cell according to any one of the above.
13. 6. The collector electrode 151 further comprising a current collecting electrode 151 electrically connected to the catalyst electrode 13 at the formation site of the counter electrode substrate 11 and functioning as the light absorbing material. 10 or 11. A method for sealing a dye-sensitized solar cell as described.
14 6. The counter substrate 11 is made of ceramic. Thru 13. A method for sealing a dye-sensitized solar cell according to any one of the above.

According to the dye-sensitized solar cell and the sealing method thereof of each of the present invention, the glass substrate that becomes the translucent substrate 12 by the laser beam is used for the wall portion 18 that joins the translucent substrate 12 and the counter electrode substrate 11. By forming by heating and melting and solidifying, the joining process can be easily performed in a short time. Further, even when the wall portion 18A is formed by heating and melting and solidifying the substrate serving as the counter electrode substrate 11 with laser light, the joining process can be easily performed in a short time. Furthermore, the bonding step can be easily performed in a short time by forming the wall portion 18B by heating the adhesive resin with laser light.
Furthermore, since it can heat only in the part which needs joining, at the time of preparation of a dye-sensitized solar cell, the temperature of the semiconductor electrode 14 weak with heat, the electrolyte solution 17, etc. rises, and a sensitizing dye becomes Desorption or degradation of the electrolyte can be suppressed. Further, as illustrated in FIG. 1, arbitrary portions such as the periphery and the center can be joined regardless of the positional relationship between the counter electrode substrate 11 and the translucent substrate 12 and the walls 18, 18 </ b> A, and 18 </ b> B. Therefore, a dye-sensitized solar cell can be easily manufactured.
Further, when the current collecting electrode 161 of the translucent substrate 12 is also provided between the translucent substrate 12 and the wall portions 18, 18 </ b> A, 18 </ b> B and used as a light absorbing material, other light absorbing materials are not prepared. The translucent substrate 12 and the wall portions 18, 18A, 18B using a laser can be easily joined. Further, when the current collecting electrode 151 of the counter electrode substrate 11 is also provided between the counter electrode substrate 11 and the wall portions 18 and 18B and used as a light absorbing material, the counter electrode substrate 11 and the wall portions 18 and 18B using the laser are similarly used. Bonding can be performed easily.
Further, when the counter electrode substrate 11 is made of ceramics, the structure of the dye-sensitized solar cell can be stabilized, and manufacture and attachment can be facilitated. Further, even if tungsten or the like is sintered on the counter electrode substrate 11 to form the current collecting electrode 15 or the like, the counter electrode substrate 11 is not deformed. Furthermore, even if the counter electrode substrate 11 is heated by the laser beam, the function as the counter electrode substrate 11 is not deteriorated, and the electrolytic solution 17 and the like can be easily sealed.
When the light absorbing material is contained in the glass flux, the glass flux can be heated more uniformly by the laser beam, and the joining can be facilitated.
When the light-absorbing material is contained in the adhesive resin, the adhesive resin can be heated in a short time, the heating by the laser light is made more efficient, and the counter electrode substrate 11 and the translucent substrate 12 are bonded. Can do.

Hereinafter, the dye-sensitized solar cell and the sealing method thereof according to the present invention will be described in detail with reference to FIGS.
As illustrated in FIG. 4, the dye-sensitized solar cell 1 includes a counter electrode substrate 11, a translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, and the one surface of the counter electrode substrate 11. Catalyst electrode 13 disposed on the side, semiconductor electrode 14 having a sensitizing dye disposed on one side of the translucent substrate 12 facing the counter electrode substrate 11, and at least a part of the semiconductor electrode 14 And the electrolyte solution 17 filled between the catalyst electrode 13 and the semiconductor electrode 14, the counter electrode substrate 11 and the translucent substrate 12, and the catalyst electrode 13 and the semiconductor electrode 14. And a wall portion 18 provided around.

The “counter electrode substrate 11” is disposed to face the translucent substrate 12. The counter electrode substrate 11 may or may not have translucency. Although the counter electrode substrate 11 which does not have translucency is not specifically limited, For example, it can form with ceramics. The counter electrode substrate 11 using a ceramic substrate has a high strength and can be a support substrate to be a dye-sensitized solar cell having excellent durability. Further, the catalyst electrode 13 and the counter electrode side collecting electrode 15 can be fired. Furthermore, the counter electrode substrate 11, the catalyst electrode 13, and the counter electrode side collector electrode 15 can be fired simultaneously.
Ceramics used for forming the ceramic substrate are not particularly limited, and various ceramics such as oxide ceramics, nitride ceramics, and carbide ceramics can be used. As the ceramic, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable. Alumina is excellent in corrosion resistance, has high strength, is excellent in electrical insulation, and can be a dye-sensitized solar cell having superior durability by using the counter electrode substrate 11 made of alumina.

  In the case where the counter electrode substrate 11 is made of ceramics, the thickness is not particularly limited, but may be 100 μm to 5 mm, particularly 500 μm to 5 mm, more preferably 1 to 5 mm, and preferably 300 μm to 3 mm. When the counter electrode substrate 11 has a thickness of 100 μm to 5 mm, particularly 300 μm to 3 mm, a dye-sensitized solar cell having sufficient strength as a support layer and excellent durability can be obtained.

The counter electrode substrate 11 having translucency can be formed using a glass plate, a resin sheet, or the like.
A material is not specifically limited when the counter electrode substrate 11 consists of a glass plate, For example, silica glass, soda-lime glass, borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, etc. can be used. Further, when the counter electrode substrate 11 is made of a resin sheet, the material is not particularly limited, and it can be produced using polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polycarbonate, polysulfone, and polyethylidene norbornene. The thickness of the counter electrode substrate 11 varies depending on the material and is not particularly limited. However, the thickness is preferably 60 to 99%, more preferably 85 to 99%, as described below, which is a light transmission index.
The translucency here means that the transmittance of visible light having a wavelength of 400 to 900 nm is 10% or more. This transmittance is preferably 60% or more, particularly 85% or more. Hereinafter, the meaning of translucency and preferable transmittance are all the same.
Transmittance (%) = (transmitted light amount / incident light amount) × 100

The “translucent substrate 12” is disposed to face the counter electrode substrate 11. As in the case where the counter electrode substrate 11 has translucency, the light transmissive substrate 12 is a glass plate when bonded to the counter electrode substrate 11 by melting and solidification, and a glass plate when bonded using an adhesive resin. It can be formed using a resin sheet or the like. The glass plate and the resin sheet are not particularly limited, and similarly to the counter electrode substrate 11, examples include various glass plates and sheets made of various resins.
The thickness of the translucent substrate 12 varies depending on the material and is not particularly limited. However, the above-described transmittance is preferably 60 to 99%, particularly 85 to 99%.

The “catalyst electrode 13” is disposed on one surface side of the counter electrode substrate 11 (see, for example, FIG. 4). The catalyst electrode 13 can be formed of a substance having catalytic activity. In addition, the catalyst has a catalytic activity such as a metal having no catalytic activity, a conductive oxide used for forming a translucent conductive film used for the catalyst electrode 13 described later, and a conductive polymer such as polyaniline and polypyrrole. It can also form using the substance which has.
Substances having catalytic activity include noble metals such as platinum and rhodium (however, gold and silver are not preferred because of their low corrosion resistance to electrolytes, etc. Hereinafter, silver is similarly applied to the parts that can be contacted with electrolytes, etc. Not preferable), carbon black and the like, and these have conductivity together. The catalyst electrode 13 is preferably formed of a noble metal that has catalytic activity and is electrochemically stable, and it is particularly preferable to use platinum that has high catalytic activity and high corrosion resistance to the electrolytic solution. Although the thickness of the catalyst electrode 13 is not particularly limited, it can be 3 nm to 10 μm, particularly 3 nm to 2 μm in both cases of a single layer and a multilayer. When the thickness of the catalyst electrode 13 is 3 nm to 10 μm, the catalyst electrode 13 having a sufficiently low resistance can be obtained.

  The catalytic electrode 13 made of a substance having a catalytic activity is formed by applying a paste containing fine particles of a substance having a catalytic activity on the surface of the counter electrode substrate 11 or the like by using an arbitrary application method such as a screen printing method or a doctor blade method. can do. Further, the catalyst electrode 13 made of a metal containing a substance having catalytic activity or a conductive oxide can also be formed by the same method as that for the substance having catalytic activity. Furthermore, these catalyst electrodes 13 can also be formed by depositing metal or the like on the surface of the counter electrode substrate 11 or the like by sputtering, vapor deposition, ion plating or the like.

The “semiconductor electrode 14” is disposed on one surface side of the translucent substrate 12 (see, for example, FIG. 4). The semiconductor electrode 14 has a semiconductor electrode base and a sensitizing dye attached to the semiconductor electrode base. The semiconductor electrode substrate can be formed of a metal oxide such as titania, tin oxide, or zinc oxide, or a metal sulfide such as zinc sulfide or lead sulfide.
The method for producing the semiconductor electrode substrate is not particularly limited. For example, a paste containing semiconductor fine particles such as a metal oxide and a metal sulfide may be applied to the surface of the light-transmitting substrate 12 or the like by a screen printing method or a doctor blade method. It can be produced by applying the above coating method to form an unsintered semiconductor electrode substrate and then firing.
Although the firing conditions are not particularly limited, the firing temperature can be 400 to 600 ° C., particularly 450 to 550 ° C., and the firing time can be 10 to 300 minutes, particularly 20 to 40 minutes. The firing atmosphere can be an oxidizing atmosphere such as an air atmosphere or an inert atmosphere such as a rare gas atmosphere such as argon and a nitrogen gas atmosphere.

As the “sensitizing dye”, a complex dye and an organic dye that improve the photoelectric conversion effect can be used. Examples of complex dyes include metal complex dyes, and examples of organic dyes include polymethine dyes and merocyanine dyes. Examples of the metal complex dye include a ruthenium complex dye and an osmium complex dye, and a ruthenium complex dye is particularly preferable. Furthermore, in order to expand the wavelength range in which photoelectric conversion is performed and improve the photoelectric conversion efficiency, two or more sensitizing dyes having different wavelength ranges in which a sensitizing action is exhibited can be used in combination.
The method for attaching the sensitizing dye to the semiconductor electrode substrate is not particularly limited. For example, the semiconductor electrode substrate is immersed in a solution in which the sensitizing dye is dissolved in an organic solvent, the solution is impregnated, and then the organic solvent is removed. It can be made to adhere. Alternatively, this solution can be applied to a semiconductor electrode substrate and then adhered by removing the organic solvent.

The “electrolytic solution 17” is contained in at least a part of each of the semiconductor electrode 14 and the catalyst electrode 13 and is filled between the semiconductor electrode 14 and the catalyst electrode 13. The electrolytic solution 17 is usually contained in the entirety of each of the semiconductor electrode 14 and the catalyst electrode 13, whereby the photoelectric conversion efficiency can be improved. The distance between the semiconductor electrode 14 and the catalyst electrode 13 is not particularly limited, but can be 200 μm or less, particularly 50 μm or less (usually 1 μm or more). When the thickness is 200 μm or less, a dye-sensitized solar cell having sufficient power generation efficiency can be obtained.
In addition to the electrolyte, the electrolytic solution 17 usually contains a solvent such as carbonates such as ethylene carbonate and propylene carbonate, various additives, and the like. This electrolyte is not particularly limited, and various electrolytes can be used. As the electrolyte, an electrolyte obtained by combining I ₂ and an iodine salt of a quaternary ammonium compound such as LiI, pyridinium iodide, and imidazolium iodide is particularly preferable. Only one type of electrolyte may be used, or two or more types of electrolytes may be used.

  In the case of using an electrolytic solution, the electrolytic solution can be injected, contained, and filled into the space formed by the counter electrode substrate 11, the translucent substrate 12, and the walls 18, 18A, and 18B. The electrolytic solution may be injected into the space from the counter electrode substrate 11 side or the translucent substrate 12 side, and it is preferable to provide an injection port on the side where perforation is easy and to inject from this injection port. In addition, although one injection port is sufficient, another hole can also be provided for air venting. Thus, by providing the hole for air venting, the electrolyte can be injected more easily.

The “walls 18, 18 </ b> A, 18 </ b> B” may be any material as long as the electrolytic solution 17 does not leak out of the compartment. Examples of this material include an adhesive resin and glass. Moreover, when the member used as the wall parts 18 and 18A is melt-solidified with a laser beam, glass etc. can be illustrated. Furthermore, a “glass-containing material” containing a glass component can be used. The “glass component” includes, in addition to silica glass and the like, substances that are in a glass state and can be melted and solidified by laser light.
As the “adhesive resin”, any resin capable of adhering the counter electrode substrate 11 and the translucent substrate 12 can be used. Thermoplastic resins such as polyolefin, polyvinyl chloride, polyamide and polyacetal, and epoxy Examples thereof include thermosetting resins such as resins, urethane resins and thermosetting polyester resins. Further, when glass is used, the same type of glass as the light-transmitting substrate 12 and the light-transmitting counter electrode substrate 11 can be used. In particular, solar cells that require long-term durability are preferably sealed with glass.
Furthermore, the wall portions 18 and 18A may be integrally formed using the same material as the counter electrode substrate 11 or the translucent substrate 12 (see, for example, FIGS. 4 and 7). Even when the wall portion 18A is formed by melting and solidifying a member made of ceramic with a laser beam, the ceramic itself or a glass component contained in the ceramic is melted and solidified by the laser beam, and the counter electrode substrate 11 and the transparent substrate 11 are transparent. If the optical substrate 12 can be bonded, the member can be used as the wall portion 18A in the present invention.

  Further, as a method of forming the wall portions 18, 18A, 18B, 1. 1. a method of forming a part of a glass substrate used for the translucent substrate 12 by melting and solidifying with a laser beam; 2. a method of forming a part of a substrate used for the counter electrode substrate 11A by melting and solidifying with a laser beam; A method of curing the adhesive resin with laser light can be given.

  1. Examples of the method of forming a wall portion 18 by melting and solidifying a part of a glass substrate used for the translucent substrate 12 with a laser beam include (1) a surface on which the wall portion 18 of the glass substrate 12 ′ is formed. The light absorbing material 3 and the glass flux 4 are attached to the “formation site” (see, for example, FIG. 2), and then (2) the light-transmitting substrate 3 is attached to the light absorption material 3 attached to the formation site. The glass flux 4 is heated by irradiating the laser beam from the vertical direction on the 12 side, and the glass substrate 12 ′ is heated and melted (see, for example, FIG. 2), and then (3) the melt is added to the counter electrode substrate A method of forming the wall portion 18 by solidifying after reaching 11 can be exemplified (see, for example, FIG. 3).

2. The method of forming a wall portion 18A by melting and solidifying a part of the substrate used as the counter electrode substrate 11A with a laser beam is, for example, (1) a formation site that is a surface that forms the wall portion 18A of the substrate 11A ′. The light absorbing material 3 and the glass flux 4 are attached to the substrate (see, for example, FIG. 5), and then (2) laser light is applied to the light absorbing material 3 attached to the formation site from the vertical direction on the translucent substrate 12 side. To heat the glass flux 4 to heat and melt the substrate 11A ′ (see, for example, FIG. 5), and then (3) after the melt reaches the light-transmitting substrate 12, A method of forming the wall portion 18A by solidifying can be mentioned (see, for example, FIG. 6).
Alternatively, a part of the substrate used for the counter electrode substrate 11A and the translucent substrate 12 may be melted by laser light, brought into contact with each other, and then solidified to form a wall portion.

  3. The method of curing the adhesive resin with laser light is, for example, (1) the light absorbing material 3 at the formation site where the wall portion 18B of the translucent substrate 12 and / or the counter electrode substrate 11 is formed. (See, for example, FIG. 8), and the adhesive resin 5 is filled between formation sites where the counter electrode substrate 11 and the light transmitting substrate 12 are to be formed with the wall portions 18B. (2) A method of forming the wall portion 18B by irradiating the light absorbing material 3 with a laser beam from the vertical direction on the light transmitting substrate 12 side to cure the adhesive resin 5 (for example, , See FIG.

The above “attachment” means that the light absorbing material 3 is provided at a formation site by any means, and examples thereof include application, printing, adhesion, adhesion, and sticking.
The object to which the light absorbing material 3, the glass flux 4 and the adhesive resin 5 are attached is not limited to the above description, and may be any of the counter substrate 11, 11A and the light transmitting substrate 12, or may be attached to both. . Further, the light absorbing material 3 may be contained in the glass flux 4 and the adhesive resin 5.

The laser used for “melting the counter electrode substrate 11 and the translucent substrate 12” or “curing the adhesive resin 5” may be any laser that can be used for ordinary heating applications. For example, a YAG laser, a carbon dioxide laser, etc. Can be used. Further, the laser light irradiation conditions such as the laser frequency and the input current value can be appropriately set so as to be efficiently cured by the composition and thickness of the walls 18, 18A and 18B.
Moreover, it is preferable to irradiate a laser beam from the perpendicular direction of the translucent board | substrate 12 (for example, refer FIG.1,2,5,8,11,14). By irradiating the laser beam from the vertical direction, it is possible to minimize the passage loss of the translucent substrate 12 and minimize the intermediate loss, and the peripheral and central portions of the counter electrode substrate 11 and the translucent substrate 12, etc. This is because the bonding at any position can be performed. Furthermore, it is preferable to irradiate the laser beam so that the light absorbing material 3 is in focus.
The “vertical direction” is not limited to a strict vertical direction, and may have an inclination of ± 15 °, particularly preferably ± 10 ° from the vertical. This is because even if there is such a slight inclination, the same effect as in the case of being substantially vertical can be obtained. Further, the irradiation target is not limited to the light absorbing material 3, and the glass flux 4, the adhesive resin 5, the counter electrode substrate 11, the translucent substrate 12, and the like can also be the irradiation target. Further, when the counter electrode substrate 11 is translucent, the light absorbing material 3 may be irradiated from the counter electrode substrate 11 side.

The “light absorbing material 3” only needs to be able to absorb laser light, and a light absorbing material used in normal laser light processing can be used. Examples of this include graphite, organic dyes and metals. If the constituent elements of the present dye-sensitized solar cell such as the collecting electrode 16 can absorb the laser beam, it can be used as the light absorbing material 3 (for example, the collecting electrode 161 in FIG. 14 (see current collecting electrode 151). The component that absorbs the laser beam uses a material that easily absorbs the wavelength of the laser beam to be used (for example, a color) or a structure that easily scatters the laser beam (for example, a porous structure). It is provided.
The “glass flux 4” is a flux for facilitating melting of the translucent substrate 12 in order to join the translucent substrate 12 using glass and the counter electrode substrate 11. As the flux, commonly used ones can be used, and examples thereof include sodium nitrate, potassium nitrate and shelf sand. The glass flux 4 is melted together with the formation site of the translucent substrate 12 and solidified to form the walls 18 and 18A.

Moreover, the current collection electrode 15 adjacent to the catalyst electrode 13 and / or the current collection electrode 16 adjacent to the semiconductor electrode 14 can be provided (for example, refer to the current collection electrodes 15 and 16 shown in FIG. 4). By providing the current collecting electrodes 15 and 16, the conductivity of the catalyst electrode 13 and the semiconductor electrode 14 can be increased, and the internal resistance of the dye-sensitized solar cell can be lowered. Examples of the current collecting electrodes 15 and 16 include a metal having an arbitrary pattern such as a lattice and a conductor such as carbon, a translucent conductive film, and a conductor using both the conductor and the translucent conductive film. can do.
Among these, metals having excellent corrosion resistance such as tungsten, titanium and nickel are preferable. Moreover, the material of the translucent conductive film is not particularly limited, and examples thereof include a thin film made of a conductive oxide, a metal thin film, and a carbon thin film. Examples of the conductive oxide include tin oxide, fluorine-doped tin oxide, indium oxide, tin-doped indium oxide, and zinc oxide. The thickness of the translucent conductive film is also different depending on the material, but are not limited to, surface resistance 100 [Omega · cm ² or less, particularly preferably 1~10Ω · cm ² become thick.
The method for forming the current collecting electrodes 15 and 16 is not particularly limited. For example, a paste containing fine particles of metal, conductive oxide or the like is applied to the surface of the counter electrode substrate 11 and / or the translucent substrate 12 by a screen printing method or a doctor. It can be formed using any coating method such as a blade method. The collecting electrodes 15 and 16 can also be formed by a sputtering method using a metal, a conductive oxide or the like, a vacuum deposition method, an ion plating method, or the like.
In addition, when making the current collection electrode 15 by the side of the counter-electrode board | substrate 11 translucent, it can be set as the structure similar to the current collection electrode 16 by the side of the translucent board | substrate 12.

  The method for producing the dye-sensitized solar cell of the present invention is not particularly limited. For example, the collector electrodes 15 and 16 are formed on the counter electrode substrate 11 and the translucent substrate 12, and the catalyst is formed on one surface side of the counter electrode substrate 11. The electrode 13 is formed, the semiconductor electrode 14 is formed on one surface side of the translucent substrate 12, and then the counter electrode substrate 11 and the translucent substrate 12 are joined with the catalyst electrode 13 and the semiconductor electrode 14 facing each other, An example is a method in which the electrolytic solution 17 is contained in at least a part of the semiconductor electrode 14.

Hereinafter, the dye-sensitized solar cell and the sealing method thereof according to the present invention will be described specifically by way of examples.
As shown in FIG. 4, Example 1 is a dye-sensitized solar cell 1 in which a wall portion 18 is formed by melting a part of a glass substrate 12 ′ that becomes a light-transmitting substrate 12. This dye-sensitized solar cell 1 was produced according to the following procedure.
(1) Production of Counter Electrode Substrate 11 Side A slurry containing alumina powder was used as a sheet, and then the solvent was volatilized to obtain an alumina green sheet to be the ceramic counter electrode substrate 11. Next, a tungsten paste to be the collector electrode 15 was applied to the alumina green sheet to be the ceramic counter electrode substrate 11 by a screen printing method to obtain an unfired body. Thereafter, the green body was fired to obtain a counter electrode substrate 11 in which the collecting electrode 15 was integrated. Next, a platinum thin film serving as the catalyst electrode 13 was formed on the collecting electrode 15 by sputtering.

(2) Production of Glass Substrate 12 ′ that Becomes Translucent Substrate 12 Provided with Semiconductor Electrode 14 An FTO transparent conductive film that becomes current collecting electrode 16 was formed on one surface of the glass substrate in a pattern that allows semiconductor electrode 14 to be connected. . Next, a paste containing titania particles having a particle size of 5 to 300 nm (Ti-Nanoxide D / SP 13um / 300um) was applied by a screen printing method and dried at 120 ° C for 30 minutes to form an unsintered semiconductor electrode substrate. . Next, the unfired semiconductor electrode substrate was fired.
Thereafter, a ruthenium organic complex ([Ru-2,2bipyridil-4,4-dicarboxylate (TBA) ₂ (NCS) ₂ ]) is dissolved in an acetonitrile / t-butanol mixed solvent, and 5 × 10 ⁻⁴ M acetonitrile / t- A butanol solution was prepared. A semiconductor electrode substrate was immersed in this solution for 18 hours, and a ruthenium complex serving as a sensitizing dye was supported on the electrode surface to produce a glass substrate 12 ′ serving as a translucent substrate 12 on which the semiconductor electrode 14 was laminated.
Next, the light absorbing material 3 and the glass flux 4 were respectively applied by screen printing to the formation site where the wall portion 18 of the glass substrate 12 ′ was to be formed. The light absorbing material 3 was a black oil paint. As the glass flux 4, sodium nitrate was used.

(3) Joining Counter Electrode Substrate 11 and Translucent Substrate 12 Next, a spacer (not shown) having a thickness of 150 μm is attached to the counter electrode substrate 11 and the glass substrate 12 ′ with the catalyst electrode 13 and the semiconductor electrode 14 facing each other. (See FIG. 2). Thereafter, the YAG laser 2 is applied to the light absorbing material 3 attached to the site of the wall portion 18 of the translucent substrate 12 from the direction perpendicular to the glass substrate 12 ′ and the glass substrate 12 ′ (see FIG. 1 and 2), the wall 18 forming part of the glass substrate 12 ′ is heated and melted, and the melt is brought into contact with the forming part of the counter electrode substrate 11 and then solidified to form a wall 18 that is a melted solidified product. The remaining part was a light-transmitting substrate 12, and the counter electrode substrate 11 and the light-transmitting substrate 12 were joined (see FIG. 3). Next, an iodine electrolyte was poured into the space formed by these from an inlet provided separately, and then the adhesive was filled to seal the inlet (see FIG. 4).
The iodine electrolyte was butyronitrile, 0.1 mol of lithium iodide, 0.05 mol of iodine, 0.5 mol of 4-tert-butylpyridine, and 0.6 mol of 1,2-dimethyl-3. A solution in which propylimidazolium iodide was dissolved was used.

As shown in FIG. 4, the dye-sensitized solar cell 1 manufactured in this way includes a counter electrode substrate 11, a translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, and a counter electrode substrate 11. Current collecting electrode 15 and catalyst electrode 13 disposed on one surface side, current collecting electrode 16 disposed on one surface side of translucent substrate 12 facing counter electrode substrate 11 and semiconductor electrode 14 having a sensitizing dye, And an electrolytic solution 17 contained in at least a part of the semiconductor electrode 14 and filled between the catalyst electrode 13 and the semiconductor electrode 14. Further, the electrolytic solution 17 is held in the dye-sensitized solar cell 1 by the wall portion 18 formed in the periphery. Furthermore, the translucent substrate 12 and the wall portion 18 are integrally formed.
The dye-sensitized solar cell 1 can be connected to an external circuit by connection terminals (not shown) formed by extending the current collecting electrodes 15 and 16 from the wall portion 18.

As shown in FIG. 5, Example 2 is a dye-sensitized solar cell 1 </ b> A in which a wall portion 18 </ b> A is formed by melting a part of a glass substrate 11 </ b> A ′ serving as a counter electrode substrate 11 </ b> A. This dye-sensitized solar cell 1A was produced according to the following procedure.
(1) Production on the side of the glass substrate 11A ′ to be the counter electrode substrate 11A A transparent conductive film made of FTO to be the collecting electrode 15A was formed on one surface of the glass substrate. Next, a platinum thin film serving as the catalyst electrode 13 was formed on the current collecting electrode 15A by sputtering to obtain a glass substrate 11A ′. Then, the light absorption material 3 and the glass flux 4 were each apply | coated to the formation site | part which is a surface which will form wall part 18A of glass substrate 11A 'by screen printing. The light absorbing material 3 and the glass flux 4 are the same materials as in the first embodiment.
(2) Production of translucent substrate 12 provided with semiconductor electrode 14 In the same manner as in production of (2) glass substrate 12 ′ to be translucent substrate 12 provided with semiconductor electrode 14 in Example 1, a semiconductor was prepared. A translucent substrate 12 on which the electrode 14 was laminated was produced.

(3) Joining of Counter Electrode Substrate 11A and Translucent Substrate 12 Next, the glass substrate 11A ′ and the translucent substrate 12 are joined to a spacer (not shown) having a thickness of 150 μm with the catalyst electrode 13 and the semiconductor electrode 14 facing each other. ) (See FIG. 5). After that, the YAG laser 2 is irradiated on the light absorbing material 3 attached to the wall portion 18A formation site of the glass substrate 11A ′ from the direction that is on the side of the transparent substrate 12 and perpendicular to the transparent substrate 12. (See FIGS. 1 and 5), the wall 18A formation site is heated and melted, and the melt is brought into contact with the wall 18A formation site of the translucent substrate 12 and then solidified to form a wall portion that is a melted solid product. 18A, the remainder being the counter electrode substrate 11A, and the counter electrode substrate 11A and the translucent substrate 12 were joined (see FIG. 6). Next, the same iodine electrolyte as in Example 1 was injected into the space formed by these from an inlet provided separately, and then the adhesive was filled to seal the inlet (see FIG. 7).

As shown in FIG. 7, the dye-sensitized solar cell 1 </ b> A produced in this way includes a counter electrode substrate 11 </ b> A, a translucent substrate 12 arranged to face one surface of the counter electrode substrate 11 </ b> A, and a counter electrode substrate 11 </ b> A. Current collecting electrode 15A and catalyst electrode 13 disposed on one surface side, current collecting electrode 16 disposed on the one surface side of translucent substrate 12 opposite to counter electrode substrate 11A, and semiconductor electrode 14 having a sensitizing dye, And an electrolytic solution 17 contained in at least a part of the semiconductor electrode 14 and filled between the catalyst electrode 13 and the semiconductor electrode 14. Further, the electrolytic solution 17 is held in the dye-sensitized solar cell 1A by a wall portion 18A formed in the periphery. Furthermore, the counter electrode substrate 11A and the wall 18A are integrally formed.
The dye-sensitized solar cell 1A can be connected to an external circuit by connection terminals (not shown) formed by extending the collecting electrodes 15A and 16 from the wall portion 18A.

As shown in FIG. 10, Example 3 is a dye-sensitized solar cell 1B in which the adhesive resin 5 is cured to form a wall portion 18B. This dye-sensitized solar cell 1B was produced according to the following procedure.
(1) Production on the counter electrode substrate 11 side As in Example 1, the collector electrode 15 was formed, and the counter electrode substrate 11 on which the platinum thin film to be the catalyst electrode 13 was formed was obtained. Next, three ionomer resin sheets 5 having a thickness of about 50 μm were laminated as a thermoplastic adhesive resin at the site where the wall portion 18B was formed.
Note that the adhesive resin sheet 5 may be laminated on the site where the wall portion 18B of the translucent substrate 12 is formed.

(2) Production of translucent substrate 12 provided with semiconductor electrode 14 In the same manner as in production of glass substrate 12 ′ to be translucent substrate 12 provided with semiconductor electrode 14 in Example 1, semiconductor electrode 14 is provided. A light-transmitting substrate 12 having a laminated structure was prepared. Next, the light absorbing material 3 was applied to the formation site where the wall portion 18B of the translucent substrate 12 was to be formed in the same manner as in Example 1. The light absorbing material 3 may be applied to a formation site where the wall portion 18B of the counter electrode substrate 11 is formed.

(3) Joining of Counter Electrode Substrate 11 and Translucent Substrate 12 Next, the counter electrode substrate 11 and the translucent substrate 12 were arranged so as to sandwich the adhesive resin sheet 5 therebetween. Thereafter, the YAG laser is irradiated on the light absorbing material 3 from the direction perpendicular to the translucent substrate 12 on the translucent substrate 12 side and the adhesive resin sheet 5 is heated and cured as shown in FIG. Then, as shown in FIG. 9, a wall 18 </ b> B that is a cured adhesive resin sheet was formed, and the counter electrode substrate 11 and the translucent substrate 12 were joined. Next, the same electrolyte as in Example 1 was injected into the space formed by these from an injection port separately provided, and then the adhesive was filled to seal the injection port (see FIG. 10).

As shown in FIG. 10, the dye-sensitized solar cell 1 </ b> B manufactured in this way includes a counter electrode substrate 11, a translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, and a counter electrode substrate 11. Current collecting electrode 15 and catalyst electrode 13 disposed on one surface side, current collecting electrode 16 disposed on one surface side of translucent substrate 12 facing counter electrode substrate 11 and semiconductor electrode 14 having a sensitizing dye, And an electrolytic solution 17 contained in at least a part of the semiconductor electrode 14 and filled between the catalyst electrode 13 and the semiconductor electrode 14. Further, the electrolytic solution 17 is held in the dye-sensitized solar cell 1B by the wall portion 18B formed in the periphery.
Such a dye-sensitized solar cell 1B can be connected to an external circuit by connection terminals (not shown) formed by extending the collecting electrodes 15 and 16 from the wall portion 18B.

As shown in FIG. 13, Example 4 is a dye-sensitized solar cell 1C in which the adhesive resin 5 is cured to form a wall portion 18B. In the fourth embodiment, the tungsten wire 162 constituting a part of the current collecting electrode 161 is used as the light absorbing material 3. This dye-sensitized solar cell 1C was produced according to the following procedure.
(1) Production on the counter electrode substrate 11 side As in Example 1, the collector electrode 15 was formed, and the counter electrode substrate 11 on which the platinum thin film to be the catalyst electrode 13 was formed was obtained. Next, the same adhesive resin sheet 5 as that of Example 3 having a thickness of about 50 μm was laminated on the formation portion to be bonded to the translucent substrate 12 of the wall portion 18B.

(2) Production of translucent substrate 12 provided with semiconductor electrode 14 FTO transparent conductive film, which is a part of current collecting electrode 161, is connected to semiconductor electrode 14 on one surface of a glass plate substrate similar to that in Example 1. The pattern was formed. Next, tungsten wires 162 having a diameter of 10 μm, which are the other part of the collecting electrode 161 and function as the light absorbing material 3, were arranged in parallel in the long direction of the pattern at intervals of 30 μm. Thereafter, a semiconductor electrode substrate was formed in the same manner as in Example 1 to fabricate a translucent substrate 12.
At this time, the current collecting electrode 161 is also formed on the site where the wall portion 18B is formed, and the tungsten wire 162 functions as the light absorbing material 3.

(3) Joining of Counter Electrode Substrate 11 and Translucent Substrate 12 Next, the counter electrode substrate 11 and the translucent substrate 12 were disposed so as to sandwich the adhesive resin sheet 5 serving as the wall portion 18B. Thereafter, as shown in FIG. 11, the YAG laser is irradiated on the tungsten wire 162 located on the formation site from the direction perpendicular to the translucent substrate 12 and the YAG laser under the same conditions as in the third embodiment. Then, the adhesive resin sheet 5 was cured by heating to form a wall portion 18B, which is a cured adhesive resin sheet, as shown in FIG. 12, and the counter electrode substrate 11 and the translucent substrate 12 were joined. At this time, the tungsten wire 162 of the collecting electrode 161 heated by being irradiated with laser light functions as the light absorbing material 3 and heats the adhesive resin sheet 5.
Thereafter, an electrolytic solution 17 was injected into the space formed by these in the same manner as in Example 1 (see FIG. 13).

As shown in FIG. 13, the dye-sensitized solar cell 1 </ b> C manufactured in this way includes a counter electrode substrate 11, a translucent substrate 12 disposed to face one surface side of the counter electrode substrate 11, and a counter electrode substrate 11. Current collecting electrode 15 and catalyst electrode 13 disposed on one surface side, current collecting electrode 161 disposed on one surface side of translucent substrate 12 facing counter electrode substrate 11 and semiconductor electrode 14 having a sensitizing dye, And an electrolytic solution 17 contained in at least a part of the semiconductor electrode 14 and filled between the catalyst electrode 13 and the semiconductor electrode 14. Further, the electrolytic solution 17 is held in the dye-sensitized solar cell 1B by the wall portion 18B formed in the periphery.
The dye-sensitized solar cell 1C can be connected to an external circuit by connection terminals (not shown) formed by extending the collecting electrodes 15 and 161 from the wall portion 18B.

Example 5 is a dye-sensitized solar cell 1 </ b> D in which a wall portion 18 is formed by melting a part of a glass substrate 12 ′ to be a light-transmitting substrate 12 as shown in FIG. 16. In Example 5, the current collecting electrode 151 was used as the light absorbing material 3. This dye-sensitized solar cell 1D was produced according to the following procedure.
(1) Production on the Counter Electrode Substrate 11 Side As in Example 1, the current collecting electrode 151 was integrally formed to obtain the counter electrode substrate 11 on which the platinum thin film to be the catalyst electrode 13 was formed. Unlike the current collecting electrode 15 in the first embodiment, the current collecting electrode 151 is also formed on a formation portion to be bonded to the light transmissive substrate 12 of the wall portion 18. Function.
Next, the glass flux 4 was applied to the current collecting electrode 151 on the site where the wall portion 18 was formed.
(2) Production of Glass Substrate 12 ′ as Translucent Substrate 12 Provided with Semiconductor Electrode 14 In the same manner as (2) Translucent substrate 12 provided with semiconductor electrode 14 in Example 1, semiconductor electrode 14 is produced. Was produced.

(3) Joining Counter Electrode Substrate 11 and Translucent Substrate 12 Next, a spacer (not shown) having a thickness of 150 μm is attached to the counter electrode substrate 11 and the glass substrate 12 ′ with the catalyst electrode 13 and the semiconductor electrode 14 facing each other. Arranged through. At this time, the glass flux 4 applied to the counter electrode substrate 11 also adheres to the glass substrate 12 ′ side (see FIG. 14). Thereafter, as shown in FIG. 14, the YAG laser is applied to the formation site of the wall portion 18 of the counter electrode substrate 11 from the direction perpendicular to the glass substrate 12 ′ and the glass substrate 12 ′ under the same conditions as in the first embodiment. The current collector electrode 151 was irradiated to heat the glass flux 4 and the glass substrate 12 ′ in contact therewith. As a result, the wall 18 forming part of the glass substrate 12 ′ is heated and melted, and the melt is brought into contact with the forming part of the counter electrode substrate 11 and then solidified to form a wall 18 that is a melted solid, and the remaining part is transparent. The counter substrate 11 and the translucent substrate 12 were joined as the optical substrate 12 (see FIG. 15).
Thereafter, an electrolytic solution 17 was injected into the space formed by them in the same manner as in Example 1 (see FIG. 16).

As shown in FIG. 16, the dye-sensitized solar cell 1 </ b> D manufactured in this way includes a counter electrode substrate 11, a translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, and a counter electrode substrate 11. Current collecting electrode 151 and catalyst electrode 13 disposed on one side, current collecting electrode 16 disposed on one side of translucent substrate 12 facing counter electrode 11 and semiconductor electrode 14 having a sensitizing dye, and And an electrolytic solution 17 contained in at least a part of the semiconductor electrode 14 and filled between the catalyst electrode 13 and the semiconductor electrode 14. Moreover, the electrolyte solution 17 is hold | maintained in the dye-sensitized solar cell 1D by the wall part 18 formed in the circumference | surroundings.
This dye-sensitized solar cell 1D can be connected to an external circuit by connection terminals (not shown) formed by extending the collecting electrodes 151 and 16 from the wall portion 18.

  The present invention is not limited to the description of the above-described embodiments, and various modifications can be made within the scope of the present invention depending on the purpose, application, and the like. For example, as the electrolytic solution 17, an ionic liquid such as a nonvolatile imidazolium salt or a gelled version of this ionic liquid can be used.

It is a model perspective view for demonstrating a mode that a laser beam is irradiated and a wall part is formed. It is a schematic cross section for demonstrating a mode that a laser beam is irradiated to a light absorption material. It is a schematic cross section for demonstrating a mode that after melting a part of translucent board | substrate with the laser beam, it solidified and it joined the wall part. It is a schematic cross section for demonstrating the structure of the dye-sensitized solar cell in which the wall part of a present Example is formed. It is a schematic cross section for demonstrating a mode that a laser beam is irradiated to a light absorption material. It is a schematic cross section for demonstrating a mode that after melting a part of counter electrode board | substrate with the laser beam, it solidified and it joined the wall part. It is a schematic cross section for demonstrating the structure of the dye-sensitized solar cell in which the wall part of a present Example is formed. It is a schematic cross section for demonstrating a mode that an adhesive resin is hardened by irradiating a laser beam to a light absorption material. It is a schematic cross section for demonstrating a mode that the counter electrode board | substrate and the translucent board | substrate were couple | bonded with the hardened | cured adhesive resin. It is a schematic cross section for demonstrating the structure of the dye-sensitized solar cell with which the counter electrode board | substrate and the translucent board | substrate were adhere | attached by the wall part of the present Example. It is a schematic cross section for demonstrating a mode that a collecting electrode which functions as a light absorption material is irradiated with a laser beam, and adhesive resin is hardened. It is a schematic cross section for demonstrating a mode that the wall part was formed with the hardened adhesive resin and the counter electrode board | substrate and the translucent board | substrate were couple | bonded. It is a schematic cross section for demonstrating the structure of the dye-sensitized solar cell with which the counter electrode board | substrate and the translucent board | substrate were adhere | attached by the wall part of the present Example. It is a schematic cross section for demonstrating a state which irradiates a laser beam to the current collection electrode which functions as a light absorption material, and fuse | melts a glass substrate. It is a schematic cross section for demonstrating a mode that after melting a part of translucent board | substrate with the laser beam, it solidified and it joined the wall part. It is a schematic cross section for demonstrating the structure of the dye-sensitized solar cell by which the wall part of a present Example is joined with the translucent board | substrate.

Explanation of symbols

  1, 1A, 1B, 1C, 1D; Dye-sensitized solar cell, 11, 11A; Counter electrode substrate, 12; Translucent substrate, 13; Catalyst electrode, 14; Semiconductor electrode, 15, 16, 151, 161; Electrode, 17; electrolyte, 18, 18A, 18B; wall, 2; laser beam, 3; light absorber, 4; glass flux, 5;

Claims (14)

A counter electrode substrate 11, a glass-made translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, a catalyst electrode 13 disposed on the one surface side of the counter electrode substrate 11, and the light-transmitting substrate A semiconductor electrode 14 having a sensitizing dye disposed on one side of the conductive substrate 12 facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and the catalyst electrode 13 and the semiconductor electrode 14 An electrolyte solution 17 filled between and a wall portion 18 provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14;
The wall portion 18 is formed by a laser beam irradiated from a vertical direction on the translucent substrate 12 side to a formation site where the wall portion 18 of the glass substrate to be the translucent substrate 12 is formed. A dye-sensitized solar cell, which is formed by a melted and solidified product obtained by melting and solidifying a formation site. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. An electrolyte solution 17 filled, and a wall portion 18A provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14,
The wall portion 18A is formed on the formation portion where the wall portion 18A of the substrate to be the counter electrode substrate 11 is formed by the laser beam irradiated from the vertical direction on the translucent substrate 12 side. A dye-sensitized solar cell, which is formed of a molten and solidified product obtained by melting and solidifying. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. An electrolyte 17 filled, and a wall portion 18B provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14,
The wall portion 18B includes a bonded surface to be bonded to the wall portion 18B of the counter electrode substrate 11, a bonded surface to be bonded to the wall portion 18B of the translucent substrate 12, A dye-sensitized solar cell, wherein the adhesive resin filled in between is cured by laser light irradiated from the vertical direction on the side of the light-transmitting substrate 12.   4. A current collecting electrode 161 which is electrically connected to the semiconductor electrode 14 and absorbs laser light is further provided on a joint surface of the translucent substrate 12 with the wall portions 18, 18A and 18B. The dye-sensitized solar cell according to any one of the above.   4. The dye sensitizing method according to claim 1, further comprising a current collecting electrode 151 that is electrically connected to the catalyst electrode 13 and absorbs laser light at a joint surface between the counter electrode substrate 11 and the wall portions 18, 18 </ b> B. Sensitive solar cell.   The dye-sensitized solar cell according to any one of claims 1 to 5, wherein the counter electrode substrate 11 is made of ceramics. A counter electrode substrate 11, a glass-made translucent substrate 12 disposed to face one surface of the counter electrode substrate 11, a catalyst electrode 13 disposed on the one surface side of the counter electrode substrate 11, and the light-transmitting substrate A semiconductor electrode 14 having a sensitizing dye disposed on one side of the conductive substrate 12 facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and the catalyst electrode 13 and the semiconductor electrode 14 And a wall portion 18 provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14. A method of sealing a sensitive solar cell,
A light absorbing material and a glass flux are attached to a formation site where the wall portion 18 of the glass substrate to be the light transmitting substrate 12 is formed, and then the light absorbing material on the light transmitting substrate 12 side is attached. The glass substrate is melted by irradiating a laser beam from the vertical direction, and then the melt reaches the counter electrode substrate 11 and then solidified to form the wall portion 18 to form the counter electrode substrate 11 and the transparent substrate. A method for sealing a dye-sensitized solar cell, comprising bonding a light-emitting substrate 12. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. A dye-sensitized solar comprising: a filled electrolyte solution 17; and a wall portion 18A provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14. A battery sealing method comprising:
A light absorbing material and a glass flux are attached to the formation site where the wall portion 18A of the substrate to be the counter electrode substrate 11 is to be formed, and then the light absorbing material is viewed from the vertical direction on the light transmitting substrate 12 side. The substrate is melted by irradiating a laser beam, and then the melt is allowed to reach the translucent substrate 12 and then solidified to form the wall portion 18A to form the counter electrode substrate 11 and the translucent substrate. A method for sealing a dye-sensitized solar cell, comprising bonding a substrate 12.   The method for sealing a dye-sensitized solar cell according to claim 7 or 8, wherein the light absorbing material is contained in the glass flux. Counter electrode substrate 11, translucent substrate 12 disposed to face one surface of counter electrode substrate 11, catalyst electrode 13 disposed on the one surface side of counter electrode substrate 11, and translucent substrate 12 A semiconductor electrode 14 having a sensitizing dye disposed on one side facing the counter electrode substrate 11, and contained in at least a part of the semiconductor electrode 14, and between the catalyst electrode 13 and the semiconductor electrode 14. A dye-sensitized solar comprising: a filled electrolyte solution 17; and a wall portion 18B provided between the counter electrode substrate 11 and the translucent substrate 12 and around the catalyst electrode 13 and the semiconductor electrode 14. A battery sealing method comprising:
A light absorbing material is attached to a formation site where the light transmitting substrate 12 and / or the wall portion 18B of the counter electrode substrate 11 is formed, and the walls of the counter electrode substrate 11 and the light transmitting substrate 12 are formed. The adhesive resin is filled between the formation sites where the portion 18B is to be formed, and then the adhesive resin is cured by irradiating the light-absorbing material with a laser beam from the vertical direction on the light-transmitting substrate 12 side. And forming the wall portion 18B, and bonding the counter electrode substrate 11 and the translucent substrate 12 through the wall portion 18B, thereby sealing the dye-sensitized solar cell.   The method for sealing a dye-sensitized solar cell according to claim 10, wherein the light absorbing material is contained in the adhesive resin.   12. The current collector electrode 161 according to claim 7, further comprising a current collecting electrode 161 that is electrically connected to the semiconductor electrode 14 at the formation site of the translucent substrate 12 and functions as the light absorbing material. Method for sealing a dye-sensitized solar cell.   The dye-sensitized solar according to claim 7, 10 or 11, further comprising a current collecting electrode 151 electrically connected to the catalyst electrode 13 at the formation site of the counter electrode substrate 11 and functioning as the light absorbing material. Battery sealing method.   The method for sealing a dye-sensitized solar cell according to any one of claims 7 to 13, wherein the counter electrode substrate 11 is made of ceramics.

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