JP2017117851A - Dye-sensitized solar cell sheet, and manufacturing method of dye-sensitized solar cell sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell sheet capable of improving designability while keeping a maximum advantage of a dye-sensitized solar cell that can be manufactured at low cost, and a manufacturing method thereof.SOLUTION: In a dye-sensitized solar cell sheet 1, in at least one of a pair of sheet-like transparent materials 2a that oppose each other, an image layer 4 consisting of complementary color image parts 31a-31c formed in a predetermined image pattern is provided, and the image pattern is formed in a semi-transparent color in a mutual complementary color relation with a color of a sensitized dye of a photoelectrode constituting a power generation layer 3. Therefore, excellent designability can be presented by the image layer 4, and increase in cost of manufacture can be suppressed as further as possible. A manufacturing method of the dye-sensitized solar cell sheet 1 includes forming the image layer 4 and the photoelectrode in the one sheet-like transparent material 2a and then bonding it with the other sheet-like transparent material, thereby accurately aligning the image layer 4 and the photoelectrode.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dye-sensitized solar cell sheet that converts light energy into electric power and a method for producing the dye-enhanced solar cell sheet.

  Dye-sensitized solar cells have the great advantage that they can be manufactured at a lower cost than silicon-type solar cells, and can be formed into a relatively thin sheet. Yes. A sheet-like dye-sensitized solar cell (hereinafter referred to as a dye-sensitized solar cell sheet) generally includes a power generation unit in which a plurality of cells are connected in series between a pair of sheet-like transparent materials facing each other. It is a thing. The power generation unit includes a photoelectrode in which porous nanoparticles of a photocatalyst are attached in a film shape on a conductive substrate and a sensitizing dye is adsorbed on the porous nanoparticles, a counter electrode such as platinum or carbon, And an electrolyte layer interposed between the photoelectrode and the counter electrode.

  The dye-sensitized solar cell sheet can be manufactured in different colors depending on the sensitizing dye used for the photoelectrode. Furthermore, it is also possible to form a pattern or a pattern using a plurality of sensitizing dyes having different colors. For example, in Patent Document 1, a plurality of sensitizing dyes are attached to porous nanoparticles of a photoelectrode. A proposed configuration has been proposed. Such a configuration has high design properties due to various patterns and patterns.

JP 2002-75472 A

  By the way, in the conventional configuration using a plurality of sensitizing dyes described above, the sensitizing dyes different from each other are adsorbed on the porous nanoparticles of the photoelectrode. There is a problem that the cost increases. For example, as a manufacturing method of the configuration of Patent Document 1 described above, after a film made of porous nanoparticles is formed on a conductive substrate, a part of the film is removed in a predetermined pattern, and a partition wall is formed at the removal site. And sensitizing dyes of different colors are attached to the respective regions partitioned by the partition walls. As described above, in order to form a pattern or a pattern having excellent design properties, a number of steps for adsorbing a plurality of sensitizing dyes are required, and thus the manufacturing cost is increased due to the increase in the number of steps. It was. And the increase in manufacturing cost will reduce the maximum advantage which the dye-sensitized solar cell mentioned above has. For these reasons, there has been a demand for a structure having excellent design properties while suppressing an increase in cost required for production.

  The present invention proposes a dye-sensitized solar cell sheet that can improve the design while maintaining the maximum advantage of a dye-sensitized solar cell that can be manufactured at low cost, and a method for manufacturing the dye-sensitized solar cell sheet. is there.

  The present invention provides a power generation layer provided with a pair of sheet-shaped transparent materials facing each other, and one or a plurality of cells provided between the sheet-shaped transparent materials, each having a photoelectrode and a counter electrode facing each other. Each cell of the power generation layer is a dye-sensitized solar cell sheet in which a predetermined sensitizing dye is adsorbed to the photoelectrode, and the outer surface of at least one sheet-like transparent material and / or Alternatively, a translucent image layer is provided on the inner surface so as to overlap the power generation layer, and is formed by a predetermined image pattern with a translucent color complementary to the color of the sensitizing dye of the cell. And a complementary color image portion.

  Here, the image layer may have a configuration including one complementary color image portion or a configuration including a plurality of complementary color image portions. In the case of a configuration including a plurality of complementary color image portions, either a configuration in which each complementary color image portion is formed by the same image pattern or a configuration in which each complementary color image portion is formed by a different image pattern is used. good.

  In such a configuration, the complementary color is reflected by the light of the color reflected by the semi-transparent portion of the complementary color image portion and the light of the color that reaches the photoelectrode of the power generation layer and is reflected by the sensitizing dye of the photoelectrode. An image part is represented. Then, the complementary color image portion can be visually recognized distinctly from the periphery of the complementary color image portion. Therefore, according to this configuration, the design property can be improved by the complementary color image portion, and further, the design property can be further improved by using the complementary color image portion as a predetermined design (character, number, picture, etc.). In addition, since the color of the sensitizing dye of the photoelectrode and the semitransparent color of the complementary color image portion are complementary to each other, when light enters the semitransparent color portion, Light of a color photoexcited by the sensitizing dye passes through the site and reaches the photoelectrode. Therefore, in the power generation layer, even if it is light of the color that has passed through such a semi-transparent part, it can be photoexcited with the sensitizing dye of the photoelectrode in the same way as the light that has passed through the transparent part. it can. That is, the power generation layer having this configuration can exhibit a desired power generation capacity without being substantially affected by the complementary color image portion of the image layer.

  Here, in this configuration, the “complementary color relationship” between the color of the sensitizing dye of the photoelectrode and the translucent color of the complementary color image portion is in addition to the strict relationship that one color is the other complementary color. In other words, the complementary color image portion can transmit light that can be sufficiently photoexcited by the sensitizing dye of the photoelectrode. That is, it is only necessary to set the complementary color relationship described above so that the sensitizing dye of the photoelectrode can be photoexcited with the light transmitted through the supplemental image portion to exhibit the above-described desired power generation capability. For example, in the color of the sensitizing dye of the photoelectrode and the translucent color of the complementary color image portion, one color is in the relationship of the other complementary color, or one color is in a hue circle of 12 hues. It is preferable that the relationship is a color adjacent to the other complementary color. As a specific example, when one is yellow, the other can be set to blue-purple (strict complementary color), blue, or purple.

  In this configuration, an image layer is provided so as to cover the power generation layer, and the image layer can be formed on a sheet-like transparent material by printing or the like, for example. Since the power generation layer and the sheet-like transparent material can apply the conventional dye-sensitized solar cell configuration, this configuration provides an image layer on a general sheet-like dye-sensitized solar cell sheet. Can be manufactured relatively easily. Therefore, according to this configuration, the manufacturing process is not complicated, and an increase in manufacturing cost can be suppressed as much as possible. Therefore, this structure has the outstanding design property, maintaining the maximum advantage of the dye-sensitized solar cell which can be manufactured cheaply.

  In the dye-sensitized solar cell sheet of the present invention described above, the image pattern of the complementary color image portion is configured by halftone dots and / or lines, and the image layer has a plurality of different densities depending on the image pattern. A configuration including the complementary color image portion is proposed.

  Here, it is preferable that the plurality of complementary color image portions have different densities by changing the size (area, width, etc.) and pitch interval (number of lines) of halftone dots and lines.

  In such a configuration, each complementary color image portion includes light of a color reflected by a semitransparent color halftone dot or line, and light of a color that reaches the photoelectrode of the power generation layer and is reflected by the sensitizing dye of the photoelectrode. And are expressed differently depending on the respective concentrations. Therefore, since various designs can be represented by a plurality of complementary color image portions, according to this configuration, the design can be further improved.

  Furthermore, each complementary color image portion of this configuration can be formed relatively easily by printing halftone dots and lines. Therefore, even in this configuration, it can be manufactured without causing complicated manufacturing processes and an increase in manufacturing cost, and has excellent design properties.

  In the dye-sensitized solar cell sheet of the present invention described above, a configuration is proposed in which a transparent layer covering the image layer is provided on the sheet-like transparent material on which the image layer is disposed.

  According to such a configuration, light hitting the sheet outer surface at a low angle can be reflected by the transparent layer, so that the so-called color shift phenomenon can be suppressed, and the complementary color image portion can be clearly expressed in a desired color. More specifically, in a configuration that does not include a transparent layer, light that hits the complementary color image portion of the image layer at the low angle is reflected by the complementary color image portion and hardly reaches the photoelectrode. With the above light, the translucent color of the complementary color image portion appears strongly. The strong translucent color that appears due to such low-angle light affects the color that appears when the light strikes the outer surface of the sheet at a high angle, so the complementary color image portion is composed of the translucent color and the sensitizing dye. It becomes difficult to appear with a desired color consisting of colors. A phenomenon that makes it difficult to be expressed in a desired color in this way is the above-described color shift phenomenon, and there is a concern that the design property may be reduced due to the color shift phenomenon. In this configuration, since the low-angle light is reflected by the transparent layer covering the image layer, the color shift phenomenon due to the low-angle light can be suppressed, and the complementary color image portion can be expressed in a desired color by the high-angle light. Therefore, according to this structure, the design property by a complementary color image part is exhibited stably.

  In this configuration, it is preferable that the transparent layer is provided so as to cover the image layer disposed on the outer surface of the sheet-like transparent material. According to this configuration, the effect of suppressing the color transition phenomenon of the image layer can be more clearly generated.

  The present invention also relates to the above-described method for producing a dye-sensitized solar cell sheet having an image layer on the outer surface of one sheet-like transparent material, wherein the image layer is formed on the outer surface of one sheet-like transparent material. And, after forming at least the photoelectrode of the power generation layer on the inner surface of the sheet-like transparent material, the one sheet-like transparent material and the other sheet-like transparent material are joined via the power generation layer. This is a method for producing a dye-sensitized solar cell sheet.

  Here, in this method, after forming a power generation layer (a photoelectrode, a counter electrode, an electrolyte layer, etc.) on one sheet-like transparent material, it may be joined to the other sheet-like transparent material. Alternatively, a photoelectrode may be formed on one sheet-shaped transparent material, and a counter electrode may be formed on the other sheet-shaped transparent material, and then these sheet-shaped transparent materials may be joined.

  In this manufacturing method, the image pattern of the image layer and the photoelectrode can be accurately aligned by forming the image layer and the photoelectrode on one sheet-like transparent material. Therefore, according to this manufacturing method, the dye-sensitized solar cell sheet which has desired designability with the translucent color of an image pattern and the color of the sensitizing dye of a photoelectrode can be manufactured stably.

  More specifically, for example, in the case of a manufacturing method in which an image layer is formed on one sheet-like transparent material and a photoelectrode is formed on the other sheet-like transparent material, the sheet-like transparent material is joined. In this case, it is difficult to align the image pattern of the image layer and the photoelectrode, and there is a possibility that desired design properties cannot be exhibited due to the shift of the position. The production method of the present invention does not cause such a problem, and can produce a dye-sensitized solar cell sheet having a desired design as described above.

  According to the dye-sensitized solar cell sheet of the present invention, as described above, while maintaining the maximum advantage of the dye-sensitized solar cell that can be manufactured at a low cost, it is possible to exhibit excellent design properties in the complementary color image portion, and to obtain a desired color. The power generation capacity can be demonstrated.

  According to the method for producing a dye-sensitized solar cell sheet of the present invention, as described above, the dye-sensitized solar cell sheet of the present invention can be accurately aligned with the image layer and has excellent design. Can be manufactured stably.

It is a top view of the dye-sensitized solar cell sheet 1 of a present Example. 1 is an exploded perspective view of a dye-sensitized solar cell sheet 1. FIG. It is a cross-sectional enlarged view explaining the structure of the dye-sensitized solar cell sheet. It is a flowchart which shows the manufacturing process of the dye-sensitized solar cell sheet 1 of a present Example. (A) Partial enlarged sectional view of the sheet-like transparent material 2a after the coating layer forming step, (b) Partial enlarged sectional view of the sheet-like transparent material 2b after the counter electrode forming step, and (c) A portion for explaining the joining step It is an expanded sectional view.

Embodiments according to the present invention will be described below with reference to the accompanying drawings.
As shown in FIGS. 1 and 2, the dye-sensitized solar cell sheet 1 of the present embodiment includes a pair of sheet-like transparent materials 2a and 2b made of a predetermined transparent film or glass plate, and the sheet-like transparent materials 2a and 2b. A power generation layer 3 interposed therebetween and an image layer 4 provided on the outer surface of one sheet-like transparent material 2a are provided. Further, the sheet-like transparent material 2a is provided with a transparent layer 5 that covers the image layer 4 from the outside.

  In this embodiment, one sheet-like transparent material 2a side on which the image layer 4 is provided is defined as the front side, and the other sheet-shaped transparent material 2b side is defined as the back side. Further, in the sheet thickness direction, the space between both sheet-shaped transparent materials 2a and 2b is defined as the inside, and the front side of one sheet-shaped transparent material 2a and the back side of the other sheet-shaped transparent material 2b are defined as the outside. Thereby, each outer side surface and inner side surface of each sheet-like transparent material 2a, 2b are prescribed | regulated.

  The pair of sheet-like transparent materials 2a and 2b and the power generation layer 3 constitute a so-called dye-sensitized solar cell. Here, the power generation layer 3 includes a plurality of band-shaped cells 11 arranged in parallel, and the cells 11 are connected in series. As shown in FIG. 3, the cell 11 includes a pair of conductive layers 21, 21 arranged in an opposing manner, a negative electrode layer 22 provided on the inner surface of one conductive layer 21, and an inner surface of the other conductive layer 21. And the electrolyte layer 24 provided between the negative electrode layer 22 and the positive electrode layer 23. Further, sealing layers 26 and 26 are provided on the left and right sides of the negative electrode layer 22, the positive electrode layer 23, and the electrolyte layer 24. The plurality of cells 11 are juxtaposed between the front and back sheet-like transparent materials 2a and 2b so that the negative electrode layer 22 is located on the front side and the positive electrode layer 23 is located on the back side. Further, between the adjacent cells 11, silver wiring layers 27 that connect the adjacent cells 11 and 11 in series are provided.

  The negative electrode layer 22 is formed by adhering porous nanoparticles as a photocatalyst in a layered manner on the inner surface of the conductive layer 21 and adsorbing a predetermined sensitizing dye to the porous nanoparticles. In this example, zinc oxide particles are used as the porous nanoparticles. In addition, the positive electrode layer 23 of this example is formed by a thin film of a conductive polymer. Further, in this embodiment, the sheet-like transparent materials 2a and 2b are made of a transparent film made of polyethylene naphthalate, and the conductive layer 21 is made of indium tin oxide provided in layers. The negative electrode layer 22 and the one conductive layer 21 on which the negative electrode layer 22 is formed constitute a photoelectrode according to the present invention, and the positive electrode layer 23 and the other positive electrode layer 23 on which the positive electrode layer 23 is formed. The conductive layer 21 constitutes the counter electrode according to the present invention.

  Further, the sensitizing dye of the negative electrode layer 22 is an organic dye having a predetermined color having translucency, and each cell 11 of the power generation layer 3 exhibits a predetermined translucent color by the sensitizing dye. In this embodiment, since the yellow sensitizing dye is used, each cell 11 is translucent yellow (clear yellow).

  Such a power generation layer 3 generates electric power when the sensitizing dye of the negative electrode layer 22 absorbs the light and is photoexcited by irradiation with sunlight. In addition, since the principle of the electric power generation in the dye-sensitized solar cell sheet 1 of a present Example is the same as a general dye-sensitized solar cell, it abbreviate | omits about the detail.

  On the other hand, the image layer 4 is provided on the outer surface of the front sheet-like transparent material 2a so as to overlap the power generation layer 3 as shown in FIGS. In the present embodiment, the image layer 4 includes a plurality of complementary color image portions 31 a to 31 c formed at predetermined positions on the cells 11 constituting the power generation layer 3. The complementary color image portions 31a to 31c are formed by image patterns composed of halftone dots, and different image patterns are set in the complementary color image portions 31a to 31c. Specifically, each image pattern of each of the complementary color image portions 31a to 31c is composed of halftone dots having the same number of lines and different sizes (halftone dot sizes). Accordingly, the densities of the complementary color image portions 31a to 31c are different. In this embodiment, since the halftone dot sizes are gradually increased in the order of the complementary color image portion 31a, the complementary color image portion 31b, and the complementary color image portion 31c, the density of the complementary color image portion 31a is the lowest, and the complementary color image portion. The concentration of 31c is the highest.

  The halftone dots of the complementary color image portions 31a to 31c are formed in a translucent color that is complementary to the color of the sensitizing dye of the power generation layer 3 described above. When sunlight is incident on this halftone dot, light having the same color as the semitransparent color of the halftone dot is transmitted, and the sensitizing dye of the power generation layer 3 can be photoexcited by the light of the color. In this way, the half-transparent color of the halftone dot and the color of the sensitizing dye are complementary to each other, so that the halftone dot of the semi-transparent color emits light of a color photoexcited by the sensitizing dye of the power generation layer 3 To Penetrate. On the other hand, in the transparent region other than the halftone dots, the sunlight is incident on the power generation layer 3, so that the sensitizing dye is photoexcited by the sunlight. Here, since the sensitizing dye of the power generation layer 3 can be photoexcited by light having a color complementary to the color of the sensitizing dye, the light transmitted through the halftone dots of the complementary color image portions 31 a to 31 c and the power generation layer 3 are transmitted. Photoexcitation can be performed in the same manner by any incident sunlight. Therefore, the power generation layer 3 can be photoexcited substantially equally throughout the entire region, and can generate desired power stably.

  In the present embodiment, the halftone dots of the complementary color image portions 31a to 31c are formed of translucent blue. Here, the blue color corresponds to a color complementary to the yellow color of the sensitizing dye of the power generation layer 3. More specifically, the yellow complementary color is strictly bluish purple, and blue is a color adjacent to bluish purple in a hue circle represented by 12 hues of RGB colors. And even if it is blue, it transmits light that can be sufficiently photoexcited by the yellow sensitizing dye, so that it can be photoexcited in the same manner as light or sunlight transmitted through a complementary color (blue violet). 3 can generate a desired power. Thus, the semitransparent colors of the halftone dots of the complementary color image portions 31a to 31c are the colors of the sensitizing dye so that the photoexcitation necessary for generating the desired power in the power generation layer 3 is generated by the sensitizing dye. Or a color adjacent to the complementary color in the hue circle of 12 hues.

  These complementary color image portions 31 a to 31 c are green mixed with blue that can be seen by the light reflected by the halftone dots and yellow that can be seen by the light reflected by the negative electrode layer 22 (sensitizing dye) of the power generation layer 3 when sunlight is applied. Appears in the colors of the system. Further, since the complementary color image portions 31a to 31c have different halftone dot densities as described above, in the complementary color image portion 31a having the lowest density, more light is reflected by the negative electrode layer 22 (sensitizing dye). Therefore, it appears with a strong greenish yellow color due to the light. On the other hand, since the complementary color image portion 31c having the highest density has a large amount of light reflected by the halftone dots, it appears as a strong greenish blue color due to the light. Then, in the complementary color image portion 31b having an intermediate density, it appears in an intermediate green color between the complementary color image portion 31a and the complementary color image portion 31c. As described above, the complementary color image portions 31a to 31c are expressed by different green colors depending on their densities, and are visually recognized by three green colors.

  Furthermore, in this embodiment, the sheet-like transparent material 2a on the front side includes a portion (hereinafter referred to as a non-image portion) 7 in which the image layer 4 is not disposed. In the non-image portion 7, Enters the power generation layer 3 through the sheet-like transparent material 2a, and the sensitizing dye of the power generation layer 3 is photoexcited by the sunlight. Therefore, in this non-image part 7, it appears yellow mainly by the light reflected by the negative electrode layer 22 (sensitizing dye) of the power generation layer 3. As described above, in the present embodiment, the three green-colored colors that are visible in the complementary color image portions 31a to 31c of the image layer 4 provided on the sheet-like transparent material 2a on the front side and the non-image portion 7 are visible. The image by the image layer 4 is expressed by the four colors of yellow. In the image layer 4 of this embodiment, an image of a pattern (flower) is formed by the complementary color image portions 31a and 31c, and an image of a character (KOB) is formed by the complementary color image portion 31b, which is clear from the surrounding non-image portion 7 It is expressed with distinction.

  A transparent layer 5 is formed on the outer surface of the front-side sheet-like transparent material 2 a so as to cover the entire area of the power generation layer 3, and the image layer 4 is completely covered with the transparent layer 5. Here, the transparent layer 5 is in this embodiment and is formed of urethane-based clear varnish.

  In the present embodiment, the image pattern according to the present invention is realized by the design of the complementary color image portions 31a to 31c, the image form of the characters, and the size of the halftone dots constituting each.

Next, the manufacturing method of the dye-sensitized solar cell sheet 1 of the above-described embodiment will be described.
In the manufacturing method of the present embodiment, the power generation layer 3, the image layer 4, and the transparent layer 5 are sequentially printed on the sheet-like transparent materials 2a and 2b by a predetermined printing apparatus. This manufacturing method is implement | achieved by the 1st photoelectrode formation process, the image layer formation process, the 2nd photoelectrode formation process, a coating layer formation process, a counter electrode formation process, and a joining process like FIG.

In the first photoelectrode forming step, a transparent film made of polyethylene naphthalate having indium tin oxide supported in a layer form on the inner surface is used, and the front side silver wiring layer 27a is printed on the inner surface of the transparent film. Here, the front-side silver wiring layer 27a is laminated with the back-side silver wiring layer 27b formed in the counter electrode forming step described later, thereby constituting the above-described silver wiring layer 27. Thereafter, an etching process is performed to remove unnecessary indium tin oxide, and the conductive layer 21 is formed. By this first photoelectrode formation step, the front-side sheet-like transparent material 2a having the conductive layer 21 and the front-side silver wiring layer 27a formed on the inner side surface is obtained (see FIG. 5A).
Next, an image layer forming process is executed. In the image layer forming step, the image layer 4 is printed on the outer surface of the front-side sheet-like transparent material 2a. Here, the image layer 4 can be accurately formed at a predetermined position in accordance with the negative electrode layer 22 to be printed in the next second photoelectrode formation step. This is a printing device that prints the image layer 4 and a printing device that prints the negative electrode layer 22, and sets the printing position of the negative electrode layer 22 and the printing position of the image layer 4 in one sheet-like transparent material 2a. This is because printing can be controlled (see FIG. 5A).
Next, a second photoelectrode forming step is performed. In the second photoelectrode formation step, after zinc oxide is printed on the conductive layer 21 formed on the inner surface of the front sheet-like transparent material 2a, a sensitizing dye is adsorbed on the zinc oxide. Thereby, the negative electrode layer 22 is formed. By forming the negative electrode layer 22 in the second photoelectrode formation step, the photoelectrode of the present invention composed of the conductive layer 21 and the negative electrode layer 22 is formed (see FIG. 5A).
Next, a coating layer forming process is performed. In the coating layer forming step, the transparent layer 5 is printed on the outer surface of the front sheet-like transparent material 2a. Here, the transparent layer 5 is formed so as to cover the image layer 4 and to cover the negative electrode layer 22 and the front side silver wiring layer 27 formed on the inner surface of the sheet-like transparent material 2a. That is, in this embodiment, the transparent layer 5 is formed so as to completely cover the entire region of the power generation layer 3.
From the first photoelectrode forming step to the covering layer forming step, as shown in FIG. 5A, the conductive layer 21, the negative electrode layer 22, the image layer 4, and the transparent layer 5 are placed inside and outside the sheet-like transparent material 2a on the front side. Is formed.

  On the other hand, in the counter electrode forming step, similarly to the first photoelectrode forming step, a transparent film made of polyethylene naphthalate in which indium tin oxide is supported in a layer form on the inner surface is used, and on the inner surface of the transparent film, the back side The silver wiring layer 27b is printed (see FIG. 5B). Thereafter, unnecessary indium tin oxide is removed by etching treatment to form the conductive layer 21. Thereby, the back side sheet-like transparent material 2b in which the conductive layer 21 and the back side silver wiring layer 27b are formed on the inner side surface is obtained. Next, a conductive polymer is printed on the conductive layer 21 formed on the inner side surface of the sheet-like transparent material 2b to form the positive electrode layer 23. By such a counter electrode forming step, the conductive layer 21 and the positive electrode layer 23 are formed on the inner surface of the sheet-like transparent material 2b on the back side, as shown in FIG. Here, the counter electrode of the present invention is formed by the conductive layer 21 and the positive electrode layer 23.

  In the joining step described above, the front-side sheet-like transparent material 2a formed in the covering layer forming step from the first photoelectrode forming step and the back-side sheet-like transparent material 2b formed in the counter electrode forming step are bonded together. In this joining step, first, a predetermined sealing agent is printed on the inner surface of the front sheet-like transparent material 2a to form the sealing layer 26 (see FIG. 5C). Then, the electrolyte solution which comprises the electrolyte layer 24 is dripped and adhered on the negative electrode layer 22 provided in the inner surface of the sheet-like transparent agent 2a on the front side. Next, as shown in FIG. 5C, the front side sheet-like transparent material 2a on which the negative electrode layer 22 and the image layer 4 are formed and the back side sheet-like transparent material 2b on which the positive electrode layer 23 and the like are formed are mutually connected. The inner surfaces of the two are bonded together. Here, the sheet-like transparent material 2a on the front side and the sheet-like transparent material 2b on the back side are positioned and joined so that the negative electrode layer 22 and the positive electrode layer 23 face each other. Thus, the electrolyte layer 24 is formed by sandwiching the electrolytic solution attached to the negative electrode layer 22 between the negative electrode layer 22 of the front sheet-shaped transparent material 2a and the positive electrode layer 23 of the back sheet-shaped transparent material 2b. Further, the front side silver wiring layer 27a of the front side sheet-like transparent material 2a and the back side silver wiring layer 27b of the back side sheet-like transparent material 2b are joined and integrated to form the silver wiring layer 27 (see FIG. 3). ). Thus, the power generation layer 3 is formed between the pair of sheet-like transparent materials 2a and 2b, and the dye-sensitized solar cell sheet 1 of this embodiment is formed.

As described above, the dye-sensitized solar cell sheet 1 of the present example has the translucent color (blue) of the complementary color image portions 31 a to 31 c of the image layer 4 and the color of the sensitizing dye (yellow) of the power generation layer 3. Are complementary to each other, so that the sensitizing dye of the power generation layer 3 is similarly photoexcited by the light transmitted through the half-transparent halftone dot and sunlight, so that the power generation layer 3 has a desired color. Electric power can be generated stably. That is, the provision of the image layer 4 has almost no influence on the power generation capability of the power generation layer 3.
Further, since the complementary color image portions 31a to 31c of the image layer 4 have different densities due to the different sizes of the halftone dots constituting each, the light of the color reflected by the halftone dots and the sensitization. It is expressed in three different green colors depending on the color of light reflected by the pigment. And these complementary color image parts 31a-31c comprise the design of the dye-sensitized solar cell sheet 1 of a present Example together with the surrounding non-image part 7 which appears in yellow. In such an image layer 4 of the present embodiment, a flower pattern image by the complementary color image portions 31a and 31c and a character image by the complementary color image portion 31b are variously expressed by the four colors. Therefore, due to the image layer 4, the dye-sensitized solar cell sheet 1 of this example has high designability.
Moreover, in this embodiment, a general sheet-like dye-sensitized solar cell can be applied to the configuration of the front and back sheet-like transparent materials 2a and 2b and the power generation layer 3. Therefore, the dye-sensitized solar cell sheet 1 according to this embodiment is relatively easy to manufacture by forming the image layer 4 and the transparent layer 5 in the general configuration. Therefore, the configuration of the present embodiment does not make the manufacturing process complicated unlike the conventional configuration described above, and can suppress the increase in manufacturing cost as much as possible.
As described above, the dye-sensitized solar cell sheet 1 of this example has excellent design properties and can exhibit a desired power generation capability while maintaining the maximum advantage of the dye-sensitized solar cell that can be manufactured at low cost.

  Further, the configuration of this embodiment is provided with a transparent layer 5. Since the transparent layer 5 can reflect light that hits at a low angle with respect to the thickness direction of the dye-sensitized solar cell sheet 1, a so-called color shift phenomenon that occurs when the low-angle light is reflected by the image layer 4. Can be prevented. Here, the color shift phenomenon will be described in detail. In the case where the transparent layer 5 is not provided, when the low-angle light strikes the image layer 4, the light is reflected by the image layer 4, Since it becomes difficult to transmit through the image layer 4, blue appears by the reflected light. Therefore, in the image layer 4, the color shift phenomenon that the blue color is visually recognized as a stronger color than the desired green color appearing with the light hit at a high angle is likely to occur. Specifically, in the case of a configuration that does not include the transparent layer 5, if the complementary color image portion 31a having a low halftone dot density is visually recognized as a strong blue green color due to the color shift phenomenon, the next lowest density is obtained. Since the difference with the color in the complementary color image part 31b becomes small, the designability by these complementary color image parts 31a and 31b reduces. That is, there arises a problem that desired design properties by the complementary color image portions 31a to 31c that are originally expressed in three colors are not exhibited correctly. On the other hand, in the case of the configuration of the present embodiment, by providing the transparent layer 5 as described above, the light hit at a low angle can be reflected by the transparent layer 5, so that reflection by the image layer 4 is possible. And the occurrence of the color shift phenomenon can be prevented. Therefore, according to the configuration of the present embodiment, the problem of reduction in the design property due to the color shift phenomenon does not occur.

  On the other hand, in the production method for producing the dye-sensitized solar cell sheet 1 of the present example, as described above, the front-side sheet-like shape is obtained by the first photoelectrode formation step, the image layer formation step, and the second photoelectrode formation step. After the negative electrode layer 22 and the image layer 4 of the power generation layer 3 are printed on the transparent material 2a, the sheet-like transparent material 2a and the back-side sheet-like transparent material 2b are joined. According to this method, the negative electrode layer 22 and the image layer 4 can be accurately positioned and printed at desired positions on the outer side surface and inner side surface of the sheet-like transparent material 2a on the front side. For this reason, the dye-sensitized solar cell sheet 1 of this example manufactured by this method stably exhibits the high designability of the image layer 4 described above. In other words, the dye-sensitized solar cell sheet 1 having high designability can be stably produced by the production method of this example.

In this invention, it is not limited to the Example mentioned above, About the structure other than the above-mentioned Example, it can change and implement suitably within the range of the meaning of this invention.
For example, if the color of the sensitizing dye in the power generation layer and the semitransparent color of the halftone dots constituting the complementary color image portion of the image layer are colors that are complementary to each other, in addition to yellow and blue in the above-described embodiments Can also be set as appropriate. For example, when the sensitizing dye of the power generation layer is yellow, it may be blue-purple or purple in addition to blue. Here, bluish violet is a complementary color of yellow, and violet is a color adjacent to the bluish purple of the complementary color in a hue circle of 12 hues, and each color has a complementary color relationship with yellow. As described above, the half-transparent color of the halftone dot of the complementary color image portion and the color of the sensitizing dye of the power generation layer are, as described above, a configuration in which one is the other complementary color, or a hue circle in which one color is 12 hues. By applying a configuration in which the color complementary to the other color is adjacent to each other, a complementary color relationship can be obtained, so that the same operational effects as in the above-described embodiment can be obtained. As specific examples other than these, complementary color relationships such as “red” and “blue-green”, “red” and “green”, “green” and “red purple” can be applied.

  Moreover, although the dye-sensitized solar cell sheet 1 of the Example mentioned above is the structure provided with the complementary color image parts 31a-31c in which the image layer 4 is comprised with a halftone dot, as another structure, a complementary color image part is a lot. It may be constituted by lines, or may be constituted by both halftone dots and lines. Furthermore, the complementary color image portion may be configured by solid coating.

  Further, the complementary color image portions 31a to 31c of the image layer 4 are configured to have different densities due to halftone dots having the same number of lines and different sizes. However, as other configurations, they are different depending on halftone dots having the same size and different numbers of lines. It can also be formed to have a concentration. Even in the case of the above-described lines, it can be similarly formed at different concentrations by appropriately setting the number of lines and the line width.

  Moreover, in the Example mentioned above, although it is the structure which provided the electric power generation layer in the substantially whole region of the dye-sensitized solar cell sheet, it can also be set as the structure which does not provide the electric power generation layer in one part area | region as another structure. And in this structure, an image layer can be provided also in the partial area | region which has not provided the electric power generation layer. Such a portion where the power generation layer and the image layer do not overlap is expressed by a translucent color of the halftone dot of the image layer, and thus appears in a color different from the portion where the power generation layer and the image layer overlap. According to such a configuration, the design is further improved because the design has more various color expressions.

  In the embodiment described above, the image layer 4 is provided on the outer surface of the front sheet-like transparent material 2a. However, the present invention is not limited to this, and the image layer is provided on the inner surface of the sheet-like transparent material 2a. It is good also as a structure provided, and it is good also as a structure provided in both the outer side surface and inner surface of this sheet-like transparent material 2a. Furthermore, it is good also as a structure which provided the image layer in the outer surface and inner surface of the sheet-like transparent material 2b of the back side. Even in these configurations, since the image layer is provided on the outer side of the power generation layer (photoelectrode), the same effects as those of the above-described embodiment can be obtained.

  Moreover, in the manufacturing method of the dye-sensitized solar cell sheet 1 of the Example mentioned above, although electrolyte solution was made to adhere to the positive electrode layer 23 formed in the sheet-like transparent material 2b on the back side, as another method, You may make it adhere electrolyte solution to the negative electrode layer 22 of the sheet-like transparent material 2a. Further, the power generation layer 3 was formed by sequentially printing the conductive layer 21, the negative electrode layer 22, the electrolyte layer 24, the positive electrode layer 23, the conductive layer 21 and the like on the sheet-like transparent material 2a on the front side, and the image layer 4 was further formed. Later, the sheet-like transparent material 2a and the back-side sheet-like transparent material 2b may be joined.

1 Dye-sensitized solar cell sheet 2a, 2b Sheet-like transparent material
3 Power generation layer 4 Image layer 5 Transparent layer 11 Cell 31a to 31c Complementary color image part

Claims (4)

A pair of sheet-like transparent materials facing each other;
A power generation layer provided between the sheet-like transparent material and provided with one or a plurality of cells each provided with a photoelectrode and a counter electrode facing each other;
Each cell of the power generation layer is a dye-sensitized solar cell sheet in which a predetermined sensitizing dye is adsorbed to the photoelectrode,
A translucent image layer disposed on the outer surface and / or inner surface of at least one sheet-like transparent material so as to overlap the power generation layer,
The dye-sensitized solar cell sheet, wherein the image layer includes a complementary color image portion formed by a predetermined image pattern in a translucent color that is complementary to the color of the sensitizing dye in the cell. The image pattern of the complementary color image portion is composed of halftone dots and / or lines,
The dye-sensitized solar cell sheet according to claim 1, wherein the image layer includes a plurality of the complementary color image portions having different densities according to the image pattern.   The dye-sensitized solar cell sheet according to claim 1 or 2, wherein the sheet-like transparent material provided with the image layer is provided with a transparent layer covering the image layer. In the manufacturing method of the dye-sensitized solar cell sheet according to any one of claims 1 to 3, comprising an image layer on an outer surface of one sheet-like transparent material,
After forming an image layer on the outer side surface of one sheet-like transparent material and forming at least a photoelectrode of the power generation layer on the inner side surface of the sheet-like transparent material,
A method for producing a dye-sensitized solar cell sheet, characterized in that the one sheet-like transparent material and the other sheet-like transparent material are bonded via a power generation layer.

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