TWI640102B - Photoelectric conversion element and method for producing photoelectric conversion element - Google Patents

Abstract

A photoelectric conversion element comprising: a photoelectrode having a semiconductor layer formed on a first electrode substrate; a counter electrode having a second electrode substrate disposed opposite to the first electrode substrate; and a sealing material; The photoelectrode is sealed between the counter electrode and the counter electrode; and the electrolyte is disposed inside the sealing material; and at least one of the first electrode substrate and the second electrode substrate is disposed opposite to each other a surface of the first electrode substrate and the surface of the second electrode substrate are enlarged by a space-enlarged wall portion, and an enlarged space is formed inside the sealing material, and the electrolyte is held on the first electrode substrate inside the enlarged space. A non-contact portion that is not in contact with the electrolyte is formed on the sealing material between the second electrode substrate.

Description

Photoelectric conversion element and method of manufacturing photoelectric conversion element

The present invention relates to a method of manufacturing a photoelectric conversion element and a photoelectric conversion element. The present application claims priority based on Japanese Patent Application No. 2013-172561, filed on Jan.

In recent years, solar cells have attracted attention as power generation devices for replacing clean energy sources of fossil fuels, and have developed silicon (Si) solar cells and dye-sensitized solar cells. In particular, a dye-sensitized solar cell is inexpensive and easily mass-produced, and its structure and production method have been extensively researched and developed (for example, Patent Document 1 below).

As shown in FIG. 7, the dye-sensitized solar cell 100 described in Patent Document 1 includes a photoelectrode 104 in which a transparent conductive film 102 is formed on a surface of a transparent substrate 101, and a surface of the transparent conductive film 102 is formed. The semiconductor layer 103 carrying the dye; the counter electrode 107 is formed on the counter substrate 105 opposite to the transparent conductive film 102; the sealing material 108 surrounds the semiconductor layer 103, and the light is made The outer peripheral wall portion of the electrode 104 is bonded to the outer peripheral wall portion of the counter electrode 107 to form the inner space S, and the inner space S is sealed; and the electrolyte 109 is injected into the upper portion Said internal space S.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-175939

However, in the case where the electrolytic solution 109 is injected into the internal space S in the dye-sensitized solar cell 100, the sealing material 108 is brought into contact with the electrolytic solution 109 to deteriorate the sealing material 108, thereby causing deterioration of the quality of the solar cell 100, and the like. The problem. When the sealing material 108 is deteriorated, the barrier property of the sealing material 108 is lowered, and the electrolytic solution 109 permeates into the inside of the sealing material 108, or the interface strength of the sealing material 108 is lowered, and the interface between the sealing material 108 and the semiconductor layer 103 or the like is peeled off. There may be a short circuit.

Therefore, in view of the above problems, an object of the present invention is to provide a photoelectric conversion element capable of suppressing contact between a sealing material and an electrolytic solution.

The photoelectric conversion device of the present invention includes: a photoelectrode having a semiconductor layer formed on the first electrode substrate; and a counter electrode having a second electrode substrate disposed opposite to the first electrode substrate via the semiconductor layer; a sealing material that seals between the photoelectrode and the counter electrode; and an electrolyte disposed inside the sealing material; and at least one of the first electrode substrate and the second electrode substrate; a space-expanded wall portion of the electrode substrate and the second electrode substrate which are enlarged in size, and an enlarged space is formed inside the sealing material The electrolyte is held between the first electrode substrate and the second electrode substrate inside the enlarged space, and a non-contact portion that does not contact the electrolyte is formed in the sealing material.

According to this configuration, since the non-contact portion that is not in contact with the electrolyte is formed in the sealing material, deterioration of the sealing material due to the electrolyte can be prevented, whereby generation of a short circuit can be suppressed.

Further, the "electrolyte" shown in the present application contains an electrolyte, a gel electrolyte, and a solid electrolyte.

Preferably, wiring is provided in the enlarged space or the inside of the sealing material, and the wiring is disposed on at least one electrode substrate selected from the group consisting of a first electrode substrate and a second electrode substrate.

According to this configuration, the wiring having a large cross-sectional area can be disposed in the enlarged space.

The space-expanding wall portion of the present invention may further include an inclined surface that gradually enlarges the distance between the seal members and the seal member.

According to this configuration, the electrolyte is held in the enlarged space formed by the enlarged wall portion, and the electrolyte can be prevented from contacting the sealing material.

In the present invention, the thickness of the sealing material (the height in the vertical direction), the difference between the size of the surface of the first electrode substrate and the surface of the second electrode substrate in the region where the semiconductor layer is formed, is preferable. It is 30 μm or more and 200 μm or less.

According to this configuration, the wiring having the largest cross-sectional area can be buried in the inside of the sealing material, and the wiring resistance can be lowered. Further, by setting it to 200 μm or less, it is possible to prevent a situation in which the effective area of power generation is lowered due to an increase in the dead space around the sealing material.

The method for producing a photoelectric conversion element according to the present invention includes an electrolyte disposing step of disposing an electrolyte in a semiconductor layer on a first electrode substrate provided on a photoelectrode; a step of disposing a sealing material on at least one of an end portion of the first electrode substrate and an end portion of the second electrode substrate; and a laminating step of the counter electrode including the second electrode substrate in the photoelectrode layer An electrolyte extending step of pressurizing the photoelectrode and the counter electrode, disposing the electrolyte in the semiconductor layer, and holding the electrode between the first electrode substrate and the second electrode substrate, and forming the above a space-expanding wall portion of the first electrode substrate adjacent to the second electrode substrate that is enlarged in size in the vicinity of the sealing material, and a non-contact portion that does not contact the electrolyte is formed in the sealing material; and a sealing step of the light The electrode is sealed to the counter electrode described above.

According to this configuration, the photoelectric conversion element described above can be easily manufactured.

In the invention, it is preferable that the stacking step, the electrolyte extending step, and the sealing step are simultaneously performed by pressurization of the photoelectrode and the counter electrode.

According to this configuration, the manufacturing steps of the photoelectric conversion element described above can be further simplified.

Preferably, the space expansion wall portion of the present invention is formed by using a flexible resin substrate on at least one of the first electrode substrate and the second electrode substrate, and the photoelectrode is When the counter electrode is pressurized, the flexible resin substrate is deformed.

According to this configuration, the photoelectrode and the counter electrode can be laminated and pressurized at the same time, and the non-contact portion in which the sealing material is not in contact with the electrolyte can be formed at the time of pressurization.

According to the present invention, it is possible to suppress the deterioration of the quality of the photoelectric conversion element by suppressing the contact of the sealing material with the electrolyte.

Moreover, according to the method for producing a photoelectric conversion element of the present invention, the effect of easily and efficiently producing the photoelectric conversion element of the present invention can be achieved.

1A‧‧‧Solar cell (photoelectric conversion element)

2‧‧‧First electrode substrate

2a‧‧‧ Surface of the first electrode substrate

2b‧‧‧ Surface of the outer side of the first electrode substrate

2p‧‧‧outer end

3‧‧‧Electrical film

3a‧‧‧ Surface of conductive film

4‧‧‧Semiconductor layer

5‧‧‧Photoelectrode

6‧‧‧Second electrode substrate

6a‧‧‧ Surface of the second electrode substrate

6p‧‧‧outer end

7‧‧‧Electrical film

7a‧‧‧ Surface of conductive film

8‧‧‧ opposite electrode

10‧‧‧ Sealing material

11‧‧‧ electrolyte (electrolyte)

15‧‧‧Space enlargement wall

15a‧‧‧Sloping surface

20‧‧‧ wiring

50‧‧‧Ultrasonic welding device

100‧‧‧Pigment sensitized solar cells

101‧‧‧Transparent substrate

102‧‧‧Transparent conductive film

103‧‧‧Semiconductor layer

104‧‧‧Photoelectrode

105‧‧‧ opposite substrate

106‧‧‧ opposite conductive film

107‧‧‧ opposite electrode

108‧‧‧ Sealing material

109‧‧‧ electrolyte

E‧‧‧Expanding space

L1, L2‧‧‧ separated dimensions

N‧‧‧ Non-contact department

P1, P2‧‧‧ resin substrate

R‧‧‧ Roll

Surface layer of R1‧‧‧ Roll

S‧‧‧Internal space

X1‧‧‧ areas with semiconductor layers

X2‧‧‧ area

Fig. 1 is a cross-sectional view schematically showing a photoelectric conversion element according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view schematically showing a part of a manufacturing procedure of a photoelectric conversion element according to an embodiment of the present invention.

Fig. 3 is a cross-sectional view schematically showing a part of a manufacturing procedure of a photoelectric conversion element according to an embodiment of the present invention.

Fig. 4 is a view schematically showing a manufacturing step of a photoelectric conversion element according to an embodiment of the present invention.

Fig. 5 is a cross-sectional view showing a manufacturing step of a photoelectric conversion element according to an embodiment of the present invention shown by a Y1-Y2 line arrow view 4.

Fig. 6 is a cross-sectional view schematically showing another example of the photoelectric conversion element according to the embodiment of the present invention.

Fig. 7 is a cross-sectional view showing a prior photoelectric conversion element.

Hereinafter, each embodiment of the photoelectric conversion element of the present invention will be described by taking a case where the photoelectric conversion element is a dye-sensitized solar cell as an example. Further, a case where a photoelectric conversion element is manufactured using an electrolytic solution as an electrolyte will be described as an example.

(First embodiment)

As shown in Fig. 1, a dye-sensitized solar cell (photoelectric conversion element) (hereinafter referred to as "solar power" The cell "1A" includes a photoelectrode 5 having a semiconductor layer 4 formed on the first electrode substrate 2, and a counter electrode 8 having a second electrode substrate disposed opposite to the first electrode substrate 2 with a space therebetween. 6.

Further, between the photoelectrode 5 and the counter electrode 8, the end portion 2p of the first electrode substrate 2 and the end portion 6p of the second electrode substrate 6 are surrounded by the sealing material 10, ultrasonic welding or the like to surround the photoelectrode. 5 and the outer periphery of the counter electrode 8 are sealed in a frame shape, and the electrolytic solution 11 is filled in the sealed internal space S and the void (not shown) in the semiconductor layer 4. In Fig. 1, a solar cell having the above configuration is continuously formed left and right as a unit cell. The shape of the unit cell is not particularly limited, and examples thereof include a triangle, a quadrangle, a polygon other than the above, a circle, an ellipse, etc., but a band shape is preferable as shown in Fig. 4 from the viewpoint of production efficiency and the like.

The sealing material 10 is provided on at least a part of the edge of the unit cell (solar cell). That is, the sealing material 10 may be completely surrounded by the unit battery, and may be provided only in one part of the edge portion of the unit cell as long as the target effect of the present invention can be achieved, and the remaining portion of the edge portion may be sealed by other means. Moreover, when the sealing material 10 is provided only in one part of the edge portion of the unit cell, a plurality of the sealing materials 10 may be intermittently provided at the edge of the unit cell.

For example, in the case where the unit cell has a strip shape as shown in FIG. 4, specific examples of the method of disposing the sealing material 10 include the following: (1) The sealing material 10 is provided only in the pair of the unit cells. (2) the sealing material 10 is disposed on one of the opposite sides of the unit cell; (3) the sealing material 10 is disposed on one of the opposite sides of the unit cell Both of them, and further arranged on one of the pair of short sides, thereby The seal member 10 is disposed in a font shape; (4) the seal member 10 is disposed on four sides of the unit battery, and the unit battery is completely surrounded by the seal member 10.

Here, the first electrode substrate 2 has a space enlarged wall portion 15 having an inclined surface 15a inside the end portion 2p on which the sealing material 10 is disposed.

Further, similarly to the first electrode substrate 2, the second electrode substrate 6 has a space enlarged wall portion 15 having an inclined surface 15a inside the outer end portion 6p. Further, the space-expanding wall portions 15 and 15 are disposed in the vicinity of the sealing material 10 such that the distance L1 between the surface 2a of the first electrode substrate 2 and the surface 6a of the second electrode substrate 6 is from the inner side of the outer end portion 2p toward the outer side. The sealing member 10 is gradually enlarged to form an enlarged space E in which one portion of the internal space S is enlarged.

The enlarged space E in the region X2 sandwiched by the space-enlarged wall portions 15 and 15 can sufficiently hold the semiconductor layer 4 and the electrolyte 11 overflowing from the region X1 in the vicinity of the region X2, so that the electrolyte 11 and the sealing material can be obtained. 10 as far as possible to separate and separate.

Moreover, it is preferable to provide a deterioration preventing member (not shown) of the sealing material 10 between the electrolytic solution 11 and the sealing material 10. Specifically, it is preferable to provide a deterioration preventing member so as to be partitioned between the space between the photoelectrode 5 and the counter electrode 8 in which the electrolytic solution 11 exists and the enlarged space E. The deterioration preventing member is preferably formed of a solid such as a fluororesin having solvent resistance and/or iodine resistance. By providing the deterioration preventing member, even if the solar cell is pressed from the top to the bottom, the space in which the electrolyte 11 is present is compressed, and the electrolyte 11 can be prevented from contacting the sealing material 10.

The first electrode substrate 2 and the second electrode substrate 6 are respectively a resin substrate mainly composed of a transparent thermoplastic resin material such as polyethylene naphthalate (PEN) or polyethylene terephthalate (PET). The surface of P1 and P2 is formed by a film having conductive films 3 and 7. Further, the resin substrates P1 and P2 may be formed into a film shape.

The shape of the first electrode substrate 2 and the second electrode substrate 6 (resin base materials P1 and P2) is not particularly limited, but is preferably a strip shape as shown in FIG.

Either or both of the conductive film 3 included in the first electrode substrate 2 or the conductive film 7 included in the second electrode substrate 6 are formed of a transparent conductive film.

As the material of the conductive films 3, 7, for example, tin-doped indium oxide (ITO), zinc oxide, fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), tin oxide (SnO), or antimony-doped tin oxide (ATO) can be used. Indium oxide/zinc oxide (IZO), gallium-doped zinc oxide (GZO), and the like.

The semiconductor layer 4 has a function of receiving electrons from a sensitizing dye described later and transporting it, and is formed on the surface of the conductive film 3 by using a semiconductor formed of a metal oxide. As the metal oxide, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), or the like can be used.

The semiconductor layer 4 carries a sensitizing dye. The sensitizing dye is composed of an organic dye or a metal complex dye. As the organic dye, various organic dyes such as a coumarin system, a polyene system, a cyanine glycoside system, a hemi-cyanine glycoside system, and a thiophene system can be used. As the metal complex dye, for example, a ruthenium complex or the like can be preferably used.

In this manner, the semiconductor layer 4 formed on one surface of the first electrode substrate 2 is provided to constitute the photoelectrode 5.

As the conductive film 7 provided in the second electrode substrate 6, any material that functions as a conductive film or that functions as both a catalyst layer and a conductive film without using a catalyst layer can be used. One. In the case of the former, a catalyst layer is further formed on the conductive film 7, and in the latter case, only the conductive film 7 is formed on the resin substrate P2.

Further, as the catalyst layer formed on the surface 7a of the conductive film 7, carbon paste, platinum, or the like can be used.

The counter electrode 8 is configured by including the second electrode substrate 6 configured in this manner.

The counter electrode 8 is such that the conductive film 7 faces the conductive film 3 and faces the photoelectrode 5 .

As the sealing material 10, a hot melt resin or the like can be used.

The sealing member 10 is disposed on the outer end portions 2p, 2p and/or the outer end portions 6p, 6p, and is heated and pressed to connect the photoelectrode 5 and the counter electrode 8. Also, with the sealing material 10 The end portions (the end portions on the near side and the deep side of the paper surface) where the outer end portions 2p and 6p intersect are not sealed by ultrasonic welding or the like without using the sealing material 10.

The wiring 20 is disposed on the surface 3a of the conductive film 3, and the electric power generated by the solar cell 1A can be collected and taken out. The wiring 20 is embedded in the enlarged sealing material 10 in a large cross-sectional area in the enlarged space E. Further, by disposing the wiring 20 formed with a large cross-sectional area, the wiring 20 provided in the solar cell 1A is reduced in resistance.

Further, the cross-sectional shape of the wiring 20 is formed to be elongated, and is disposed thicker in the direction between the first electrode substrate 2 and the second electrode substrate 6, in a direction crossing the direction (the sealing members 10, 10 are mutually opposed) The direction is thinner. By arranging the wiring 20 in this manner, it is easy to embed in the sealing material 10.

Furthermore, as shown in FIG. 1, it is preferable that the height of the enlarged inclined surface is larger than the height of the wiring inside the sealing material (that is, the height of the sealing material in the vertical direction is greater than the height of the wiring in the vertical direction) . Thereby, when the force of compressing in the thickness direction is applied, the sealant portion is preferentially deformed, and the effect of suppressing deformation of the wiring portion can be obtained. Thereby, when the force of compressing in the thickness direction is applied, the supply of the generated electric power can be continuously performed.

The electrolytic solution 11 permeates into the inside of the semiconductor layer 4, and is applied to substantially the entire surface thereof, and is held in the vicinity of the region X1 which is further inside the sealing member 10 via the enlarged space E.

The electrolytic solution 11 has a specific viscosity and a surface tension, and is in close contact with the first electrode substrate 2 and the second electrode substrate 6, respectively. Therefore, the electrolytic solution 11 does not easily flow from the region X1 and its vicinity to the sealing material 10 side.

In addition, an enlarged space E between the electrolyte solution 11 and the sealing material 10 so as to be spaced apart from each other is formed inside the sealing material 10, and a non-contact portion that does not contact the electrolytic solution 11 is formed in the sealing material 10. N.

The non-contact portion N is preferably a non-contact portion N that is not in contact with the electrolyte over the entire surface of the sealing material 10 that faces the electrolyte.

Further, the ratio (a/b) of the volume (a) of the enlarged space E to the volume (b) of the electrolytic solution 11 (electrolyte) is preferably more than 1/3, more preferably 1/2 or more, and particularly preferably It is 1 or more.

Further, as the electrolytic solution 11, for example, a nonaqueous solvent such as acetonitrile or propionitrile may be used; and lithium iodide may be mixed in a liquid component such as an ionic liquid such as 2-methylpropylimidazolium iodide or butylmethylimidazolium iodide. Support solutions such as electrolyte and iodine. Further, in order to prevent reverse electron transfer, the electrolyte 11 may be a compound containing a third butyl pyridine.

Next, a method of manufacturing the solar cell 1A will be described with reference to Figs. 2 to 5 .

Further, the parts, materials, and the like which can be used in the production method of the present invention can be the same as those described above for the photoelectric conversion element.

The manufacturing method of the solar cell 1A of the first embodiment includes (I) an electrolyte disposing step of disposing the electrolyte 11 on the semiconductor layer 4 on the first electrode substrate 2 of the photoelectrode 5; (II) sealing material arrangement a step of disposing the sealing material 10 on any of the outer end portions 2p and 2p of the first electrode substrate 2 and the outer end portions 6p and 6p of the second electrode substrate 6; (III) a lamination step of the photoelectrode 5 laminated counter electrode 8; (IV) an electrolyte extending step of pressurizing the photoelectrode 5 and the counter electrode 8 to allow the electrolyte 11 to penetrate into the semiconductor layer 4 and hold it on the first electrode substrate 2 and the second Between the electrode substrates 6, a space expansion wall portion 15 that enlarges the size between the first electrode substrate 2 and the second electrode substrate 6 between the semiconductor layer 4 and the sealing material 10 is formed, so that the sealing material 10 is formed without electrolysis. The non-contact portion N in contact with the liquid 11; and (V) a sealing step of sealing the photoelectrode 5 and the counter electrode 8.

The steps are explained below.

<Preparation of Photoelectrode 5 and Counter Electrode 8>

As shown in FIG. 4, before the electrolyte disposing step, the resin substrate P1 wound in a roll shape is first drawn in one direction (arrow L direction), and the conductive film 3 is formed on one surface thereof as a first electrode substrate. 2. The semiconductor layer 4 is formed on the surface of the conductive film 3, and the semiconductor layer 4 carries a dye as the photoelectrode 5. The carrying of the dye to the semiconductor layer 4 can be carried out, for example, by spraying. Further, a roll-shaped resin substrate in which the conductive film 3 is formed on one surface of the resin substrate P1 in advance may be used.

In addition, the resin substrate P2 wound in a roll shape is drawn in the opposite direction of the first electrode substrate 2 in the opposite direction, for example, and the conductive film 7 is formed on one surface thereof as the counter electrode 8. Thereafter, the surface of the counter electrode 8 is reversed, and the conductive film 7 is opposed to the conductive film 3, and is extended in the same direction as the photoelectrode 5.

(I) <electrolyte configuration step>

As shown in FIG. 2, in the electrolyte disposing step, the electrolytic solution 11 is dropped onto the surface of the semiconductor layer 4 of the photoelectrode 5 to be taken out. At this time, the total capacity of the electrolytic solution 11 is previously set to sufficiently cover the surface of the semiconductor layer 4 and is smaller than the volume of the internal space S of the solar cell 1A.

(II) Sealing material configuration steps

As shown in FIG. 3 and FIG. 4, in the sealing material disposing step, the sealing material 10 is placed between the ends 2p and 2p at the positions other than the outer ends of the semiconductor layer 4 via the semiconductor layer 4. At this time, the wiring member 20 having a large cross-sectional area may be disposed at the end portion where the current collecting is performed, and then the sealing material 10 may be placed on the wiring 20 to embed the wiring 20 in the sealing material 10.

Furthermore, the electrolyte disposing step and the sealing material disposing step may be performed first.

(III) Lamination step

In the lamination step, as shown in FIG. 4, the photoelectrode 5 and the counter electrode 8 are guided by the rollers R and R so as to overlap each other, and the semiconductor layer 4 and the electroconductive film 7 are opposed to each other, and the photoelectrode 5 and the counter electrode 8 are opposed. Laminated.

(IV) <electrolyte extension step>

The electrolyte extension step is performed substantially simultaneously with the above lamination step. Specifically, in the stacking step, the photoelectrode 5 and the counter electrode 8 which are guided to overlap each other are superposed on each other, and as shown in FIG. 5, the surface 2b from the outer side of the first electrode substrate 2 by the rollers R and R and Both of the surfaces 6b on the outer side of the second electrode substrate 6 are pressurized. Here, as the roller R, for example, the surface layer portion R1 is formed of a material such as rubber which can be elastically deformed, and is elastically deformable under a pressing force of a specific pressure or more, and is elastically restored under a pressing force of a specific pressure or less.

In this manner, since the sealing material 10 has a specific thickness (height in the vertical direction) and is substantially not elastically deformed, the surface layer portion R1 is elastically deformed by applying a pressing force of a specific pressure or more to the surface portion R1 of the rolls R and R. Thereby, the outer end portions 2p and 6p of the sealing material 10 are disposed, and the thickness of the sealing material 10 is substantially maintained, and the first electrode substrate 2 and the second electrode substrate 6 are extended in parallel.

On the other hand, the resin substrates P1 and P2 have flexibility on the inner side of the sealing material 10, so that the first electrode substrate 2 and the second electrode substrate 6 are opposed to the rolls R and R during the process of traveling between the rolls R and R. The applied pressure below a certain pressure is applied. Thereby, the surface layer portion R1 of the rolls R and R deforms (i.e., inclines) the first electrode substrate 2 and the second electrode substrate 6 in the direction in which they approach each other, thereby forming the space enlarged wall portion 15. As a result, as shown in FIG. 5, the first electrode substrate 2 and the second electrode substrate 6 are formed with the enlarged space portions 15, 15 having the inclined faces 15a and 15a which are mutually expanded in the vicinity of the sealing member 10, and by These spaces enlarge the wall portions 15 and 15 to form an enlarged space E in which the internal space S is enlarged. Moreover, the first electrode substrate 2 and the second electrode are further formed in the region X1 as shown in FIG. The electrode substrate 6 extends in parallel with a distance L1 which is slightly larger than the thickness of the semiconductor layer 4.

Further, at this time, as shown in FIG. 4, as the photoelectrode 5 and the counter electrode 8 travel between the rolls R and R, the electrolytic solution 11 dropped at a predetermined interval gradually extends in the traveling direction, and the surface tension is applied to the semiconductor layer 4 by the surface tension. The surface and the vicinity of the air are adhered to the first electrode substrate 2 and the second electrode substrate 6 to be applied to the entire semiconductor layer 4.

Further, the electrolytic solution 11 is dropped by a total volume smaller than the internal space S formed by the first electrode substrate 2, the second electrode substrate 6, and the sealing material 10 and the volume of the void formed in the semiconductor layer 4. As a result, the elongated electrolytic solution 11 stops extending in the middle of the enlarged space E formed by the space enlarged wall portion 15, and stops in the vicinity of the semiconductor layer 4 with little penetration into the enlarged space E. As a result, the sealing material 10 is separated from the electrolytic solution 11, and the non-contact portion N (see FIG. 1) that does not come into contact with the electrolytic solution 11 is formed in the sealing material 10.

(V) <sealing step>

After the electrolyte extending step, in the sealing step, the photoelectrode 5 and the counter electrode 8 are bonded by heating the portion where the sealing material 10 is disposed, and as shown in FIG. 4, with the photoelectrode 5 and the counter electrode. The direction in which the transport direction of the 8 (arrow L1 direction) intersects is obtained by bonding by the ultrasonic welding device 50, and the solar battery 1A shown in Fig. 1 is obtained.

As described above, according to the solar cell 1A shown in FIG. 1, the electrolyte solution 11 is held in a region X1 in the enlarged space E so as to be in close contact with the first electrode substrate 2 and the second electrode substrate 6 without flowing, and is sealed. The material 10 forms the non-contact portion N of the electrolytic solution 11 and is disposed as far as possible. Therefore, it is obtained that the solar cell 1A can be provided with an effect of suppressing the deterioration of the sealing material 10 by the electrolytic solution 11 as much as possible, thereby maintaining high performance for a long period of time.

Moreover, the prior solar cell has a flat plate shape due to the resin substrates P1 and P2. In the material formation, it is considered that the electron transporting resistance by the electrolytic solution 11 may increase, and the interval between the resin substrates P1 and P2 is suppressed to several tens of micrometers or less. In other words, when the interval between the resin substrates P1 and P2 is increased, the performance of the battery is largely lowered. Therefore, the distance between the resin substrates P1 and P2 is at most about 30 μm. Therefore, the wiring member or the like interposed between the resin base materials P1 and P2 is also limited to the range limited by the distance between the resin base materials P1 and P2.

On the other hand, according to the solar cell 1A, as shown in FIG. 1, the region X1 in which the electrolytic solution 11 is disposed can be formed to be as thin as possible, and the distance L2 between the outer end portions 2p and 6p of the sealing member 10 can be disposed. The distance L1 between the first electrode substrate 2 and the second electrode substrate 6 in the region X1 is used to be 20 times or more (wherein, since FIG. 1 is a schematic view, the distance of L2 is not expressed as the distance of L1). 20 times or more), and the wiring 20 for collecting electricity having a large cross-sectional area can be disposed in the sealing material 10 or adjacent to the enlarged space E of the sealing material 10. Therefore, the effect of the solar cell 1A of high quality which can reduce the electric resistance of the wiring 20 can be acquired.

Further, the cross-sectional shape of the wiring 20 is formed to be elongated, and is disposed thicker in the direction between the first electrode substrate 2 and the second electrode substrate 6, in a direction crossing the direction (the sealing members 10, 10 are mutually opposed) The direction is thinner. Therefore, it is possible to obtain an effect that it is easy to be buried in the sealing material 10, and the product as the effective area for power generation in the semiconductor layer 4 can be increased as much as possible, so that the photoelectric conversion efficiency can be improved as much as possible.

Moreover, by increasing the thickness (height in the vertical direction) of the sealing material 10 as much as possible and making the thickness 200 μm or less, it is possible to prevent the power generation of the semiconductor layer 4 from being effectively caused by the increase in the dead space around the sealing material 10. The effect of the decline in area.

Further, in the solar cell 1A, the semiconductor layer 4 having a lower conductivity is interposed between the conductive film 3 and the conductive film 7, and the first electrode substrate 2 and the second electrode are provided in other portions. The substrate 6 is formed in a direction which is curved away from each other and gradually separated. Therefore, it is possible to obtain an effect of forming the solar cell 1A which is less likely to be short-circuited even if the spacer formed of the nonwoven fabric or the like is not interposed between the conductive film 3 and the conductive film 7.

Further, the effect of the low-cost solar cell 1A capable of forming the cost of the spacer and the step of interposing the spacer can be obtained. Furthermore, the spacer may also be interposed between the photoelectrode 5 and the counter electrode 8.

Moreover, since the electrolytic solution 11 filled in the internal space S can be minimized, the effect of forming the solar cell 1A whose manufacturing cost is controlled can be obtained.

Further, as shown in FIG. 4, in the method of manufacturing the solar cell 1A of the present invention, the electrolytic solution 11 is dropped onto the semiconductor layer 4 before sealing between the photoelectrode 5 and the counter electrode 8, and thereafter The photoelectrode 5 is bonded to the counter electrode 8. Further, the electrolytic solution 11 used at this time does not overflow from the internal space S. Therefore, when the solar cell 1A is manufactured, it is not necessary to place the bonded photoelectrode 5 and the counter electrode 8 in a vacuum environment, and the photoelectrode 5 and the counter electrode 8 are not immersed in the electrolyte 11 in a bonded state. Therefore, the operation of wiping the electrolyte 11 on the outer surface of the solar cell 1A can be omitted.

Therefore, it is possible to obtain the effect of manufacturing the solar cell 1A without using an expensive vacuum apparatus in a simple manufacturing step.

Further, according to the method for manufacturing the solar cell 1A of the above-described embodiment, the step of stacking and the step of extending the electrolyte can be simultaneously performed while pressurizing the photoelectrode 5 and the counter electrode 8 by the rolls R and R.

Further, the method can send the respective manufacturing steps in one direction, and the end portions 2p, 6p extending in the longitudinal direction (arrow L direction) by the sealing members 10, 10‧‧ can be used, and The front end of the anode battery 1A is sealed and cut at any position by ultrasonic welding or the like in a direction in which the sealing material 10 intersects. In other words, the so-called Roll to Roll manufacturing in which the solar cell 1A is manufactured while the photoelectrode 5 and the counter electrode 8 are formed in a strip shape and transported in the longitudinal direction can be obtained, regardless of the photoelectrode 5 and the pair. The solar cell 1A is extremely simple, efficient, and rapid to be applied to the bonding position of the electrode 8.

In the above-described embodiment, the solar cell 1A is configured such that the flexible resin substrates P1 and P2 are used for both the first electrode substrate 2 and the second electrode substrate 6. However, the present invention is not limited to the configuration of the embodiment. By. In other words, as shown in FIG. 6, even if only one of the first electrode substrate 2 and the second electrode substrate 6 is provided with a flexible resin substrate, the non-contact portion N can be formed in the enlarged space E and the sealing member 10. . Therefore, substantially the same functions, functions, and effects as those described above can be obtained.

Further, in the above-described embodiment and its modifications, the semiconductor layer 4 is formed so as not to be in contact with the sealing material 10, but the present invention is not limited to such a constitution. In other words, the semiconductor layer 4 may be placed in contact with the sealing material 10 as long as the electrolytic solution 11 is disposed at a distance from the sealing material 10 with the enlarged space E interposed therebetween.

Further, in the above embodiment, the wiring 20 is embedded in the sealing material 10, but the wiring 20 may be disposed in the enlarged space E. When the wiring 20 is disposed in the enlarged space E, the thickness of the wiring 20 is increased in the direction between the first electrode substrate 2 and the second electrode substrate 6 to reduce the electric resistance of the wiring 20, and the sealing material 10, The thickness of the wiring 20 is thinned in the direction of 10 to thin the line, whereby the effect of increasing the effective area of power generation of the semiconductor layer 4 (i.e., the surface area when the semiconductor layer 4 is viewed) can be obtained as much as possible.

Moreover, in the above embodiment, the photoelectrode 5 and the counter electrode 8 are used. The present invention has been described by arranging an electrolyte 11 between them, but the present invention can be preferably carried out even if a gel-like or solid electrolyte is used. Further, when a gel-like or solid electrolyte is used, a gel-like or solid electrolyte is disposed on the semiconductor layer 4, and then the photoelectrode 5 and the counter electrode 8 are laminated, followed by heating and pressurization to make the gel The electrolyte of a shape or solid penetrates into the semiconductor layer 4.

Further, in the above-described embodiment, the outer end portion where the outer end portions 2p and 6p of the sealing members 10 and 10 are disposed is ultrasonically welded and sealed, but may be suitably carried out by a sealing method other than ultrasonic welding. seal.

Further, in the above-described embodiment, the configuration in which the semiconductor layers 4 are arranged in two rows in the width direction of the first electrode substrate 2 will be described as an example. However, the configuration of the present invention is not limited to such a configuration, and the semiconductor layer 4 is also It can be one or more rows of film formation.

Claims (10)

A photoelectric conversion element comprising: a photoelectrode formed with a semiconductor layer on a first electrode substrate; a counter electrode provided with a second electrode substrate disposed opposite to the first electrode substrate; and a sealing material that reflects the light Sealing between the electrode and the counter electrode; and an electrolyte disposed on the inner side of the sealing material; and disposing at least one of the first electrode substrate and the second electrode substrate to face the first electrode substrate a surface of the surface of the second electrode substrate that is enlarged in size and enlarged in size, and an enlarged space is formed inside the sealing material, and the electrolyte is held on the inner side of the enlarged space on the first electrode substrate and the first Between the two electrode substrates, a non-contact portion that does not contact the electrolyte is formed in the sealing material. The photoelectric conversion element according to claim 1, wherein the wiring is provided in the enlarged space or the sealing material, and the wiring is disposed on at least one electrode selected from the group consisting of the first electrode substrate and the second electrode substrate. On the substrate. The photoelectric conversion element according to claim 1 or 2, wherein the space expansion wall portion has an inclined surface that gradually enlarges the size of the space toward the sealing material. The photoelectric conversion element according to claim 1 or 2, wherein a thickness dimension of the sealing material, a surface of the first electrode substrate and a surface of the second electrode substrate, a region where the semiconductor layer is formed, The maximum difference in size is set to 30 μm or more and 200 μm or less. The photoelectric conversion element of claim 2, wherein a height of the sealing material in a vertical direction is greater than a height of the wiring in a vertical direction. For example, the photoelectric conversion element of claim 1 or 2, wherein the enlarged space body The product is greater than 1/3 of the volume of the electrolyte. The photoelectric conversion element according to claim 1 or 2, wherein a deterioration preventing member of the sealing material is provided between the electrolyte and the sealing material. A method for producing a photoelectric conversion element, comprising: an electrolyte disposing step of disposing an electrolyte in a semiconductor layer on a first electrode substrate provided in the photoelectrode; and a sealing material disposing step of the end portion of the first electrode substrate And a sealing material is disposed on at least one of the end portions of the second electrode substrate; a laminating step of the photoelectrode laminate having the counter electrode of the second electrode substrate; and an electrolyte extending step of the photoelectrode and the counter electrode Pressurizing the electrode, disposing the electrolyte in the semiconductor layer and holding it between the first electrode substrate and the second electrode substrate, and forming the first electrode substrate and the second electrode in the vicinity of the sealing material The space in which the substrate is enlarged in size increases the wall portion, and the sealing material forms a non-contact portion that does not contact the electrolyte; and a sealing step of sealing the photoelectrode with the counter electrode. The method of manufacturing a photoelectric conversion element according to claim 8, wherein the laminating step, the electrolyte extending step, and the sealing step are simultaneously performed by pressurization of the photoelectrode and the counter electrode. The method for manufacturing a photoelectric conversion element according to claim 8 or 9, wherein the space expansion wall portion is formed by: using at least one of the first electrode substrate and the second electrode substrate The flexible resin substrate deforms the flexible resin substrate when the photoelectrode and the counter electrode are pressurized.