JP4570867B2 - Photoelectric conversion element - Google Patents

Description

The present invention relates to a photoelectric conversion element such as a dye-sensitized solar cell. More specifically, the cell component and the package material disposed outside the cell are sealed together without applying a load such as heating to the cell itself composed of a laminate formed by sandwiching the electrolyte layer between the working electrode and the counter electrode. What can be relates to a photoelectric conversion element.

Against the backdrop of environmental problems and resource problems, solar cells as clean energy are attracting attention. Some solar cells use single crystal, polycrystalline or amorphous silicon. However, conventional silicon-based solar cells still have problems such as high manufacturing costs and insufficient raw material supply, and have not yet been widely spread.
In addition, compound solar cells such as Cu-In-Se (also referred to as CIS) have been developed and have excellent features such as extremely high conversion efficiency, but problems such as cost and environmental impact It is still an obstacle to widespread use.

On the other hand, the dye-sensitized solar cell has been proposed by a group such as Gretzel of Switzerland, and has attracted attention as a photoelectric conversion element that can be obtained at low cost and high conversion efficiency.
FIG. 3 is a schematic cross-sectional view showing an example of a conventional dye-sensitized solar cell.
The dye-sensitized solar cell 50 includes a first substrate 51 having a porous semiconductor electrode 53 (hereinafter also referred to as a dye-sensitized semiconductor electrode) 53 carrying a sensitizing dye formed on one surface, and a conductive film 54. The main component is the second substrate 55 on which is formed, and an electrolyte layer 56 made of, for example, a gel electrolyte enclosed between them.

A light-transmitting plate material is used as the first substrate 51, and a transparent conductive layer 52 is disposed on the surface of the first substrate 51 in contact with the dye-sensitized semiconductor electrode 53 in order to provide conductivity. A window electrode 58 is formed by the substrate 51, the transparent conductive layer 52 and the dye-sensitized semiconductor electrode 53.
On the other hand, as the second substrate 55, a conductive layer 54 made of, for example, carbon or platinum is provided on the surface on the side in contact with the electrolyte layer 56, and the counter electrode 59 is formed by the second substrate 55 and the conductive layer 54. Is configured.

  The first substrate 51 and the second substrate 55 are arranged at a predetermined interval so that the dye-sensitized semiconductor electrode 53 and the conductive layer 54 face each other, and a sealant made of a thermoplastic resin is provided in the peripheral portion between the two substrates. 57 is provided. Then, the two substrates 51 and 55 are bonded together through the sealant 57 to assemble the cell, and oxidation / reduction species such as iodine / iodide ions are introduced between the electrodes 58 and 59 through the electrolyte inlet 60. What filled the organic electrolyte solution containing and formed the electrolyte layer 56 for electric charge transfer is mentioned. That is, the sealing agent 57 plays a role of preventing the electrolyte contained in the electrolyte layer 56 from leaking out or volatilization of volatile components. As the injection of the electrolytic solution, the cells of the solar battery are assembled and then injected in a batch manner using a capillary phenomenon, a pressure difference and the like from a liquid injection port provided on the back surface or the like.

However, the conventional dye-sensitized solar cell described above forms the sealant 57 by sealing with a thermoplastic resin. Specifically, as shown in FIG. 3, the resin was melted by applying heat to bond the two electrodes (window electrode 58 and counter electrode 59). At that time, since heat reaches the dye-sensitized semiconductor electrode 53 through the first substrate 51, the dye adsorbed on the dye-sensitized semiconductor electrode 53 may be adversely affected.
Moreover, since the sealing agent 57 is formed of resin, there is a problem in terms of weather resistance when used for a long time.
Furthermore, when injecting the electrolytic solution, first, two electrode plates are fused to form a cell shape, and then two electrodes forming an extremely narrow space through an injection port 50 opened in advance. There was a problem that the manufacturing process was complicated because it was necessary to inject in the middle and finally cover the inlet 50. In addition, if the viscosity of the electrolytic solution is high, it takes a lot of time and labor to inject the electrolytic solution, which increases the manufacturing cost.

  Therefore, the present inventors have suppressed the influence of the heat applied when bonding the electrodes to the dye adsorbed on the dye-sensitized semiconductor electrode, are excellent in weather resistance during long-term use, and are injected with an electrolyte. As a photoelectric conversion element that can be easily performed, a photoelectric conversion element 70 having a configuration as shown in FIG. 4 has been developed. In the photoelectric conversion element 70, the two electrodes (window electrode (working electrode) 78, counter electrode 79) are not sealed so as to be fused, but in a casing 81 including a box body 82 and a lid body 85. In addition, the laminated body 80 in which the electrolyte layer 76 is sandwiched between the working electrode 78 and the counter electrode 79 is accommodated, and the box body 82 and the lid body 85 are sealed, so that the laminated body 80 that forms the cell is collectively sealed. can do.

  According to the configuration of FIG. 4, since heat is not directly applied to the two electrodes, that is, the working electrode 78 and the counter electrode 79, the influence of heat on the dye described above can be avoided. Moreover, since the laminated body 80 sandwiched between the working electrode 78 and the counter electrode 79 can be formed by dropping and sandwiching the electrolyte solution in the dye-sensitized semiconductor electrode 73, the electrolyte solution injection step can be omitted. There is. Furthermore, since the working electrode 78 and the counter electrode 79 are housed inside the housing 81, they do not receive a direct impact from the outside, so that the strength against external force is ensured.

However, in the photoelectric conversion element 70, when the sealing is performed, pressure is applied to the stacked body 80 from the vertical direction (the direction of the arrow illustrated in FIG. 4) through the first substrate 71. Since the gap 80s and the elastic member 86a are arranged on the sides of the first substrate 71, pressure is applied to the central portion of the first substrate 71 in contact with the region where the laminated body 80 exists substantially uniformly in the plane. Pressure is applied to the end portion of the first substrate 71 at a position in contact with 86a in a state different from the central portion, and the first substrate 71 may be distorted or damaged. This problem has been a major obstacle in adopting a thin plate for the first substrate 71 and reducing the thickness of the entire photoelectric conversion element 70. Further, the conductor 88 having one end connected to the working electrode 78 is arranged to pass through the elastic member 86a in order to make the shortest path. However, when the elastic member 86a is deformed, the conductor 88 and the working electrode are arranged. There is a possibility that a problem occurs in the electrical connection with 78.
JP 2002-184478 A N. Papageorgiou et al., J. Electrochem. Soc., 143 (10), 3099, 1996

  The present invention has been made in view of the above circumstances, and can be sealed without causing distortion or breakage in the substrate constituting the electrode, the substrate can be thinned, and electrical connection stability is ensured. It is an object of the present invention to provide a photoelectric conversion element and a manufacturing method thereof.

The photoelectric conversion device according to the present invention includes a working electrode having a porous oxide semiconductor layer having a sensitizing dye supported on the surface thereof, and a counter electrode disposed opposite to the working electrode on the porous oxide semiconductor layer side. , And a photoelectric conversion element in which an electrolyte layer is disposed on at least a part between these two electrodes,
A laminate comprising the electrolyte layer sandwiched between a working electrode and a counter electrode is housed in a housing, and the upper and lower surfaces of the laminate are in direct or indirect contact with the inner surface of the housing, and at least of the housings. The part in contact with the working electrode consists of a member with optical properties that transmit sunlight,
One end is connected to each of the counter electrode and the working electrode so as not to pass through the inside of the case and contact the side surface of the stacked body, and separately provided conductors each extending the other end outside the case,
The conductor having one end connected to the working electrode is disposed so as to extend along a contact surface between the casing and the elastic member disposed between one side surface of the multilayer body and the casing. It is characterized by being.

  In the above photoelectric conversion element, a laminate in which an electrolyte layer is sandwiched between a working electrode and a counter electrode is stored so that the upper and lower surfaces thereof are in direct or indirect contact with the inner surface of the housing. In other words, since the inner surface of the casing is configured to sandwich the upper and lower surfaces of the laminate, it is possible to seal the casing in a lump including the cell constituent members made of the laminate by sealing the casing. The influence of heat applied to the laminate can be significantly reduced. Therefore, the conventional problem that the dye is impeded by a predetermined function under the influence of heat applied at the time of electrode adhesion is solved, and the dye can exhibit its performance stably, so that the photoelectric conversion characteristics can be stabilized. Further, if at least a portion of the housing that is in contact with the working electrode is formed of a member having an optical characteristic that transmits sunlight, the sunlight can be taken into the cell constituent member formed of the laminate.

  In the photoelectric conversion element having such a configuration, one end is connected to each of the counter electrode and the working electrode and the other end is extended to the outside of the casing so as not to contact the side surface of the multilayer body through the inside of the casing. Thus, the photoelectric conversion element can be electrically connected to the outside. In particular, the conductor having one end connected to the working electrode is disposed so as to extend along the contact surface between the elastic member disposed between one side surface of the multilayer body and the housing and the housing. Therefore, the conductor can be prevented from coming into contact with the side surface of the laminated body and short-circuiting, and even if the elastic member is deformed when sealed, the conductor is not affected by this. And the stability of the electrical connection between the working electrode and the working electrode.

  In addition, in the photoelectric conversion element adopting this configuration, a laminate in which an electrolyte layer is sandwiched between a working electrode and a counter electrode can be used. For example, a liquid electrolyte solution is dropped (filled) on one electrode, A stacked body can be formed by sandwiching the other electrode. At that time, the electrolytic solution sandwiched between the electrodes does not spill out of the gap due to the capillary phenomenon. It is also possible to sandwich and fill the gel electrolyte. Therefore, it is possible to omit the electrolytic solution injection process which has conventionally required a lot of time, and thus it is possible to further reduce the cost of the photoelectric conversion element.

Furthermore, according to the above configuration, since it is not necessary to use a sealing agent made of resin as in the prior art, the weather resistance at the time of long-term use is improved, so that the photoelectric conversion excellent in the long-term stability of the photoelectric conversion characteristics An element can be provided.
Furthermore, in the said photoelectric conversion element, the cell structural member which consists of a laminated body is installed in the housing | casing, and the structure which does not touch external air is employ | adopted. That is, since the cell constituent member is housed in a sealed space, a photoelectric conversion element having better environmental characteristics than before can be obtained.

In the above-described photoelectric conversion element, the housing is preferably disposed so as to be in contact with the side surface of the stacked body. By not providing a gap and / or an elastic member on the side of the laminated body, the working electrode is always kept in contact with the laminated body not only in the center but also in the vicinity of the end. Therefore, since the working electrode does not receive a biased pressure in the vicinity of the end portion during sealing, the problem that the substrate constituting the working electrode is distorted or damaged is solved.
A configuration in which the housing is arranged so as to be in contact with all the side surfaces of the laminated body is most preferable, but only the portion where the conductor having one end connected to the working electrode is guided in the thickness direction of the laminated body is provided between the housing and the laminated body. A configuration may be adopted in which an elastic member is disposed therebetween. Even when the latter form is adopted, the same action as that of the former form can be obtained almost similarly.

  In this way, by making the working electrode less susceptible to biased pressure in the vicinity of its end, the thickness of the (first) substrate constituting the working electrode is reduced to a range of 0.1 mm to 0.5 mm. It becomes possible to set. If the thickness is less than 0.1 mm, the mechanical strength of the substrate itself is reduced, and the substrate may be deformed or damaged when the substrate is handled in manufacturing or when pressure is applied to store and seal the housing. It is not good because there is a risk of doing. When the thickness exceeds 0.5 mm, the substrate is likely to be distorted or warped, and pressure may be applied nonuniformly from the lid constituting the housing, and the distance between the working electrode and the counter electrode is not uniform. Therefore, the stability of the power generation characteristics is reduced. Therefore, the thickness of the (first) substrate constituting the working electrode is preferably in the range of 0.1 mm or more and 0.5 mm or less, and the adoption of such a thin substrate results in a thinner photoelectric conversion element. preferable.

  Hereinafter, the present invention will be described based on the embodiments. However, the present invention is not limited to these embodiments as long as the above-described functions and effects are satisfied.

FIG. 1 is a schematic cross-sectional view showing an example of a photoelectric conversion element according to the present invention.
The dye-sensitized solar cell (photoelectric conversion element) 10 includes a working electrode (also referred to as a window electrode) 18 having a porous oxide semiconductor layer (also referred to as an oxide electrode) 13 having a sensitizing dye supported on a surface thereof. The counter electrode 19 disposed opposite to the porous oxide semiconductor layer 13 of the working electrode 18 and the electrolyte layer 16 disposed at least at a part between the two electrodes. The working electrode 18 includes, for example, the first substrate 11 and the transparent conductive film 12 and the oxide electrode 13 that are sequentially disposed thereon. One counter electrode 19 includes, for example, a second substrate 15 and a conductive film 14 disposed thereon.

  A laminate 20 in which the electrolyte layer 16 is sandwiched between the working electrode 18 and the counter electrode 19 functions as a cell constituent member, that is, a photoelectric conversion element. In the dye-sensitized solar cell 10, the stacked body 20 is housed inside a casing 21 that surrounds the stacked body 20, and the upper and lower surfaces of the stacked body 20 are in contact with the inner surface of the casing 21. Here, at least a portion of the housing 21 that is in contact with the working electrode 18, that is, the lid body 25 shown in FIG. 1 is composed of a member having optical characteristics that transmit sunlight.

  In the dye-sensitized solar cell 10, a laminate 20 in which the electrolyte layer 16 is sandwiched between the working electrode 18 and the counter electrode 19 is stored so that the upper and lower surfaces thereof are in contact with the inner surface of the housing 21. A configuration in which the inner surface sandwiches the upper and lower surfaces of the laminate 20 is provided. Therefore, for example, if the casing 21 is sealed at a portion where the lid 25 and the side portion 24 of the box 22 are in contact with each other, it is possible to collectively seal the cell components including the laminate 20.

  In addition, the arrow which goes to the laminated body 20 in FIG. 1 has shown the direction of the force added to the laminated body 20 when the housing | casing 21 is sealed. When an external force is applied to the laminate 20 in such a direction, the lateral displacement of the laminate 20 is suppressed, or the laminate 20 is firmly fixed while maintaining flexibility in the vertical direction. Thus, for the purpose of sealing the stacked body 20, it is preferable to provide an elastic member 26 between the counter electrode 19 and the bottom 23 constituting the housing 21.

For the same reason, a gap filler 27 is inserted between the working electrode 18 and the lid 25 constituting the housing. However, as is apparent from the fact that the gap filler 27 is disposed on the working electrode 18, a material excellent in sunlight transmission characteristics is preferably used as the gap filler 27.
The installation of the elastic member 26 and the gap filling material 27 is desirable because the upper and lower electrodes suppress relative displacement in the in-plane direction and provide high shape stability and earthquake resistance against external forces.

Furthermore, in the dye-sensitized solar cell 10, one end is connected to each of the counter electrode 19 and the working electrode 18 so as to pass through the inside of the housing 21 and not come into contact with the side surface of the stacked body 20. A configuration in which the conductors 28 and 29 each having an end extending individually is employed.
According to this configuration, the other ends of the conductors 28 and 29 used to connect to an external circuit (not shown) can be freely led out of the housing from any location of the housing 21, so that the external circuit It can meet various installation conditions according to the system.

  In the conductor 28 having one end connected to the working electrode 18 and the other end extending to the outside of the housing 21, in order not to pass through the inside of the housing 21 and contact the side surface of the stacked body 20, for example, FIG. As shown in FIG. 1, the elastic member 26 a may be provided between the side surfaces of the oxide electrode 13, the conductive film 14, and the second substrate 15 that constitute a part of the stacked body 20 and the conductor 28. I do not care. As a result, it is possible to individually provide a conductor whose one end is connected to the counter electrode and the working electrode and the other end extends outside the case so that it does not pass through the inside of the case and contact the side surface of the laminate. Thus, the photoelectric conversion element can be electrically connected to the outside.

  In particular, in the photoelectric conversion element 10, the conductor 28 having one end connected to the working electrode 18 includes an elastic member 26 a provided between one side surface of the multilayer body 20 and the housing 21, and an end portion of the working electrode 12. It arrange | positions so that it may extend along the surface which 12a contacts. This arrangement prevents the conductor 28 from coming into contact with the side surface of the stacked body 20 and short-circuiting. Further, even when the elastic member 26a contracts and changes its shape when sealed, the conductor 28 does not pass through the elastic member 26a, and the contact between the end 12a of the working electrode 12 and the elastic member 26a. Because it exists on the surface, it is hardly affected. Therefore, since the electrical connection between one end of the conductor 28 and the working electrode 18 is kept extremely stable, the improvement in the electrical connection brings about long-term stability of the output characteristics of the photoelectric conversion element.

  FIG. 2 is a schematic cross-sectional view showing another example of the photoelectric conversion element according to the present invention. The photoelectric conversion element 30 illustrated in FIG. 2 is different from the above-described embodiment (photoelectric conversion element 10) in that the housing 41 is disposed so as to be in contact with the side surface 40t of the stacked body 40. In this way, by adopting a configuration in which no gap is provided on the side of the laminated body 40, the working electrode 38 is always kept in contact with the laminated body not only in the central part but also in the vicinity of the end part. Then, when sealing, the working electrode 38 does not receive a biased pressure in the vicinity of the end portion, so that the risk of the first substrate 31 and the like constituting the working electrode 38 being distorted or broken can be kept low. It becomes.

  A configuration in which the housing is disposed so as to be in contact with all the side surfaces of the multilayer body is most preferable. However, as shown in FIG. 2, a conductor 48 having one end connected to the working electrode 38 is guided in the thickness direction of the multilayer body 38. The elastic member 46a may be arranged between the side portion 44 of the housing 41 and the photoelectric conversion element 10 only at the location. It is preferable to use an insulating member as the elastic member 46a because the risk of a short circuit between the laminate 40 and the conductor 48 can be avoided. If the elastic member 46a is provided only in the vicinity where the conductor 48 exists, and the other side portion of the housing 41 and the laminated body 40 are disposed in contact with each other, the above-described operation can be obtained in substantially the same manner.

The method for producing a photoelectric conversion device according to the present invention includes a working electrode having a porous oxide semiconductor layer having a sensitizing dye supported on the surface thereof, and is disposed opposite to the working electrode on the porous oxide semiconductor layer side. A counter electrode, and a method for producing a photoelectric conversion element in which an electrolyte layer is disposed at least in part between the two electrodes,
Filling the porous oxide semiconductor layer constituting the working electrode with a liquid or gel electrolyte to form an electrolyte layer; and
The counter electrode is provided on the inner bottom surface of the box constituting the housing, the working electrode is stacked so that the electrolyte layer is in contact with the counter electrode, a laminate is formed, and the housing is configured to cover the working electrode A load is applied in the stacking direction of the stacked body from the outside of the housing via the working electrode, and the load is applied substantially uniformly to the first substrate surface constituting the working electrode. Sealing the housing, and
It is characterized by comprising at least.

  In such a manufacturing method, first, the step of forming an electrolyte layer by filling the porous oxide semiconductor layer constituting the working electrode with a liquid or gel electrolyte is performed on the surface of the porous oxide semiconductor layer. The electrolytic solution can be applied uniformly. That is, according to this process, there is no need to forcibly inject the electrolytic solution through the inlet into the narrow space between the working electrode and the counter electrode as in the prior art. Problems such as the occurrence of a region that does not spread or the localized presence of the electrolyte are eliminated. This action / effect works effectively even if the electrolyte is not only liquid but also gel.

  Next, the counter electrode is provided on the inner bottom surface of the box constituting the casing, the working electrode is stacked so that the electrolyte layer is in contact with the counter electrode, a laminate is formed, and the casing is covered so as to cover the working electrode. After the lid constituting the body is disposed, a load is applied from the outside of the housing through the working electrode in the stacking direction of the laminated body, and the load is substantially uniform on the first substrate surface constituting the working electrode. In the step of sealing the casing as it is added to the case, it is possible to seal the casing in a lump including the cell constituent member made of a laminate by sealing the casing. Even when heat is locally applied to the housing when the housing is sealed, the laminate is hardly heated. Therefore, if this process is adopted, the problem that the dye is impeded by a predetermined function under the influence of heat applied during the conventional electrode bonding is solved. Further, since the casing is sealed so that the load is applied substantially uniformly to the first substrate surface constituting the working electrode, it is possible to prevent the substrate constituting the working electrode from being distorted or damaged.

  Therefore, the manufacturing method according to the present invention can suppress the influence exerted on the dye adsorbed on the dye-sensitized semiconductor electrode by the heat applied when adhering the photoelectric conversion element having the above-described features, that is, the electrode, and for a long time. This contributes to stable production of a photoelectric conversion element that has excellent weather resistance during use and can be easily injected with an electrolyte. Furthermore, since the problem that has occurred at the working electrode due to sealing is also eliminated and the stability of electrical connection is improved, the manufacturing method of the present invention provides a photoelectric conversion element with excellent long-term reliability.

In the following, each of the suitable constituent members will be described by taking the above-described photoelectric conversion element 10 as an example, but it goes without saying that the same constituent members can also be used in the photoelectric conversion element 30.
As the first substrate 11 according to the present invention, a plate made of a light-transmitting material is used, and glass, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, etc. are usually used as transparent substrates for solar cells. Anything can be used. The substrate may be appropriately selected in consideration of resistance to the electrolytic solution and the like, but a substrate having as high a light transmittance as possible is preferable for use.

It is preferable to provide conductivity by forming a transparent conductive film 12 made of a metal, carbon, conductive metal oxide layer or the like on the surface of the first substrate 11 on the dye-sensitized semiconductor electrode 13 side. When forming a metal layer or a carbon layer as the transparent conductive film 12, it is preferable to have a structure that does not significantly impair the transparency, and the type of metal is also appropriately selected from the viewpoint that a thin film that does not impair the conductivity and transparency can be formed. Selected. As the conductive metal oxide, for example, ITO, SnO ₂ , fluorine-doped SnO ₂ or the like can be used.

On the transparent conductive layer 2 placed on the first substrate 11, there is further provided a dye-sensitized semiconductor electrode 13 in which a sensitizing dye is supported on a semiconductor porous film. The first substrate 11, the transparent conductive layer 2, and the dye-sensitized semiconductor electrode 13 constitute a working electrode (window electrode) 18. The semiconductor for forming the semiconductor porous film of the dye-sensitized semiconductor electrode 13 is not particularly limited, and any semiconductor can be used as long as it is usually used for forming a porous semiconductor for solar cells. can, for _example, be _{TiO 2, SnO 2, WO 3} , ZnO, and _Nb 2 _{O 5} is used. Examples of the method for forming a porous film include a film formation from a sol-gel method, electrophoretic electrodeposition of fine particles, making it porous with a foaming agent, and removing excess components after applying a mixture with polymer beads. However, it is not limited to these.

  As sensitizing dyes, ruthenium complexes containing bipyridine structure, terpyridine structure, etc. as ligands, metal-containing complexes such as porphyrin, phthalocyanine, and organic dyes such as eosin, rhodamine, merocyanine, etc. can be used. Those having an excitation behavior suitable for the semiconductor used can be selected without particular limitation.

  As the second substrate 15, a metal plate can be used because it does not need to have light transmittance, and the same material as the first substrate 11 may be used. An electrode provided with a conductive film 14 is used as the counter electrode 19 on the second substrate 15. As the conductive film 14, for example, a layer of carbon, platinum, or the like, which has been heat-treated after vapor deposition, sputtering, and chloroplatinic acid coating is preferably used, but is not particularly limited as long as it functions as an electrode. Absent.

An electrolyte layer 16 is provided between the working electrode 18 and the counter electrode 19 described above, and constitutes a cell constituent member made of the laminate 20. As will be described later, in the laminate 20 according to the present invention, the porous oxide semiconductor layer 13 constituting the working electrode 18 is filled with a liquid or gel electrolyte to form the electrolyte layer 16, and then the electrolyte is applied to the counter electrode 19. The stacked body 20 is formed by stacking the working electrodes 18 so that the layer 16 is in contact with the layer 16, and then a load is applied in the stacking direction of the stacked body 20.
Therefore, as the electrolyte layer 16 of the present invention, since it is possible to use a highly viscous material that has been difficult to inject into a narrow electrode gap from the injection port, the electrolyte solution is gelled using an appropriate gelling agent. (Pseudo-solidified) and high-viscosity materials can be used, but any material conventionally used may be used.

  A laminate 20 in which the electrolyte layer 16 is sandwiched between the working electrode 18 and the counter electrode 19 is housed in a casing 21, and the upper and lower surfaces of the laminate 20 are in contact with the inner surface of the casing 21. The portion of the casing 21 that is in contact with at least the working electrode 18, that is, the lid body 25, is composed of a member having optical properties that transmit sunlight, and is transparent and rigid, such as acrylic, polycarbonate, polyvinyl chloride, and soda glass. The material is mentioned. The other part of the casing 21, that is, the box 22 composed of the bottom 23 and the side 24, is even insulated from the conductors 28 and 29 extending from the two electrodes to the external circuit of the casing 21. If so, the material is not particularly limited.

  A counter electrode 19 is provided on the inner bottom surface of the box 22 constituting the casing 21, and a stacked body 20 is formed by overlapping the working electrode 18 so that the electrolyte layer 16 is in contact with the counter electrode 19, and the casing is covered so as to cover the working electrode 18. After the cover 25 constituting the body 22 is arranged, the dye-sensitized solar cell 10 is obtained by sealing the housing 21 by applying a load from the outside of the housing 21 in the stacking direction of the stacked body 20. .

  The casing 21 is sealed by, for example, applying pressure or heat to the contact portion between the side portion 24 of the casing 21 and the lid body 25. However, although the laminated body 20 is accommodated in the housing 21, the laminated body 20 is disposed so as to be located away from the sealing portion of the housing 21, so that heat accompanying this sealing reaches the laminated body 20. There is no fear. For example, if sealing is performed with a laser, a configuration in which a thermoplastic resin is not used can be achieved.

  In addition, after the electrolytic solution forming the electrolyte layer 16 is dropped on the working electrode (window electrode) 18 (when the electrolytic solution is liquid) or disposed on the working electrode (window electrode) 18 (when the electrolytic solution is in a gel form). It can be filled by sandwiching with the counter electrode 19. Therefore, it is possible to omit the complicated process of making a hole in the counter electrode 19, injecting an electrolyte, and closing the hole as in the conventional case, so that the manufacturing process can be simplified and labor can be reduced, so that the cost can be reduced. A photoelectric conversion element is obtained. Furthermore, when silicone oil is filled as the gap filling material 27 between the first substrate 11 constituting the working electrode (window electrode) 18 and the lid 25 constituting the housing 21, the first substrate 11 and the lid It is desirable because the air layer existing between 25 can be removed and the transparency is increased.

  ADVANTAGE OF THE INVENTION According to this invention, the photoelectric conversion element which can be sealed without generating distortion and a damage | wound in the board | substrate which comprises an electrode, can achieve thickness reduction of a board | substrate, and electrical connection stability is ensured, and its manufacturing method Can be provided. Therefore, the present invention contributes to the manufacture of a photoelectric conversion element having high reliability in electrical connection and long-term stability of output characteristics.

It is sectional drawing which shows an example of the photoelectric conversion element which concerns on this invention. It is sectional drawing which shows another example of the photoelectric conversion element which concerns on this invention. It is sectional drawing which shows an example of the conventional photoelectric conversion element. It is sectional drawing which shows another example of the conventional photoelectric conversion element.

Explanation of symbols

  10, 30 Dye-sensitized solar cell (photoelectric conversion element), 11, 31 First substrate, 12, 32 Transparent conductive film, 13, 33 Porous oxide semiconductor layer (oxide electrode), 14, 34 Conductive film, 15, 35 Second substrate, 16, 36 Electrolyte layer, 18, 38 Working electrode (window electrode), 19, 39 Counter electrode, 20, 40 Laminate, 21, 41 Housing, 22, 42 Box, 23, 43 Bottom 24, 44 Side, 25, 45 Lid (portion in contact with working electrode), 26, 26a, 46, 46a Elastic member, 27, 47 Gap filler, 28, 29, 48, 49 Conductor.

Claims (3)

A working electrode having a porous oxide semiconductor layer carrying a sensitizing dye on its surface, a counter electrode disposed opposite to the working electrode on the porous oxide semiconductor layer side of the working electrode, and at least one of the two electrodes A photoelectric conversion element in which an electrolyte layer is arranged in a part,
A laminate comprising the electrolyte layer sandwiched between a working electrode and a counter electrode is housed in a housing, and the upper and lower surfaces of the laminate are in direct or indirect contact with the inner surface of the housing, and at least of the housings. The part in contact with the working electrode consists of a member with optical properties that transmit sunlight,
One end is connected to each of the counter electrode and the working electrode so as not to pass through the inside of the case and contact the side surface of the stacked body, and separately provided conductors each extending the other end outside the case,
The conductor having one end connected to the working electrode is disposed so as to extend along a contact surface between the casing and the elastic member disposed between one side surface of the multilayer body and the casing. A photoelectric conversion element characterized by comprising: The photoelectric conversion element according to claim 1, wherein the casing is disposed so as to be in contact with a side surface of the stacked body. The photoelectric conversion element according to claim 1 or 2, wherein the thickness of the first substrate constituting the working electrode is 0.1 mm or more and 0.5 mm or less.

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