JP2005302499A - Dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell which maintains stable power generation performance by making a conductive body such as a current collection body with a metal having excellent resistance to the corrosion of an electrolyte and by doing things like that. <P>SOLUTION: The dye-sensitized solar cell comprises a translucent substrate (such as a glass substrate); a substrate (such as a ceramic substrate) facing the translucent substrate; a semiconductor electrode (made of titanium and others) which is placed on one surface of the translucent substrate and has a sensitized dye; a catalyst electrode (made of platinum and others) which is placed on one surface of the substrate; and an electrolyte (such as an electrolyte composed of I<SB>2</SB>and LiI) which is included at least in a part of the semiconductor electrode, and filled between the semiconductor electrode and the catalyst electrode. A current of a metal is measured by a specified method, the metal (such as platinum) is included in the semiconductor (of the current collector electrode and others) placed in the solar cell, and the value of the current of the metal (such as platinum) is 5 to 60% of the current value of nickel. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dye-sensitized solar cell that directly converts light energy into electric energy. More specifically, the present invention relates to the fact that a conductor such as a collecting electrode contains a metal having excellent corrosion resistance against an electrolyte, and a tungsten film having high corrosion resistance is formed on the surface of the conductor such as a collecting electrode. The provision relates to a dye-sensitized solar cell in which stable power generation performance is maintained.

  At present, in solar power generation, solar cells using single crystal silicon, polycrystalline silicon, amorphous silicon, and HIT (Heterojunction with Intrinsic Thin-layer) combined with these have been put into practical use and have become the main technology. These solar cells have an excellent 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 electrolyte is interposed between a titania porous electrode supporting a sensitizing dye and a counter electrode, and although the photoelectric conversion efficiency is lower than that of the current silicon-based solar cell, the material, Significant cost reduction is possible in terms of manufacturing method.

  In a dye-sensitized solar cell, various conductors such as a collecting electrode are disposed. Conventionally, these conductors are generally used for applications that have excellent corrosion resistance and require corrosion resistance. Often formed of nickel.

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

However, the electrolyte often used in this dye-sensitized solar cell has a severe effect of corroding a metal, and nickel has insufficient corrosion resistance, so that it cannot be a solar cell with stable performance. is there.
The present invention solves the above-mentioned conventional problems, and various conductors such as a collecting electrode disposed in a dye-sensitized solar cell are metals having excellent corrosion resistance against an electrolyte. And providing a dye-sensitized solar cell in which stable power generation performance is maintained by providing a highly corrosion-resistant tungsten film on the surface of a conductor such as a collecting electrode. To do.

The present invention is as follows.
1. Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, semiconductor electrode 3 having a sensitizing dye disposed on one surface side of translucent substrate 1, and the substrate 2, a catalyst electrode 4 disposed on one surface side, an electrolyte 5 contained in at least a part of the semiconductor electrode 3 and filled between the semiconductor electrode 3 and the catalyst electrode 4, and the semiconductor electrode 3, a dye-sensitized solar cell including a negative electrode-side conductor that is electrically connected to the catalyst electrode 3 and a positive electrode-side conductor that is electrically connected to the catalyst electrode 4. The negative electrode-side conductor is an electrolyte solution in which an iodine-based electrolyte is dissolved. The current value at −0.8 V when a potential of −0.8 to +0.8 V is swept between the negative electrode side conductor using platinum as a counter electrode is 5 to 60% of the current value when nickel is used. The negative electrode side metal is contained, and the positive electrode side conductor is the positive electrode with platinum as a counter electrode in the electrolyte solution. A current value at +0.8 V when a potential of −0.8 to +0.8 V is swept between the conductor and the conductor contains a metal on the positive electrode side that is 5 to 60% of the current value at the time of nickel. Dye-sensitized solar cell characterized.
The current value can be measured by, for example, the apparatus shown in FIG.
A counter electrode made of a platinum wire with a diameter of 2 mm and a wire made of a negative electrode side metal or a positive electrode side metal with a diameter of 2 mm (spaced 5 mm away from the counter electrode) are immersed in the following electrolyte solution. -0.8 to +0 between a counter electrode and a wire made of a metal on the negative electrode side or a wire made of a metal on the positive electrode side by a click voltammetry measuring device (for example, model “HSV-100” manufactured by Hokuto Denko Co., Ltd.) .8V is swept, and in the case of the negative electrode side metal, the current value (mA / cm ² ) at a potential of −0.8V is measured, and in the case of the positive electrode side metal, the current value (mA / cm ² ) at the potential of + 0.8V. cm ² ).
Electrolyte solution; 0.1 mol lithium iodide, 0.05 mol iodine, 0.5 mol 4-tert-butylpyridine and 0.6 mol 1,2-dimethyl-3-propylimidazolium iodide A solution dissolved in 1000 ml of acetonitrile. As the electrolyte solution, for example, trade name “Iodolyte PN-50” manufactured by Solaronix Co., Ltd. or an equivalent product can be used.
Similarly, the current value when the metal is nickel is measured, and the current value of each of the negative electrode side metal and the positive electrode side metal is divided by the current value when the metal is nickel and multiplied by 100 to obtain the current value when nickel. The percentage of the current value is calculated.
2. The negative electrode side metal is at least one of titanium and molybdenum, and the positive electrode side metal is molybdenum. 2. A dye-sensitized solar cell according to 1.
3. The negative electrode side conductor is a negative electrode side collector electrode 6111, 6112, 6113, 6114 for collecting current from the semiconductor electrode 3, and the positive electrode side conductor is a positive electrode for collecting current from the catalyst electrode 4. 1. The side current collecting electrodes 6121, 6122, 6123 above. Or 2. 2. A dye-sensitized solar cell according to 1.
4). 2. The tungsten film is provided on at least a part of at least one of the negative electrode side current collecting electrodes 6111, 6112, 6113, 6114 and the positive electrode side current collecting electrodes 6121, 6122, 6123. 2. A dye-sensitized solar cell according to 1.
5). Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, semiconductor electrode 3 having a sensitizing dye disposed on one surface side of translucent substrate 1, and the substrate 2, a catalyst electrode 4 disposed on one surface side, an electrolyte 5 contained in at least a part of the semiconductor electrode 3 and filled between the semiconductor electrode 3 and the catalyst electrode 4, and the semiconductor electrode 3, a dye-sensitized solar cell including a negative electrode-side conductor that conducts to 3 and a positive electrode-side conductor that communicates with the catalyst electrode 4, at least one surface of the negative-side conductor and the positive-side conductor A dye-sensitized solar cell, characterized in that a tungsten film is provided on at least a part thereof.
6). The negative electrode side conductor is a negative electrode side collector electrode 6111, 6112, 6113, 6114 for collecting current from the semiconductor electrode 3, and the positive electrode side conductor is a positive electrode for collecting current from the catalyst electrode 4. 5. The side current collecting electrodes 6121, 6122, 6123 above. 2. A dye-sensitized solar cell according to 1.
7). 1. The substrate 2 is made of ceramic. To 6. The dye-sensitized solar cell of any one of these.

The dye-sensitized solar cell of the present invention in which a conductor such as a collecting electrode contains a metal having high corrosion resistance, and another dye of the present invention in which a tungsten film is provided on at least a part of the surface of the conductor In a sensitized solar cell, a conductor such as a collecting electrode has sufficient corrosion resistance against an electrolyte, and excellent power generation performance is stably maintained.
Tungsten is excellent in corrosion resistance, but it is not always easy to bak it on a thick film or to deposit it thickly by sputtering or the like. Therefore, by providing a tungsten film on at least a part of the surface of a conductor made of titanium, molybdenum, or the like that can be easily baked or sputtered, a conductor having excellent corrosion resistance and low resistance can be easily manufactured. be able to.
Moreover, when the negative electrode side metal is at least one of titanium and molybdenum and the positive electrode side metal is molybdenum, the corrosion resistance of each of the negative electrode side conductor and the positive electrode side conductor can be sufficiently improved. .
Further, the negative electrode side conductors are negative electrode side current collecting electrodes 6111, 6112, 6113, 6114 for collecting current from the semiconductor electrode 3, and the positive electrode side conductors are collected from the catalyst electrode 4 for positive electrode side current collecting. In the case of the electrode 6121, 6122, 6123, stable current collecting performance is maintained.
Further, when a tungsten film is provided on at least a part of the surface of at least one of the negative electrode side collector electrodes 6111, 6112, 6113, 6114 and the positive electrode side collector electrodes 6121, 6122, 6123, it is more excellent. It can be set as the current collection electrode which has high corrosion resistance.
Furthermore, when the board | substrate 2 consists of ceramics, it can be set as the dye-sensitized solar cell excellent in durability.

Hereinafter, the dye-sensitized solar cell of the present invention and other dye-sensitized solar cells of the present invention will be described in detail with reference to FIGS.
Various negative electrode side conductors and positive electrode side conductors are disposed in the dye-sensitized solar cell of the present invention. And the electric current value measured by the said method of the negative electrode side metal contained in a negative electrode side conductor is 5 to 60% of the electric current value of nickel measured by this method, and especially 5 to 25%, and also 5 to 5%. It is preferably 20%. Moreover, the current value measured by the above method of the positive electrode side metal contained in the positive electrode side conductor is 5 to 60% of the current value of nickel measured by this method, in particular 5 to 40%, and further 5 to 5%. 30% is preferred.

  Titanium and molybdenum are mentioned as a negative electrode side metal whose electric current value measured by said method is 5 to 60% of the electric current value of nickel measured similarly. The negative electrode side conductor may contain only one of these highly corrosion-resistant metals, or may contain both. Furthermore, titanium having higher corrosion resistance is preferable as the negative electrode side metal. Moreover, molybdenum is mentioned as a positive electrode side metal whose electric current value measured by said method is 5 to 60% of the electric current value of nickel measured similarly. The content of the metal having high corrosion resistance in the negative electrode side conductor and the positive electrode side conductor is preferably 10% by mass or more, particularly preferably 50% by mass or more, when each conductor is 100% by mass. 100% by mass is particularly preferable.

  Examples of the negative electrode-side conductor include negative electrode-side current collecting electrodes 6111, 6112, 6113 and 6114 for collecting current from the semiconductor electrode 3. In addition, negative through-hole conductors 6211 and 6212 that are filled in through holes provided through the light-transmitting substrate 1 or the substrate 2 and are conducted to the semiconductor electrode 3, and negative conductivity that are conducted to the semiconductor electrode 3. Examples include negative electrode side extraction electrodes 6411 and 6412 that are electrically connected to the bonding layer 63 and the semiconductor electrode 3. Among these negative electrode-side conductors, the negative electrode-side collector electrode and the negative electrode-side extraction electrode may be provided with a tungsten film having higher corrosion resistance on at least a part of its surface.

  Examples of the positive electrode side conductor include positive electrode side current collecting electrodes 6121, 6122, 6123 for collecting current from the catalyst electrode 4. Further, the through hole provided through the substrate 2 is filled and the positive side through hole conductors 6221 and 6222 connected to the catalyst electrode 4, the positive side conductive bonding layer connected to the catalyst electrode 4 and the catalyst electrode 4. And positive electrode side extraction electrodes 6421, 6422, 6423 and the like that are electrically connected to each other. Among these positive electrode side conductors, the positive electrode side collector electrode and the positive electrode side extraction electrode may be provided with a tungsten film having higher corrosion resistance on at least a part of the surface thereof.

  In addition, a tungsten film may be provided on the entire surface of each conductor on the negative electrode side and the positive electrode side, but since the conductor itself contains a highly corrosion-resistant metal, only the portions that are in direct contact with the electrolyte, etc. May be coated. Thereby, the corrosion resistance of each conductor can be made higher. The thickness of the tungsten film is not particularly limited, but is preferably 0.1 μm or more, particularly 0.2 μm or more, and more preferably 0.5 μm or more (usually 1.0 μm or less). If the thickness of this film is 0.1 μm or more, the corrosion resistance of each conductor can be further improved.

  Various negative electrode side conductors and positive electrode side conductors are also disposed in other dye-sensitized solar cells of the present invention. In another dye-sensitized solar cell of the present invention, a tungsten film is provided on at least a part of the surface of at least one of the negative electrode side conductor and the positive electrode side conductor. Although the metal which forms a negative electrode side conductor and a positive electrode side conductor is not specifically limited, Nickel, gold | metal | money, silver, copper, etc. are mentioned. If the conductor is made of a metal having low corrosion resistance such as silver and copper, or if the metal having low corrosion resistance is contained in a large amount of 50% by mass or more, particularly 80% by mass, the entire surface of the conductor It is preferable that a tungsten film is provided. Thereby, the corrosion resistance of the whole conductor can be improved reliably. The thickness of the tungsten film is not particularly limited, but is preferably 0.1 μm or more, particularly 0.2 μm or more, and more preferably 0.5 μm or more (usually 1.0 μm or less). If the thickness of this film is 0.1 μm or more, the corrosion resistance of each conductor can be further improved.

Other examples of the negative electrode-side conductor in the dye-sensitized solar cell of the present invention include negative electrode-side current collecting electrodes 6111, 6112, 6113, 6114, and negative electrode-side extraction electrodes 6411, 6412. Moreover, as a positive electrode side conductor, the positive electrode side current collection electrode 6121, 6122, 6123, the positive electrode side extraction electrode 6421, 6422, 6423, etc. are mentioned.
Incidentally, the catalyst electrode 4 in each of the dye-sensitized solar cell of the present invention and the other dye-sensitized solar cells of the present invention is almost in direct contact with the electrolyte 5 and has high resistance to the electrolyte. Although it is necessary to have corrosiveness, the catalyst electrode 4 is usually formed of platinum having high corrosion resistance.

Hereinafter, each negative electrode side conductor and positive electrode side conductor will be described in detail.
The negative electrode side collector electrode for collecting current from the semiconductor electrode 3 is one of the “negative electrode side collector electrode 6111” (see FIGS. 3 and 4) and the “negative electrode side collector electrode 6114” (see FIGS. 9 and 10). As described above, the light-transmitting substrate 1 can be provided on one surface side. Moreover, it can also be provided on the other surface side of the translucent substrate 1 as in the “negative electrode side collecting electrode 6113” (see FIGS. 6 and 7). The planar shape of these negative electrode-side current collecting electrodes is not particularly limited as long as the light-transmitting property is maintained, and can be formed so as to surround the semiconductor electrode 3. Furthermore, it can be an electrode made of a linear electrode and formed by a specific electrode pattern, for example, a lattice shape (see FIGS. 3, 4, 6, 7, 9, 10), a comb shape, a radial shape. It can be set as the electrode of planar shape, such as.

  In the case of the negative electrode side collector electrode made of this linear electrode and formed by a specific electrode pattern, the width and thickness of the linear electrode are not particularly limited, and are set in consideration of the electrical resistance, cost, etc. It is preferable to do. The total area of the negative electrode side collecting electrodes 6111, 6113, 6114 is 0.1 to 20%, particularly 0.1 to 5%, and more preferably 0.1 to 1% with respect to the total area of the semiconductor electrode 3. preferable. If the total area of the negative electrode side collector electrode is 0.1 to 20% with respect to the total area of the semiconductor electrode, the amount of light applied to the semiconductor electrode 3 can be sufficiently maintained, and the current collection efficiency is increased. be able to.

  The positive electrode side collector electrode for collecting current from the catalyst electrode 4 is a substrate like the above “positive electrode side collector electrode 6121” (see FIG. 4) and the above “positive electrode side collector electrode 6123” (see FIG. 10). 2 can be provided on one side. Moreover, it can also be provided on the other surface side of the substrate 2 like the “positive electrode side current collecting electrode 6122” (see FIG. 7). The positive current collecting electrodes 6121, 6122, 6123 are formed by forming the catalyst electrode 4 from a noble metal excellent in conductivity such as platinum, and in particular, when the thickness is 20 nm or more, and further 1 μm or more (usually 10 μm or less) However, it is preferably provided from the viewpoint of cost. That is, since platinum or the like is expensive, it is preferable to make the catalyst electrode 4 as thin as possible. However, if it is thin, the resistance becomes high. Thus, by providing the positive-side current collecting electrodes 6121, 6122, and 6123, the current collecting efficiency can be improved and the cost can be reduced. Further, when the catalyst electrode 4 is formed of a composition in which the conductive oxide is mixed with a substance having catalytic activity, the resistance of the catalyst electrode 4 becomes higher. Therefore, the positive electrode side current collecting electrodes 6121, 6122, It is more preferable to provide 6123 to increase the current collection efficiency.

  The planar shape of the positive-side current collecting electrodes 6121, 6122, and 6123 is not particularly limited. However, since the translucency is not essential on the substrate 2 side, it can be planar. When this positive electrode side collecting electrode is planar, in order to obtain a positive electrode side collecting electrode with low resistance, it has a planar shape similar to that of the catalyst electrode 4 and is 50% or more with respect to the catalyst electrode 4, in particular It is preferably a planar electrode having an area of 65% or more, and further 80% or more (may have substantially the same area as in FIGS. 4, 7, and 10). More preferably, the catalyst electrode 4 is arranged in a similar shape.

  The positive-side current collecting electrodes 6121, 6122, and 6123 may be electrodes that are linear electrodes and are formed with a specific electrode pattern. This specific pattern is not particularly limited, and may be, for example, a lattice shape, a comb shape, a radial shape, or the like. In the case of a positive electrode side collector electrode made of this linear electrode and formed by a specific electrode pattern, the width and thickness of the linear electrode are not particularly limited, and are set in consideration of the electrical resistance, cost, etc. It is preferable to do. When the positive electrode side collector electrode is an electrode formed of a linear electrode and formed by a specific electrode pattern, the total area of the positive electrode side collector electrodes 6121, 6122, 6123 is not particularly limited. The total area can be 0.1% or more, particularly 5% or more, and further 10% or more. In addition, the total area can be 90% or more, and the current collecting efficiency can be further improved if the positive electrode side current collecting electrode having such a large area is used.

  A method of providing the negative electrode side current collecting electrodes 6111, 6112, 6113, 6114 and the positive electrode side current collecting electrodes 6121, 6122, 6123 is not particularly limited. For example, using a mask on which a predetermined pattern is formed, Examples include a method of depositing a metal such as titanium or molybdenum by a physical vapor deposition method such as an electron beam vapor deposition method, and then patterning by photolithography or the like. Moreover, it can form by the method of patterning by the screen-printing method etc. using the metallized ink containing each metal component, and baking it after that.

  As the through-hole conductor, a negative electrode-side through-hole conductor 6211 (see FIGS. 6 and 7), a conductor filled in a through-hole provided through the front and back of the translucent substrate 1, and the wall surface of the through-hole The conductor layer etc. which were formed in are mentioned. Further, through-holes provided through the front and back of the substrate 2 such as a positive-side through-hole conductor 6221 (see FIG. 7), a negative-side through-hole conductor 6212, and a positive-side through-hole conductor 6222 (see FIGS. 9 and 10). Examples thereof include a conductor filled in a hole and a conductor layer formed on the wall surface of the through hole. The through hole can be formed by various methods such as irradiation with a laser beam such as a YAG laser or a carbon dioxide laser, drilling, or punching using a punch. In the case where the substrate 2 is a ceramic substrate, a through hole can be easily formed in a green sheet using a punch or the like.

  The cross-sectional shape of the through hole formed through the front and back of the translucent substrate 1 and the substrate 2 is not particularly limited, and may be a circle, an ellipse, a polygon such as a triangle, a quadrangle, or the like. This cross-sectional shape is preferably circular. Moreover, the dimension in the radial direction of the through hole is not particularly limited. When the through hole has a circular cross section, the through hole can have a diameter of 0.05 to 1 mm, particularly 0.1 to 0.8 mm. Furthermore, when it is not circular in cross section, it can be a through hole having an opening size equivalent to that in the case of circular cross section.

  The method of filling the through hole with the conductor is not particularly limited. For example, a conductor paste is injected from at least one opening of the through hole by a hole filling printing method or the like, and then fired to obtain a conductor filled in the through hole. be able to. The conductor paste is not particularly limited, and a paste prepared by mixing a metal powder having high corrosion resistance such as titanium or molybdenum, an organic binder, an organic solvent, a solvent such as water, or the like can be used. Further, a metal powder such as titanium or molybdenum, a metal powder such as gold, platinum, palladium, copper, or nickel, and an alloy powder such as a silver-platinum alloy or a silver-palladium alloy can be used in combination. Furthermore, the paste for conductors can also contain a glass component. A glass component is preferable because it can be fired at a lower temperature. The conductor layer can be formed on the wall surface of the through hole by an electroless plating method or the like.

  The conductive bonding layer 63 is provided at a required place such as one side of each of the translucent substrate 1 and the substrate 2. A method for providing the conductive bonding layer 63 is not particularly limited, but the conductive bonding layer 63 can be formed using a conductive adhesive. As this adhesive, a conductive resin in which a conductive component is blended with a resin can be used. Examples of the resin include polyamide resins, thermoplastic polyester resins, modified polyolefin resins such as maleic acid-modified polyethylene, and thermoplastic resins such as polyolefin resins having adhesiveness such as ethylene-ethyl acrylate copolymer resins. Moreover, thermosetting resins, such as an epoxy resin, a urethane resin, a polyimide resin, and a thermosetting polyester resin, are mentioned. As the conductive component, titanium, molybdenum, or the like is used, and other metals and carbon black can be used in combination.

  For the conductive bonding layer 63, a conductive adhesive is prepared, and this conductive adhesive is applied to a required portion, for example, one side of each of the translucent substrate 1 and the substrate 2, and heated as necessary. It can be formed by such processes. In addition, a molded body having a predetermined shape and thickness made of a conductive adhesive is formed in advance, and this molded body is placed on one side of each of the translucent substrate 1 and the substrate 2, and then other The substrate can be formed by a process such as disposing and heating as necessary.

  The negative electrode side extraction electrodes 6411 and 6412 are terminals for extracting electric power from the semiconductor electrode 3. Further, the positive electrode side extraction electrodes 6421, 6422, and 6423 are terminals for extracting electric power from the catalyst electrode 4. The negative electrode side extraction electrode 6411 (see FIGS. 3 and 4) is provided on one side of the translucent substrate 1, that is, the surface on which the semiconductor electrode 3 and the like are formed, and the negative electrode side extraction electrode 6412 (see FIGS. 6 and 7). Is provided on the other surface side of the translucent substrate 1. The positive electrode side extraction electrodes 6421 (see FIGS. 3 and 6) and 6422 (see FIG. 4) are provided on one surface side of the substrate 2, that is, the surface on which the catalyst electrode 4 and the like are formed. Is provided on the other side of the substrate 2. These extraction electrodes are deposited with a metal such as titanium, molybdenum, etc. by physical vapor deposition such as magnetron sputtering and electron beam vapor deposition using a mask on which a predetermined pattern is formed. It can be formed by a method of patterning by photolithography or the like, and a method of patterning by a screen printing method or the like using a paste containing powders of various metals as described above, followed by baking.

In the dye-sensitized solar cell, as a structure in which a translucent substrate and a negative-side through-hole conductor and a positive-side through-hole conductor filled in a through-hole provided through each front and back of the substrate are disposed, For example, the following are mentioned.
Negative electrode side current collecting electrodes 6111, 6112, 6114 provided on one surface side of translucent substrate 1 and positive electrode side current collecting electrodes 6121, 6123 provided on one surface side of the substrate are in contact with electrolyte 5 respectively. There is. In particular, the negative electrode side collecting electrodes 6111, 6112, 6114 are usually disposed between the translucent substrate 1 and the semiconductor electrode 3. However, since the semiconductor electrode 3 is a porous body, the electrolyte is transmitted therethrough. In many cases, the negative electrode side collector electrode comes into contact. Therefore, the negative electrode side current collecting electrode is provided on the other surface side of the translucent substrate 1, and the negative electrode side through hole conductor 6211 filled in the through hole provided so as to penetrate the front and back of the translucent substrate 1 provides a semiconductor electrode. 3 and the negative electrode side collecting electrode 6113 can be connected (see FIGS. 6 and 7). Further, the positive electrode side current collecting electrode is provided on the other surface side of the substrate 2, and the positive electrode side through hole conductor 6221 filled in the through hole provided so as to penetrate the front and back of the substrate 2, thereby the catalyst electrode 4 and the positive electrode side current collecting electrode. A structure in which the electrode 6122 is connected can be employed (see FIG. 7). In this case, each of the negative electrode side collector electrode 6113 and the positive electrode side collector electrode 6122 may be formed of titanium, molybdenum, or the like that has high corrosion resistance. It can also be formed of nickel, copper or the like having low corrosion resistance.

Furthermore, in the dye-sensitized solar cell, as a structure in which a translucent substrate and a through-hole conductor filled in a through-hole provided through each surface of the substrate and a conductive bonding layer are disposed, For example, the following are mentioned.
A dye-sensitized solar cell can be used as a solar cell unit panel by arranging a large number of batteries in a panel body. For example, a dye having a substrate 2 provided with electrode terminals that can be easily attached to and detached from the panel body 101 A sensitized solar cell can be obtained. As the electrode terminals, there are a negative electrode terminal which is electrically connected to the semiconductor electrode 3 and a positive electrode terminal which is electrically connected to the catalyst electrode 4, and these electrode terminals are usually provided on the other surface side of the substrate 2. In this case, the substrate 2 may be any of a glass substrate, a resin substrate, a ceramic substrate, and the like, but it is easy to dispose the negative electrode terminal and the positive electrode terminal, and the dye sensitization has excellent durability. A ceramic substrate that can be a type solar cell is preferred.

  The negative electrode side electrode terminal and the positive electrode side electrode terminal are not particularly limited as long as the dye-sensitized solar cell can be disposed on the panel body 101 of the solar cell unit panel. For example, as shown in FIGS. 9 and 10, each of the negative electrode terminal and the positive electrode terminal can be a pin P <b> 1 or P <b> 2 that constitutes a pin connector, respectively. As described above, in the dye-sensitized solar cell in which the negative electrode terminal and the positive electrode terminal are pins, the pins P1 and P2 are connected to the sockets S1 and S2 on the panel body 101 including the sockets S1 and S2 corresponding to the pins. It can arrange by inserting in (refer FIG. 13, 14).

  The pin P1 and the pin P2 are not particularly limited as long as the dye-sensitized solar cell can be disposed on the panel body 101 of the solar cell unit panel. The pins P1 and P2 can be formed of copper, brass or the like, and the surface may be covered with gold, tin, nickel or the like. Further, the shape of the cross section of each of the pins P1 and P2 may be any of a circle, an ellipse, a polygon such as a triangle and a quadrangle. Furthermore, the pins P1 and P2 can be joined and fixed to the other end surface side of each of the through-hole conductors 6212 and 6222 using a brazing material such as a silver-palladium brazing material. Further, the pins P1 and P2 can be joined and fixed to the other end surface side of each of the through-hole conductors 6212 and 6222 by irradiation with laser light.

  The panel body 101 includes sockets S1 and S2 corresponding to the pins P1 and P2, respectively. By inserting the pins P1 and P2 into the sockets S1 and S2, the conduction and fixing of the dye-sensitized solar cell to the panel body are performed. And a solar cell unit panel can be manufactured (see FIGS. 13 and 14). In this solar cell unit panel, each solar cell can be connected in series or in parallel, and a solar cell unit panel having a predetermined voltage and capacity can be obtained. The solar cell unit panel is preferably provided with a protective material 1011 for protecting each arranged dye-sensitized solar cell from dust, wind and rain. As this protective material, what consists of resin, such as glass and highly transparent polycarbonate, polysulfone, can be used.

  The semiconductor electrode 3 and the negative electrode side electrode terminal may be electrically connected in any way. For example, as shown in FIGS. 9 and 10, the negative electrode side current collecting electrode provided on one surface side of the translucent substrate 1. The conductive bonding layer 63 disposed so as to surround the semiconductor electrode 3 and the catalyst electrode 4 between at least one of 6114 and the translucent conductive layer 7 and one surface side of the substrate 2, and the substrate 2 It is possible to conduct through the negative through hole conductor 6212 filled in the through hole 21 formed so as to penetrate therethrough. Further, the catalyst electrode 4 and the positive electrode terminal P2 may be electrically connected in any way. For example, as shown in FIGS. 9 and 10, the through hole 22 formed through the substrate 2 is filled. The positive electrode side through-hole conductor 6222 can be conducted.

  The other end surface side of the negative electrode side through hole conductor 6212 is connected to the negative electrode side electrode terminal P1, and one end surface side of the negative electrode side through hole conductor 6212 is connected to the conductive bonding layer 63, so that the semiconductor electrode 3 and the negative electrode side electrode terminal are connected. P1 is conducted. In order to make the electrical connection more reliable, a connecting conductor 9 is provided on one surface side of the substrate 2 so as to surround the catalyst electrode 4, and the one surface side of the conductive bonding layer 63 and the translucent substrate 1 are arranged. Connecting at least one of the negative electrode side collecting electrode 6114 and the translucent conductive layer 7 provided on the one surface side, and connecting the other surface side of the conductive bonding layer 63 and the connecting conductor 9. Is preferred. In particular, as shown in FIGS. 9 and 10, a negative electrode side collector electrode 6114 having a portion surrounding the semiconductor electrode 3 and a lattice-like portion is provided on one surface side of the translucent substrate 1, and one surface of the conductive bonding layer 63 is provided. More preferably, the side of the negative electrode side collector electrode 6114 is connected to the entire surface of the portion surrounding the semiconductor electrode 3, and the other surface side of the conductive bonding layer 63 is connected to the entire surface of the connecting conductor 9. The connecting conductor 9 can be formed by the same method using the same metal as the negative electrode side collecting electrode 6114 and the like.

  Further, as shown in FIG. 9, the one end surface side of the positive electrode side through-hole conductor 6222 is connected to the positive electrode side electrode terminal P <b> 2 and the other end surface side of the positive electrode side through hole conductor 6222 is connected to the catalyst electrode 4. 4 and the positive electrode terminal P2 are electrically connected. Further, as shown in FIG. 10, when the positive electrode side collector electrode 6123 is provided on one surface side of the substrate 2, the other end surface side of the positive electrode side through-hole conductor 6222 is connected to the positive electrode side collector electrode 6123. Also good. The other end surface side of the positive electrode side through-hole conductor 6222 may be directly connected to the catalyst electrode 4 and may be in contact with the positive electrode side collecting electrode 6123.

Hereinafter, other configurations of the dye-sensitized solar cell of the present invention and other dye-sensitized solar cells of the present invention will be described in detail.
Examples of the “translucent substrate 1” include substrates made of glass, resin sheets, and the like. The resin sheet is not particularly limited, and examples thereof include resin sheets made of polyester such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polycarbonate, polysulfone, and polyethyleneidene norbornene. When a plurality of solar cells are used while being arranged on the panel body, the light-transmitting substrate 1 of each solar cell may be a glass substrate or a resin substrate. Moreover, when it is a resin substrate, the resin may be the same resin or a different resin.
In addition, translucency means that the transmittance | permeability of visible light with a wavelength of 400-900 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 thickness of the translucent substrate 1 varies depending on the material and is not particularly limited. However, it is preferable that the transmissivity is 60 to 99%, particularly 85 to 99%.

  The “substrate 2” disposed opposite to the light-transmitting substrate 1 may have a light-transmitting property or may not have a light-transmitting property. The substrate 2 having a light-transmitting property can be formed using glass, a resin sheet, or the like as in the case of the light-transmitting substrate 1. When this board | substrate 2 consists of resin sheets, said various thermoplastic resins are mentioned as resin used for formation of this resin sheet. When the substrate 2 is a light-transmitting substrate, the thickness varies depending on the material and is not particularly limited. However, the thickness may be 60 to 99%, particularly 85 to 99%. preferable.

  The substrate 2 that does not have translucency can be formed of ceramic. The ceramic substrate has high strength, and this substrate can be used as a support substrate to provide a dye-sensitized solar cell having excellent durability. The ceramic used for forming the ceramic substrate is not particularly limited, and various ceramics such as oxide ceramics, nitride ceramics, and carbide ceramics can be used. Examples of the oxide ceramic include alumina, mullite, zirconia and the like. Examples of the nitride ceramic include silicon nitride, sialon, titanium nitride, and aluminum nitride. Further, examples of the carbide-based ceramic include silicon carbide, titanium carbide, and aluminum carbide. As the ceramic, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable.

When the board | substrate 2 consists of ceramics, the thickness is not specifically limited, However, It can be referred to as 100 micrometers-5 mm, 300 micrometers-4 mm, Especially 500 micrometers-2 mm, Furthermore, it can be set as 700 micrometers-1.5 mm. When the thickness of the ceramic substrate is 100 μm to 5 mm, particularly 500 μm or more, the substrate having this high strength becomes a support substrate, and a dye-sensitized solar cell having excellent durability can be obtained.
When a plurality of solar cells are arranged and used in the panel body, the substrate 2 may be any of a glass substrate, a resin substrate, and a ceramic substrate. Furthermore, when it is a resin substrate, the resin may be the same resin or a different resin. When the ceramic substrate is used, the ceramics may be the same ceramic or different ceramics.

  The light-transmitting substrate 1 can be formed of glass, resin, or the like, and the substrate 2 can be formed of glass, resin, ceramic, or the like. The light-transmitting substrate 1 is a glass substrate, and the substrate 2 is A ceramic substrate is preferred. As the ceramic used for the ceramic substrate, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable. Thus, the translucent substrate 1 is a glass substrate, the substrate 2 is preferably a ceramic substrate made of alumina, silicon nitride, zirconia, etc., the translucent substrate 1 is a glass substrate, and the substrate 2 is alumina. More preferably, it is a substrate.

  The “semiconductor electrode 3” is disposed on one side of the translucent substrate 1. The electrode substrate of the semiconductor electrode 3 can be formed of metal oxide, metal sulfide, or the like. Examples of the metal oxide include titania, tin oxide, zinc oxide, niobium oxide such as niobium pentoxide, tantalum oxide, and zirconia. Also, double oxides such as strontium titanate, calcium titanate, and barium titanate can be used. Furthermore, examples of the metal sulfide include zinc sulfide, lead sulfide, and bismuth sulfide.

  The method for producing the electrode substrate is not particularly limited. For example, the electrode substrate can be produced by applying a paste containing fine particles such as metal oxide and metal sulfide on the surface of the light-transmitting substrate 1 and baking the paste. The method for applying the paste is not particularly limited, and examples thereof include a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. The electrode substrate produced in this way is formed in the form of an aggregate made up of fine particles.

  The electrode substrate is coated with a colloidal solution in which fine particles such as metal oxide and metal sulfide and a small amount of organic polymer are dispersed on the surface of the translucent substrate 1 and the like, then dried and then heated. It can also be produced by a process such as decomposing and removing the organic polymer. This colloidal solution can also be applied by various methods such as a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. The electrode substrate produced by this method is also formed in the form of an aggregate made up of fine particles.

  The thickness of the semiconductor electrode 3 is not particularly limited, but may be 0.1 to 100 μm, preferably 1 to 50 μm, particularly 2 to 40 μm, and more preferably 5 to 30 μm. If the thickness of the semiconductor electrode 3 is 0.1 to 100 μm, photoelectric conversion is sufficiently performed and power generation efficiency is improved. Further, the semiconductor electrode 3 is preferably heat-treated in order to improve its strength and adhesion to the translucent substrate 1 and the substrate 2. The temperature and time of the heat treatment are not particularly limited, but the heat treatment temperature is preferably 40 to 700 ° C., particularly 100 to 500 ° C., and the heat treatment time is preferably 10 minutes to 10 hours, particularly preferably 20 minutes to 5 hours. In addition, when using a resin sheet as the translucent board | substrate 1 and the board | substrate 2, it is preferable to heat-process at low temperature so that resin may not thermally deteriorate.

  As said "sensitizing dye" which the semiconductor electrode 3 has, the complex dye and organic dye which improve the effect | action of a photoelectric conversion 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. In this case, it is preferable to set the type of sensitizing dye to be used in combination and the amount ratio thereof depending on the wavelength range and intensity distribution of the irradiated light. The sensitizing dye preferably has a functional group for bonding to the semiconductor electrode. Examples of this functional group include a carboxyl group, a sulfonic acid group, and a cyano group.

  The method for attaching the sensitizing dye to the electrode substrate is not particularly limited. For example, the 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. Can be attached. Alternatively, this solution can be applied to the electrode substrate and then adhered by removing the organic solvent. Examples of the coating method include a wire bar method, a slide hopper method, an extrusion method, a curtain coating method, a spin coating method, and a spray coating method. Furthermore, this solution can also be applied by a printing method such as offset printing, gravure printing or screen printing.

  The adhesion amount of the sensitizing dye is preferably 0.01 to 1 mmol, particularly 0.5 to 1 mmol with respect to 1 g of the semiconductor electrode. When the adhesion amount is 0.01 to 1 mmol, photoelectric conversion in the semiconductor electrode is efficiently performed. Moreover, if the sensitizing dye that has not adhered to the semiconductor electrode is liberated around the electrode, the conversion efficiency may be lowered. For this reason, it is preferable to remove the excess sensitizing dye by washing the semiconductor electrode after the treatment for attaching the sensitizing dye. This removal can be performed by washing with a polar solvent such as acetonitrile and an organic solvent such as an alcohol solvent using a washing tank. In order to attach a large amount of sensitizing dye to the electrode substrate, it is preferable to heat the semiconductor electrode and perform a treatment such as dipping or coating. In this case, in order to avoid water adsorbing on the surface of the semiconductor electrode, it is preferable to perform the treatment promptly at 40 to 80 ° C. without heating to room temperature after heating.

  The “catalyst electrode 4” is disposed on one side of the substrate 2. The catalyst electrode 4 is composed of a metal having a catalytic activity or a material having a catalytic activity, a conductive oxide used for forming a light-transmitting conductive layer 7 described later, and a conductive polymer. It can be formed by at least one kind. As a substance having catalytic activity, noble metals such as platinum, gold and rhodium (however, silver is not preferred because of its low corrosion resistance to electrolytes, etc. Hereinafter, silver is also not preferred for the parts where the electrolyte etc. can contact) .), Carbon black and the like, and these have conductivity together. The catalyst electrode is preferably formed of a noble metal having catalytic activity and electrochemically stable, and it is particularly preferable to use platinum having high catalytic activity and high corrosion resistance to the electrolyte.

In the case of using a metal, a conductive oxide, a conductive polymer, or the like that does not have catalytic activity, examples of the metal used by mixing with the catalyst electrode include aluminum, copper, chromium, nickel, tungsten, and the like. Furthermore, polyaniline, polypyrrole, polyacetylene, etc. are mentioned as a conductive polymer used by mixing with a catalyst electrode. Moreover, as this conductive polymer, what was prepared by mix | blending various electroconductive substances with resin which does not have electroconductivity is mentioned. The resin not having conductivity is not particularly limited, and may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include thermoplastic polyester resin, polyamide, polyolefin, and polyvinyl chloride. Furthermore, examples of the thermosetting resin include an epoxy resin, a thermosetting polyester resin, and a phenol resin. The conductive substance is not particularly limited, and examples thereof include metals such as carbon black, copper, aluminum, nickel, chromium, and tungsten, and conductive polymers such as polyaniline, polypyrrole, and polyacetylene. As the conductive substance, a noble metal and carbon black having both conductivity and catalytic activity are particularly preferable. Only one type of conductive material may be used, or two or more types may be used.
When metals, conductive oxides, conductive polymers, etc. that do not have catalytic activity are used, the content of the above-mentioned substances having catalytic activity is 100 masses of metals, conductive oxides, conductive polymers, etc. Parts, preferably 1 to 99 parts by mass, particularly 50 to 99 parts by mass.

  Thus, the catalyst electrode 4 can be formed of a substance having conductivity and catalytic activity. Further, it can be formed of at least one of a metal, a conductive oxide and a conductive polymer containing a substance having catalytic activity. Furthermore, the catalyst electrode 4 may be a layer made of only one kind of material or a mixed layer made of two or more kinds of materials. Further, the catalyst electrode 4 may be a single layer, a metal layer, a conductive oxide layer, a conductive polymer layer, and a mixed layer composed of two or more of metal, conductive oxide and conductive polymer. A multilayer catalyst electrode composed of two or more of them may be used. The thickness of the catalyst electrode is not particularly limited, but 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 is 3 nm to 10 μm, the catalyst electrode can have a sufficiently low resistance.

  The catalytic electrode 4 made of a substance having catalytic activity can be formed by applying a paste containing fine particles of a substance having catalytic activity to the surface of the substrate 2 or the like. Further, the catalyst electrode 4 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. Examples of the coating method include various methods such as a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. Furthermore, these catalyst electrodes 4 can also be formed by depositing metal or the like on the surface of the substrate 2 or the like by sputtering, vapor deposition, ion plating, or the like.

  Further, the catalyst electrode 4 made of a conductive polymer containing a substance having a catalytic activity is composed of a conductive polymer and a substance having a catalytic activity such as a powder or a fiber, a Banbury mixer, an internal mixer, an open The resin composition prepared by kneading with a roll or the like can be formed into a film, and the film can be bonded to the surface of the substrate 2 or the like. Further, a solution or dispersion prepared by dissolving or dispersing the resin composition in a solvent can be applied to the surface of the substrate 2 and the like, dried, the solvent removed, and heated as necessary. . In addition, when the catalyst electrode 4 is a mixed layer, it can be formed by an appropriate method among the above-described various methods according to the type of material contained.

  The “electrolyte 5” is contained in at least a part of the semiconductor electrode 3 and is filled between the translucent substrate 1 and the substrate 2. The electrolyte 5 is usually contained in the entire semiconductor electrode 3 and filled in the entire gap between the translucent substrate 1 and the substrate 2.

Examples of the electrolyte include (1) I ₂ and iodide, (2) Br ₂ and bromide, (3) metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ion, and (4) sodium polysulfide. And electrolytes containing sulfur compounds such as alkylthiol-alkyldisulfides, (5) viologen dyes, (6) hydroquinone-quinones, and the like. As iodide in (1) is, LiI, NaI, KI, CsI, metal iodide such as CaI _2, and tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide iodine salt of quaternary ammonium compounds such as id, etc. Is mentioned. As the bromide in (2), LiBr, NaBr, KBr, CsBr, CaBr 2 , etc. of the metal bromide, and tetra-alkyl ammonium bromide, bromine salts of quaternary ammonium compounds such as pyridinium bromide and the like. Among these electrolytes, 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. These electrolytes may use only 1 type and may use 2 or more types.

  The electrolyte 5 can be blended in a solvent together with various additives and used as an electrolyte solution. This solvent preferably has a low viscosity, a high ion mobility, and sufficient ion conductivity. Examples of such solvents include (1) carbonates such as ethylene carbonate and propylene carbonate, (2) heterocyclic compounds such as 3-methyl-2-oxazolidinone, (3) ethers such as dioxane and diethyl ether, (4 ) Chain ethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, (5) methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl Monoalcohols such as ether and polypropylene glycol monoalkyl ether, (6) ethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as polyglycol, polypropylene glycol and glycerin, (7) nitriles such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, and (8) aprotic such as dimethyl sulfoxide and sulfolane. Examples include polar substances. These solvent may use only 1 type and may use 2 or more types.

  When an electrolyte solution is used, this solution is sealed between the light-transmitting substrate 1 and the substrate 2 with a resin or glass around the semiconductor electrode 3 or the like, and the electrolyte solution is injected into a gap formed thereby. Can be made. The electrolyte solution may be injected into the gap from the translucent substrate 1 side or the substrate 2 side, and it is preferable to provide an injection port on the side that is easily perforated 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 solution can be injected more easily.

  The distance between the semiconductor electrode 3 and the catalyst electrode 4 is not particularly limited, but can be 200 μm or less, particularly 100 μm or less, and further 50 μm or less (usually 1 μm or more). If this interval is less than or equal to a predetermined value, the conversion efficiency can be sufficiently increased.

  Examples of the resin used for sealing around the semiconductor electrode 3 and the like include polyamide resins, thermoplastic polyester resins, modified polyolefin resins such as maleic acid-modified polyethylene, and polyolefin resins having adhesive properties such as ethylene-ethyl acrylate copolymer resins. These thermoplastic resins can be mentioned. Moreover, thermosetting resins, such as an epoxy resin, a urethane resin, a polyimide resin, and a thermosetting polyester resin, are mentioned. Furthermore, this sealing can also be performed with glass, and it is preferable to seal with glass particularly in a solar cell that requires long-term durability.

The translucent conductive layer 7 should just have translucency and electroconductivity. The material of the translucent conductive layer 7 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. Examples of the metal include platinum, gold, copper, aluminum, rhodium and indium. The thickness of the light transmitting conductive layer 7 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.

  In the case where the negative electrode side current collecting electrodes 6111, 6112, 6113, and 6114 are provided, the current collecting efficiency is further improved if the light transmitting conductive layer 7 is provided, but the light transmitting conductive layer 7 is not necessarily provided. For example, in particular, in a dye-sensitized solar cell having a structure as shown in FIG. 5, a solar cell with sufficiently high power generation efficiency can be obtained without providing the translucent conductive layer 7. In this dye-sensitized solar cell, a porous insulating layer I that electrically insulates the catalyst electrode 4, the negative electrode side, and the positive electrode side in this order from the substrate 2 side between the substrate 2 and the translucent substrate 1. The negative current collecting electrode 6112 and the semiconductor electrode 3 are stacked and provided. An electrolyte is filled and contained between the interface between the catalyst electrode 4 and the porous insulating layer I and the interface between the translucent substrate 1 and the semiconductor electrode 3. Therefore, when the negative electrode side collector electrode 6112 is flat, the negative electrode side collector electrode 6112 needs to be a porous body. The porosity of the negative electrode side collector electrode 6112 made of this porous body is not particularly limited, but may be 2 to 40%, particularly 10 to 30%, and further 15 to 25%. If the porosity is 10 to 30%, the electrolyte can be easily contained without lowering the current collection efficiency. The negative current collecting electrode 6112 may be an electrode made of the above-described linear electrode and formed by a specific electrode pattern.

  The material of the porous insulating layer I is not particularly limited, and examples thereof include ceramic, resin, and glass, and ceramic is preferable. As the ceramic, various ceramics such as oxide ceramics, nitride ceramics, and carbide ceramics can be used. Examples of the oxide ceramic include alumina, mullite, zirconia and the like. Examples of the nitride ceramic include silicon nitride, sialon, titanium nitride, and aluminum nitride. Further, examples of the carbide-based ceramic include silicon carbide, titanium carbide, and aluminum carbide. As the ceramic, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable.

  The planar shape of the porous insulating layer I is not particularly limited as long as the negative electrode side and the positive electrode side can be electrically insulated. For example, the planar shape may be a planar shape, and may be a specific shape such as a lattice shape, a comb shape, or a radial shape. It may be a shape. Furthermore, the porosity of the porous insulating layer I is not particularly limited, but is preferably 2 to 40%, particularly 10 to 30%, and more preferably 15 to 25%. When the porosity is 10 to 30%, the electrolyte is easily contained, and the function as a solar cell is not impaired. Further, the thickness of the porous insulating layer I is not particularly limited, but also varies depending on the method of manufacturing the dye-sensitized solar cell. For example, this dye-sensitized solar cell includes a laminate in which a substrate 2, a catalyst electrode 4, a porous insulating layer I, a negative-side current collecting electrode 612, and a semiconductor electrode 3 are arranged in this order, and a translucent substrate. In the case of manufacturing by laminating 1 and facing, the thickness of the porous insulating layer I can be 0.5 to 20 μm, particularly 1 to 10 μm, and further 2 to 5 μm. When the thickness of the porous insulating layer I is 0.5 to 20 μm, the negative electrode side and the positive electrode side can be sufficiently electrically insulated.

The porous insulating layer I may be formed by forming a coating film on the surface of the catalyst electrode 4 by a screen printing method or the like using a paste containing each ceramic component or the like, and then firing at a predetermined temperature. it can. Further, a ceramic such as alumina, silicon nitride, zirconia, or the like can be deposited on the surface of the catalyst electrode 4 by a physical vapor deposition method such as a magnetron sputtering method or an electron beam vapor deposition method.
In the dye-sensitized solar cell of FIG. 5, the positive electrode side collecting electrode 6121 can be provided between the substrate 2 and the catalyst electrode 4.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
The dye-sensitized solar cell 201 of FIG. 3 was produced as follows.
[1] Production of one laminate of glass substrate 1 having a length of 100 mm, a width of 100 mm, a thickness of 1 mm, and a transparent conductive layer 7 made of fluorine-doped tin oxide having a sheet resistance of 10 Ω / □ on the surface The surface of the light-transmitting conductive layer 7 is formed by DC sputtering with titanium (the current value at −0.8 V measured by the above method is 14% of the current value of nickel similarly measured) of 500 nm. Deposited to a thickness, a grid-like negative electrode side collecting electrode 6111 having a width of 30 μm and an interval of 500 μm and a negative electrode side extracting electrode 6411 having a thickness of 500 nm (see FIG. 8) were formed by photolithography. Thereafter, a slurry containing titania particles having a particle diameter of 10 to 20 nm (trade name “manufactured by Solaronix Co., Ltd., trade name”, on the surface of the translucent conductive layer 7 on which the negative electrode side collecting electrode 6111 and the negative electrode side extraction electrode 6411 are formed. Ti-Nonoxide D / SP ”) was applied by screen printing, dried at 120 ° C. for 1 hour, and then fired at 480 ° C. for 30 minutes to sinter a titania sintered layer (electrode, 96 mm long, 96 mm wide, 20 μm thick) Substrate) was formed. Next, this laminate is immersed in an ethanol solution of a ruthenium complex (manufactured by Solaronix, trade name “535bis-TBA”) for 10 hours, and the titania sintered particles absorb light in a wavelength region of 400 to 600 nm. A ruthenium complex, which is a dye, was attached to form the semiconductor electrode 3 to produce one laminate.

[2] Production of the other laminate A mixture of 5 parts by mass of magnesia, calcia, and silica, 2 parts by mass of binder and solvent as a sintering aid is added to 100 parts by mass of alumina powder with a purity of 99.9% by mass. A slurry was prepared, and an alumina green sheet was prepared by the doctor blade method using this slurry. Thereafter, a conductive coating film to be the catalyst electrode 4 was formed on one surface side of the alumina green sheet by screen printing using a metallized ink containing a platinum component. Further, a positive electrode side extraction electrode by screen printing using a metallized ink containing molybdenum (current value at +0.8 V measured by the above method is 20% of the current value of nickel similarly measured) A conductive coating film to be 6421 was formed at a position facing the negative electrode-side extraction electrode 6411. Next, the substrate is integrally fired at 1500 ° C. in a reducing atmosphere, and the catalyst electrode 4 having a length of 96 mm, a width of 96 mm, and a thickness of 500 nm is formed on one surface of the alumina substrate 2 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm. A laminate in which the positive electrode-side extraction electrode 6421 was formed was formed, and the other laminate was produced.

[3] Preparation of dye-sensitized solar cell The thermosetting resin is formed on the surface of the other laminate on the surface of the alumina substrate 2 where the catalyst electrode 4 is not formed and on the portion where the positive electrode-side extraction electrode 6421 is formed. A coating film having a width of 1 mm and a thickness of 60 μm is formed by screen printing using an adhesive composed of the following: After that, one laminate is formed so that the semiconductor electrode 3 faces the catalyst electrode 4 of the other laminate. And then placed on a hot plate adjusted to 100 ° C. with the glass substrate 2 side down, heated for 60 minutes, and the light-transmitting conductive layer 7 and the negative electrode-side extraction electrode 6411 of one laminate, The glass substrate 2 of the other laminate and the positive electrode side extraction electrode 6421 are bonded, and the bonding layer 8 having a width of 5 mm and a thickness of 30 μm (29 μm between the negative electrode side extraction electrode 6411 and the positive electrode side extraction electrode 6421) is formed. Formed. Thereafter, an iodine electrolyte solution (product name “Iodolyte PN-50” manufactured by Solaronix Co., Ltd.) is injected from an electrolyte solution injection port provided at a predetermined position of one of the laminates, and the electrolyte 5 is contained in the semiconductor electrode 3. At the same time, an electrolyte 5 was filled between the semiconductor electrode 3 and the collector electrode 4. After injection of the iodine electrolyte, the inlet was sealed using the above adhesive.

[4] Performance Evaluation of Dye-Sensitized Solar Cell An irradiation intensity of 100 mW / cm ^{2 is} applied to the dye-sensitized solar cell 201 produced by the above [1] to [3] using a solar simulator whose spectrum is adjusted to AM1.5. When irradiated with simulated sunlight, it had a characteristic of an open circuit voltage of 0.7 V per 1 cm ² .

Example 2
The dye-sensitized solar cell 202 of FIG. 4 was produced as follows.
[2] In the production of the other laminate in Example 1, on one surface side of the alumina green sheet, a conductive coating film serving as a lower layer of the positive current collecting electrode 6121 is screen-printed using a metallized ink containing a nickel component. Formed. Further, a positive electrode side extraction electrode by screen printing using a metallized ink containing molybdenum (current value at +0.8 V measured by the above method is 20% of the current value of nickel similarly measured) A conductive coating film to be 6421 was formed at a position facing the negative electrode-side extraction electrode 6411. Thereafter, the substrate was integrally fired in a reducing atmosphere at 1500 ° C., and the alumina substrate 2, the lower layer 6121 a of the positive electrode side collecting electrode 6121 and the positive electrode side extraction electrode 6422 were produced. Next, an upper layer 6121b of the positive current collecting electrode 6121 is produced by sputtering tungsten on the surface of the lower layer 6121a of the positive current collecting electrode 6121. Thereafter, platinum is deposited on the surface of the upper layer 6121b of the positive current collecting electrode 6121. The catalyst electrode 4 was produced by sputtering. In this way, on one surface side of the alumina substrate 2 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm, a positive electrode side current collector having a length of 96 mm, a width of 96 mm, a thickness of the lower layer 6121a of 250 nm, and a thickness of the upper layer 6121b of 250 nm. Example 1 except that a laminate in which the electrode 6121, the catalyst electrode 4 having a length of 96 mm, a width of 96 mm, a thickness of 500 nm, and a positive electrode side extraction electrode 6422 having a thickness of 500 nm were formed and the other laminate was produced was obtained. In the same manner, a dye-sensitized solar cell 202 was produced.
When this dye-sensitized solar cell 202 was irradiated with pseudo-sunlight with an irradiation intensity of 100 mW / cm ² by a solar simulator whose spectrum was adjusted to AM 1.5, it had a characteristic of an open circuit voltage of 0.7 V per 1 cm ^2. It was.

Example 3
The dye-sensitized solar cell 206 of FIG. 9 and the solar cell unit panels of FIGS. 13 and 14 were produced as follows.
[1] Production of one laminated body Glass substrate 1 having a length of 100 mm, a width of 100 mm, a thickness of 1 mm, and a translucent conductive layer 7 made of fluorine-doped tin oxide having a sheet resistance of 10 Ω / □ attached to one side. Titanium was deposited to a thickness of 500 nm on one surface side of the translucent conductive layer 7 by DC sputtering, and a negative current collecting electrode 6114 was formed by photolithography. The negative electrode side collector electrode 6114 has a width of 1 mm and a thickness of 500 nm, and a portion having a shape surrounding the semiconductor electrode 3 fabricated in a later step, and a grid-like shape having a width of 30 μm, a spacing of 500 μm, and a thickness of 500 nm. And formed with parts. Thereafter, a paste containing titania particles having a particle diameter of 10 to 20 nm (manufactured by Solaronix, trade name “Ti-Nonoxide D / SP”) was applied by screen printing, dried at 120 ° C. for 1 hour, and then 480 ° C. Was fired for 30 minutes to form a titania sintered layer (electrode substrate) having a length of 95 mm, a width of 95 mm, and a thickness of 20 μm. Thereafter, this laminate was immersed in an ethanol solution of a ruthenium complex (manufactured by Solaronix, trade name “535bis-TBA”) for 10 hours to attach a ruthenium complex, which is a sensitizing dye, to the titania sintered particles. 3 was formed.

[2] Production of laminate comprising catalyst electrode 100 parts by mass of alumina powder having a purity of 99.9% by mass, 5 parts by mass of magnesia, calcia and silica mixed powder, 2 parts by mass of binder and solvent as a sintering aid A slurry was prepared by blending and using this slurry, an alumina green sheet was prepared by the doctor blade method. Thereafter, two through-holes 21 and 22 were formed at predetermined locations on the alumina green sheet by punching holes. Next, using a metallized ink containing a tungsten component (content of tungsten component: 90% by mass), a conductive coating film that becomes the conductive joined body 9 by screen printing is formed on one side of the alumina green sheet in a later step. The catalyst electrode 4 was formed in a shape surrounding the catalyst electrode 4. At the same time, the through hole 21 was filled with the metallized ink containing the above tungsten component. Then, it dried at 100 degreeC for 30 minutes, the surface of the electrically conductive coating film was pressed with the pressure of 0.2 MPa, and the smoothness was improved.

  Next, a conductive coating film to be the catalyst electrode 4 was formed on one surface side of the alumina green sheet by screen printing using a metallized ink containing a platinum component. At the same time, metallized ink containing a tungsten component was filled into the through hole 22. Next, it is integrally fired at 1500 ° C. in a reducing atmosphere, and a conductive joint 9 having a width of 1 mm and a thickness of 500 nm is formed on one side of an alumina substrate 2 having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm, and a length of 90 mm, A laminate in which the catalyst electrode 4 having a thickness of 90 mm and a thickness of 500 nm was formed was produced. Further, a negative electrode side through hole conductor 6212 was formed in the through hole 21, and a positive electrode side through hole conductor 6222 was formed in the through hole 22.

[3] Joining of pins P1 and P2 Joined to the other end surface of the two negative electrode side through-hole conductors 6212 on the other surface side of the alumina substrate 2 in a circular cross section and joined to one end surface (the other end surface side of the negative electrode side through hole conductor 6212) The pin P1 having a diameter of 4 mm on the other end side, a diameter of the other end surface (tip side) of 3.5 mm, and a length of 10 mm was joined using a silver-palladium raw material. In addition, the other side of the two positive electrode side through-hole conductors 6222 on the other surface side of the alumina substrate 2 has a rectangular cross section and the long side of one end surface (the side joined to the other end surface side of the positive electrode side through-hole conductor 6222). A pin P2 having a length of 6 mm, a short side of 3 mm, a long side of the other end surface (tip side) of 5 mm, a short side of 2.5 mm, and a length of 10 mm was joined using a silver-palladium raw material.

[4] Fabrication of dye-sensitized solar cell A negative electrode side collector electrode 6114 formed on one surface side of the glass substrate 1 using a conductive adhesive in which 99% by mass of tungsten powder is blended in a thermosetting resin. A film having a width of 1 mm and a thickness of 60 μm is formed by screen printing so as to cover a portion of the shape surrounding the semiconductor electrode 3, and then the glass substrate 1 is attached to the semiconductor electrode 3 of the negative-side current collecting electrode 6114. The surrounding portion is disposed so as to face the conductive joined body 9 provided on one surface side of the alumina substrate 2 and the semiconductor electrode 3 faces the catalyst electrode 4. It was left to stand in a drier adjusted to 100 ° C. with the side down, and the translucent conductive layer 7 and the negative electrode side collecting electrode 6114 were bonded to the alumina substrate 2 and the conductive joined body 9. . The conductive bonding layer 63 had a width of 2 mm and a thickness of 30 μm. Thereafter, an iodine electrolyte solution (product name “Iodolyte PN-50”, manufactured by Solaronix Co., Ltd.) is injected from an electrolyte solution injection port provided at a predetermined position of the alumina substrate 2, and the electrolyte 5 is contained in the semiconductor electrode 3. The electrolyte 5 was filled between the semiconductor electrode 3 and the collector electrode 4. After injection of the iodine electrolyte, the inlet was sealed using the above adhesive.

[5] Performance Evaluation of Dye-Sensitized Solar Cell The irradiation intensity of 100 mW / cm ^{2 is} applied to the dye-sensitized solar cell 206 prepared by the above (1) to (3) using a solar simulator whose spectrum is adjusted to AM1.5. When irradiated with simulated sunlight, it had characteristics of an open current of about 10 mA per cm ² , an open circuit voltage of 0.55 V, and a conversion efficiency of 3.8%.

[6] Manufacture of solar cell unit panel Each of panel-sensitized solar cells manufactured in the above [1] to [4] can be arranged in a panel main body 101 in which a total of 20 pieces can be arranged, 4 vertically and 5 horizontally. Pins P1 and P2 of the dye-sensitized solar cell are inserted into S1 and S2 of the panel body 101 corresponding to the pins P1 and P2, respectively, and simultaneously fixed and arranged to produce a solar cell unit panel. did. In addition, each of the four pieces in the vertical direction was connected in parallel, and in the horizontal direction, each of the four pieces in the vertical direction connected in parallel was connected in series.

  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 electrolyte 5, it is also possible to use an ionic liquid such as a nonvolatile imidazolium salt, a gel obtained by gelling this ionic liquid, and a solid such as copper iodide or copper thiocyanide. The distance between the semiconductor electrode 3 and the catalyst electrode 4 is not particularly limited, but can be 200 μm or less, particularly 100 μm or less, and further 50 μm or less (usually 1 μm or more). If the interval in each case is not more than a predetermined value, the conversion efficiency can be sufficiently increased.

It is a schematic diagram which shows the method and apparatus which measure the electric current of the metal contained in a conductor. 2 is a graph showing changes in current versus voltage for various metals measured by the method and apparatus of FIG. 3 is a schematic diagram showing a cross section of a dye-sensitized solar cell 201 of Example 1. FIG. In the dye-sensitized solar cell 201 of FIG. 3, the dye-sensitized solar cell of Example 2 in which a positive electrode-side extraction electrode 6422 is provided instead of the positive electrode-side extraction electrode 6421 and a positive electrode-side collector electrode 6121 is further provided. It is a schematic diagram which shows the cross section of 202. FIG. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 203 of the other aspect in which the translucent conductive layer 7 is not provided. FIG. 3 is a schematic view showing a cross section of a dye-sensitized solar cell 204 in which a negative electrode side collecting electrode 6113 is provided on the other surface side of the translucent substrate 1. FIG. 7 is a schematic diagram showing a cross section of a dye-sensitized solar cell 205 in which a positive-side current collecting electrode 6122 is further provided on the other surface side of the substrate 2 in the dye-sensitized solar cell 204 of FIG. 6. It is explanatory drawing which looked at the dye-sensitized solar cells 201, 202, 204, and 205 of FIGS. 3, 4, 6, and 7 from the glass substrate 1 side. 6 is a schematic view showing a cross section of a dye-sensitized solar cell 206 of Example 3. FIG. FIG. 10 is a schematic diagram showing a cross section of a dye-sensitized solar cell 207 in which a positive electrode side collecting electrode 6123 is further provided on one surface side of the substrate 2 in the dye-sensitized solar cell 206 of FIG. 9. It is explanatory drawing which looked at the dye-sensitized solar cells 206 and 207 of FIG. 9 and 10 from the glass substrate 1 side. It is explanatory drawing which looked at the dye-sensitized solar cells 206 and 207 of FIG. 9 and 10 from the ceramic substrate 2 side. It is a front view which shows a mode that the three dye-sensitized solar cells 206 are arrange | positioned at the panel main body 101 provided with socket S1, S2. It is a schematic diagram which shows the cross section in the AA cross section of FIG. 13, and also shows a mode that the dye-sensitized solar cell 206 is arrange | positioned.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Translucent board | substrate, 2; Board | substrate, 21 and 22; Through hole, 3; Semiconductor electrode, 4; Catalyst electrode, 5; Electrolyte, 6111, 6112, 6113, 6114; 6123; positive electrode side collecting electrode, 6121a; lower layer, 6121b; upper layer, 6211, 6212; negative electrode side through hole conductor, 6221, 6222; positive electrode side through hole conductor, 63; conductive bonding layer, 6411, 6412; Electrode, 6421, 6422, 6423; positive electrode side extraction electrode, 7: translucent conductive layer, 8; bonding layer, 9; conductive bonding body, I: porous insulating layer, 101; panel body, P1, P2; S1, S2; socket, 1011; protective material, 201, 202, 203, 204, 205, 206, 207; dye-sensitized solar cell.

Claims (7)

Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, semiconductor electrode 3 having a sensitizing dye disposed on one surface side of translucent substrate 1, and the substrate 2, a catalyst electrode 4 disposed on one surface side, an electrolyte 5 contained in at least a part of the semiconductor electrode 3 and filled between the semiconductor electrode 3 and the catalyst electrode 4, and the semiconductor electrode In a dye-sensitized solar cell comprising a negative electrode-side conductor that is electrically connected to 3 and a positive-electrode-side conductor that is electrically connected to the catalyst electrode 4,
The negative electrode side conductor is -0.8 V when a potential of -0.8 to +0.8 V is swept between the negative electrode side conductor and platinum as an opposite electrode in an electrolyte solution in which an iodine-based electrolyte is dissolved. Containing a negative electrode side metal whose current value is 5 to 60% of the current value when nickel,
The positive electrode side conductor has a current value at +0.8 V when a potential of −0.8 to +0.8 V is swept between the positive electrode side conductor and platinum as a counter electrode in the electrolyte solution. A dye-sensitized solar cell comprising a positive electrode side metal that is 5 to 60% of the current value at the time.   The dye-sensitized solar cell according to claim 1, wherein the negative electrode side metal is at least one of titanium and molybdenum, and the positive electrode side metal is molybdenum.   The negative electrode side conductor is a negative electrode side collector electrode 6111, 6112, 6113, 6114 for collecting current from the semiconductor electrode 3, and the positive electrode side conductor is a positive electrode for collecting current from the catalyst electrode 4. The dye-sensitized solar cell according to claim 1, which is a side current collecting electrode 6121, 6122, 6123.   The tungsten film is provided on at least a part of at least one of the negative electrode side collector electrodes 6111, 6112, 6113, 6114 and the positive electrode side collector electrodes 6121, 6122, 6123. Dye-sensitized solar cell. Translucent substrate 1, substrate 2 disposed opposite to translucent substrate 1, semiconductor electrode 3 having a sensitizing dye disposed on one surface side of translucent substrate 1, and the substrate 2, a catalyst electrode 4 disposed on one surface side, an electrolyte 5 contained in at least a part of the semiconductor electrode 3 and filled between the semiconductor electrode 3 and the catalyst electrode 4, and the semiconductor electrode In a dye-sensitized solar cell comprising a negative electrode-side conductor that is electrically connected to 3 and a positive-electrode-side conductor that is electrically connected to the catalyst electrode 4,
A dye-sensitized solar cell, wherein a tungsten film is provided on at least part of the surface of at least one of the negative electrode side conductor and the positive electrode side conductor.   The negative electrode side conductor is a negative electrode side collector electrode 6111, 6112, 6113, 6114 for collecting current from the semiconductor electrode 3, and the positive electrode side conductor is a positive electrode for collecting current from the catalyst electrode 4. The dye-sensitized solar cell according to claim 5, which is a side current collecting electrode 6121, 6122, 6123.   The dye-sensitized solar cell according to any one of claims 1 to 6, wherein the substrate 2 is made of ceramic.

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