KR102276767B1 - Photoelectric conversion element and method for manufacturing photoelectric conversion element - Google Patents

Abstract

The present invention provides a counter electrode comprising a photoelectrode having a semiconductor layer formed on a first electrode substrate, a second electrode substrate facing the first electrode substrate, and a sealing material sealing between the photoelectrode and the counter electrode; an electrolyte disposed inside the sealing material, and on at least one of the first electrode substrate and the second electrode substrate, a distance between the surfaces of the first electrode substrate and the second electrode substrate facing each other A space expanding wall portion for enlarging is provided to form an enlarged space inside the sealing material, and the electrolyte is held between the first electrode substrate and the second electrode substrate inside the enlarged space, and the sealing material is provided with the It relates to a photoelectric conversion element characterized in that a non-contact portion not in contact with an electrolyte is formed.

Description

A photoelectric conversion element and the manufacturing method of a photoelectric conversion element TECHNICAL FIELD

The present invention relates to a photoelectric conversion element and a method for manufacturing the photoelectric conversion element. This application claims priority on August 22, 2013 based on Japanese Patent Application No. 2013-172561 for which it applied to Japan, The content is used here.

In recent years, a solar cell has been attracting attention as a power generation device of clean energy replacing fossil fuel, and development of a silicon (Si)-based solar cell and a dye-sensitized solar cell is progressing. In particular, dye-sensitized solar cells are inexpensive and easy to mass-produce, and their structures and manufacturing methods have been widely researched and developed (eg, Patent Document 1 below).

As shown in FIG. 7 , in the dye-sensitized solar cell 100 described in Patent Document 1, a transparent conductive film 102 is formed on the plate surface of a transparent substrate 101 , and a dye is applied to the surface of the transparent conductive film 102 . A photoelectrode 104 having a supported semiconductor layer 103 formed thereon; a counter electrode 107 in which a counter conductive film 106 provided on a counter substrate 105 to face the transparent conductive film 102 is formed; a semiconductor; A sealing material 108 enclosing the layer 103 and joining the outer peripheral wall portion of the photoelectrode 104 and the outer peripheral wall portion of the counter electrode 107 to form an inner space S and sealing the inner space S ) and the electrolyte 109 injected into the inner space S.

Japanese Patent Application Laid-Open No. 2011-175939

However, in the dye-sensitized solar cell 100, when the electrolyte solution 109 is injected into the internal space S, the sealing material 108 and the electrolyte solution 109 come into contact with the sealing material 108 to deteriorate the solar cell ( 100), there was a problem that the quality was lowered. When the sealing material 108 deteriorates, the electrolyte 109 penetrates into the inside of the sealing material 108 due to a decrease in the barrier properties of the sealing material 108 , or the sealing material 108 and the semiconductor due to a decrease in the adhesive strength of the sealing material 108 . There is a fear that a short circuit may occur, such as the interface of the layer 103 or the like peeling off.

Therefore, this invention makes it a subject to provide the photoelectric conversion element which can suppress that a sealing material and electrolyte solution contact in view of the said subject.

The photoelectric conversion element of the present invention includes a counter electrode including a photoelectrode having a semiconductor layer formed on a first electrode substrate, and a second electrode substrate facing the first electrode substrate through the semiconductor layer, the photoelectrode and the photoelectric conversion element A sealing material for sealing between the counter electrodes, and an electrolyte disposed inside the sealing material, wherein at least one of the first electrode substrate and the second electrode substrate is formed of the first electrode substrate and the second electrode substrate. A space expansion wall portion for enlarging the separation dimension is provided to form an enlarged space inside the sealing material, the electrolyte is held between the first electrode substrate and the second electrode substrate inside the enlarged space, and the sealing material It is characterized in that a non-contact portion not in contact with the electrolyte is formed.

According to this structure, since the non-contact part which does not contact with electrolyte is formed in the sealing material, deterioration of the sealing material by electrolyte can be prevented, and generation|occurrence|production of a short circuit can be suppressed by it.

In addition, the "electrolyte" shown in this application contains electrolyte solution, a gel electrolyte, and a solid electrolyte.

It is preferable that a wiring arranged on at least one electrode substrate selected from the group consisting of a first electrode substrate and a second electrode substrate is provided in the expanded space or the sealing material.

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

The space expanding wall portion of the present invention may have an inclined surface that gradually enlarges the separation dimension toward the sealing material.

According to this configuration, it is possible to prevent the electrolyte from coming into contact with the sealing material by holding the electrolyte in the expanded space formed by the space expanding wall portion.

In the present invention, the difference between the thickness (height in the vertical direction) of the sealing material and 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 30 μm or more and 200 μm or less. It is preferable to be

According to this structure, the wiring with the cross-sectional area as large as possible can be embedded in the inside of the sealing material, and wiring resistance can be reduced. Moreover, by setting it as 200 micrometers or less, it can prevent from causing the fall of the effective power generation area by the dead space increasing around the sealing material.

The method of manufacturing a photoelectric conversion device of the present invention includes an electrolyte disposing process of disposing an electrolyte in a semiconductor layer on a first electrode substrate provided in a photoelectrode, and at least one of an end of the first electrode substrate and an end of the second electrode substrate a sealing material disposing step of disposing a sealing material on the substrate; a laminating step of laminating a counter electrode including a second electrode substrate on the photoelectrode; and pressing the photoelectrode and the counter electrode, and disposing the electrolyte in the semiconductor layer while forming a space expanding wall portion that is held between the first electrode substrate and the second electrode substrate and enlarges the separation dimension between the first electrode substrate and the second electrode substrate in the vicinity of the sealing material, It is characterized by comprising: an electrolyte stretching step of forming a non-contact portion not in contact with the electrolyte in a sealing material; and a sealing step of sealing the photoelectrode and the counter electrode.

According to this structure, the photoelectric conversion element described above can be manufactured simply.

In this invention, it is preferable that the said lamination|stacking process, the said electrolyte stretching process, and the said sealing process are performed simultaneously by pressurization of the said photoelectrode and the said counter electrode.

According to this structure, the manufacturing process of the photoelectric conversion element described above becomes further simpler.

The space expansion wall portion of the present invention uses a flexible resin substrate for at least one of the first electrode substrate and the second electrode substrate, and the flexible resin when pressing the photoelectrode and the counter electrode It is preferably formed by deforming the substrate.

According to this structure, lamination|stacking and pressurization of a photoelectrode and a counter electrode can be performed simultaneously, and also the structure which forms the non-contact part which does not contact electrolyte with a sealing material can be shape|molded at the time of pressurization.

ADVANTAGE OF THE INVENTION According to this invention, it suppresses contact of a sealing material and electrolyte, and exhibits the effect that quality deterioration of a photoelectric conversion element can be prevented.

Moreover, according to the manufacturing method of the photoelectric conversion element of this invention, the effect that the photoelectric conversion element of this invention can be manufactured simply and efficiently is exhibited.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the photoelectric conversion element of one Embodiment of this invention.
2 is a cross-sectional view schematically showing a part of a manufacturing process of a photoelectric conversion element according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing a part of a manufacturing process of a photoelectric conversion element according to an embodiment of the present invention.
4 is a diagram schematically illustrating a manufacturing process of a photoelectric conversion element according to an embodiment of the present invention.
Fig. 5 is a cross-sectional view taken along the line Y1-Y2 in the direction of the arrow of the photoelectric conversion element of the embodiment of the present invention shown in Fig. 4;
6 is a cross-sectional view schematically showing another example of the photoelectric conversion element according to the embodiment of the present invention.
7 is a cross-sectional view showing a conventional photoelectric conversion element.

EMBODIMENT OF THE INVENTION Hereinafter, each embodiment of the photoelectric conversion element of this invention is described with reference to drawings, taking the case where a photoelectric conversion element is a dye-sensitized solar cell as an example and demonstrating. In addition, the case where a photoelectric conversion element is manufactured using electrolyte solution as electrolyte is taken as an example and demonstrated.

(First embodiment)

As shown in Fig. 1, a dye-sensitized solar cell (photoelectric conversion element) (hereinafter referred to as "solar cell") 1A is a photoelectrode ( 5) and the counter electrode 8 provided with the 2nd electrode board|substrate 6 opposingly arrange|positioned with the 1st electrode board|substrate 2 spaced apart.

Then, between the photoelectrode 5 and the counter electrode 8, the sealing material 10 and the outer end portion 2p of the first electrode substrate 2 and the outer end portion 6p of the second electrode substrate 6 are provided. The electrolytic solution 11 is sealed in a frame shape to surround the outer periphery of the photoelectrode 5 and the counter electrode 8 by ultrasonic welding or the like, and in the sealed internal space S and the voids (not shown) in the semiconductor layer 4 . ) is charged. In FIG. 1, the solar cell which has the above structure is continuously formed as a unit cell on the left and right. The shape of the unit cell is not particularly limited, and can be exemplified by a triangle, a quadrangle, a polygon other than these, a circle, an ellipse, and the like, but is preferably a band shape as shown in FIG. 4 from the viewpoint of manufacturing efficiency and the like.

The sealing material 10 is installed on at least a part of the edge of the unit cell (solar cell). That is, the sealing material 10 may be installed to completely surround the unit cell, and as long as the desired effect in the present invention can be achieved, only a part of the edge of the unit cell is installed, and the rest of the edge is used by other means. It may be sealed. In the case where the sealing material 10 is provided only in a part of the edge portion of the unit cell, a plurality of the sealing material 10 may be intermittently provided in the edge portion of the unit cell.

For example, as a specific example of the arrangement method of the sealing material 10 in the case where the unit cell has a band-like shape as shown in FIG. 4 , the following are exemplified: (1) The sealing material 10 is a unit cell provided only on one side of the pair of opposing long sides, (2) the sealing material 10 is provided on both sides of the pair of long sides facing the unit cell, (3) the sealing material 10 is provided on the unit cell By providing both sides of the opposite pair of long sides and one of the other pair of short sides, the sealing material 10 is arranged in an inverted U-shape, and (4) the sealing material 10 is placed on the four sides of the unit cell. It is installed in both and completely surrounds the unit cell with the sealing material (10).

Here, the 1st electrode substrate 2 has the space expansion wall part 15 provided with the inclined surface 15a inside the outer edge part 2p where the sealing material 10 is arrange|positioned.

Further, the second electrode substrate 6 also has a space expansion wall portion 15 having an inclined surface 15a inside the outer end portion 6p, similarly to the first electrode substrate 2 . And, in the vicinity of the sealing material 10, these space expansion wall parts 15 and 15 measure the distance L1 of the surface of the 1st electrode substrate 2 and the surface of the 2nd electrode substrate 6 to the outer edge part ( 2p) from the inside to the outside, ie, toward the sealing material 10, it enlarges gradually, and forms the enlarged space E in which a part of the internal space S was enlarged.

In the meantime, the enlarged space E located in the region X2 sandwiched between the enlarged wall portions 15 and 15 can sufficiently hold the electrolyte 11 protruding from the semiconductor layer 4 and the region X1 adjacent thereto. , so that it can be separated by pushing as much as possible between the electrolyte 11 and the sealing material 10 .

In addition, it is preferable to provide a deterioration preventing member (not shown) of the sealing material 10 between the electrolyte solution 11 and the sealing material 10 . Specifically, it is preferable to provide a deterioration preventing member so as to partition the space in which the electrolyte 11 exists between the photoelectrode 5 and the counter electrode 8 and the expanded space E. As shown in FIG. It is preferable that this deterioration prevention member is formed of solids, such as a fluororesin which has solvent resistance and/or iodine resistance, for example. By providing the deterioration preventing member, even if the space in which the electrolyte 11 is present is compressed due to pressure being applied to the solar cell from above, it is possible to prevent the electrolyte 11 from contacting the sealing material 10 .

The first electrode substrate 2 and the second electrode substrate 6 are each, for example, a resin substrate P1 mainly made of a transparent thermoplastic resin material such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET); The conductive films 3 and 7 are formed on the surface of P2). In addition, the resin base material P1, P2 may be formed in the form of a film.

Although there is no restriction|limiting in particular about the shape of the 1st electrode substrate 2 and the 2nd electrode substrate 6 (resin base material P1 and P2), It is preferable that it is a strip|belt shape as shown in FIG.

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

Examples of the material of the conductive films 3 and 7 include tin-doped indium oxide (ITO), zinc oxide, fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), tin oxide (SnO), and antimony doping. Tin oxide (ATO), indium oxide/zinc oxide (IZO), gallium-doped zinc oxide (GZO), etc. are used.

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

The semiconductor layer 4 carries a sensitizing dye. The sensitizing dye is composed of an organic dye or a metal complex dye. As an organic pigment|dye, various organic pigments, such as a coumarin type, a polyene type, a cyanine type, a hemicyanine type, a thiophene type, can be used, for example. As a metal complex dye, a ruthenium complex etc. are used suitably, for example.

In this way, the photoelectrode 5 is constituted by providing the semiconductor layer 4 formed on one plate surface of the first electrode substrate 2 .

As the conductive film 7 provided on the second electrode substrate 6, any one of a material having a role as a conductive film without having a role of a catalyst layer or a material capable of serving as both a catalyst layer and a conductive film is employed. have. In the former case, the 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.

In addition, as a catalyst layer formed into a film on the surface of the conductive film 7, carbon paste, platinum, etc. are employ|adopted.

The counter electrode 8 is comprised with the 2nd electrode board|substrate 6 comprised in this way.

The counter electrode 8 is disposed to face the photoelectrode 5 with the conductive film 7 facing the conductive film 3 .

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

This sealant 10 is disposed on the pair of outer ends 2p, 2p and/or the pair of outer ends 6p, 6p, and is heat-pressed to bond between the photoelectrode 5 and the counter electrode 8 . are doing In addition, the ends (ends provided on the front side and inner side of the paper) intersecting the outer ends 2p and 6p on which the sealing material 10 is disposed are sealed by ultrasonic welding or the like without using the sealing material 10 .

The wiring 20 is disposed on the surface of the conductive film 3 so as to collect electricity generated in the solar cell 1A and take it out. This wiring 20 is embedded in the enlarged space E with a large cross-sectional area in the thickly arranged sealing material 10 . Further, by disposing the wiring 20 having a large cross-sectional area, the resistance of the wiring 20 provided in the solar cell 1A is reduced.

In addition, the cross-sectional shape of the wiring 20 is long and thin, thick in the direction between the first electrode substrate 2 and the second electrode substrate 6, and the direction intersecting it (the sealing materials 10 and 10). direction) so as to be thinner. By arranging the wiring 20 in this way, it is easy to be embedded in the sealing material 10 .

Also, as shown in Fig. 1, it is preferable that the height of the inclined surface to be enlarged 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 a compressive force in the thickness direction is applied, the sealant portion is preferentially deformed, and an effect of suppressing deformation of the wiring portion is obtained. Thereby, in the case where the force to compress in the thickness direction is applied, it becomes possible to continue the supply of the generated electric power.

The electrolyte 11 penetrates into the inside of the semiconductor layer 4, is coated on substantially the entire surface, and is held in the vicinity of the region X1 inside the sealing material 10 through the enlarged space E. .

Since this electrolyte solution 11 has a predetermined viscosity and surface tension, it is closely_contact|adhered to each of the 1st electrode substrate 2 and the 2nd electrode substrate 6 . Accordingly, the electrolyte 11 does not easily flow from the region X1 and its vicinity to the sealing material 10 side.

And by this, between the electrolyte 11 and the sealing material 10, an enlarged space E spaced therebetween is formed inside the sealing material 10, and the electrolyte 11 does not contact the sealing material 10. A non-contact portion N is formed.

About this non-contact part N, it is preferable that the whole surface of the said sealing material 10 which opposes electrolyte becomes the non-contact part N which does not contact with electrolyte.

In addition, the volume a of the expanded space E is a ratio (a/b) to the volume b of the electrolyte 11 (electrolyte), preferably greater than 1/3, and not less than 1/2. It is more preferable, and it is especially preferable that it is 1 or more.

Moreover, as electrolyte solution 11, For example, Non-aqueous solvents, such as acetonitrile and propionitrile; The solution etc. which mixed support electrolytes, such as lithium iodide, and iodine, are used for liquid components, such as ionic liquids, such as dimethyl propyl imidazolium iodide or butyl methyl imidazolium iodide. In addition, in order to prevent the reverse electron transfer reaction, the electrolyte solution 11 may contain t-butylpyridine.

Next, a method for manufacturing the solar cell 1A will be described with reference to FIGS. 2 to 5 . In addition, as for the components, materials, etc. which can be used for the manufacturing method of this invention, the thing similar to what was mentioned above regarding the photoelectric conversion element can be used.

In the manufacturing method of the solar cell 1A of 1st Embodiment, (I) the electrolyte arrangement|positioning process of arrange|positioning the electrolyte solution 11 in the semiconductor layer 4 on the 1st electrode substrate 2 with which the photoelectrode 5 was equipped. and (II) a sealing material arrangement step of disposing the sealing material 10 on either one of the outer ends 2p and 2p of the first electrode substrate 2 and the outer ends 6p and 6p of the second electrode substrate 6 and (III) a lamination process of laminating the counter electrode 8 on the photoelectrode 5; (IV) pressurizing the photoelectrode 5 and the counter electrode 8 so that the electrolytic solution 11 is applied to the semiconductor layer 4 ) while being held between the first electrode substrate 2 and the second electrode substrate 6, and between the semiconductor layer 4 and the sealing material 10, the first electrode substrate 2 and the second electrode An electrolyte stretching step of forming a space expanding wall portion 15 that enlarges the separation dimension of the substrate 6 to form a non-contact portion N not in contact with the electrolyte 11 in the sealing material 10; (V) a photoelectrode (5) and a sealing step of sealing the counter electrode 8 are provided.

Hereinafter, each process is demonstrated.

<Preparation of the photoelectrode 5 and the counter electrode 8>

As shown in Fig. 4, before the electrolyte disposing step, first, the resin substrate P1 wound in a roll shape is drawn out in one direction (arrow L direction), and a conductive film 3 is formed on one plate surface thereof. Thus, a first electrode substrate 2 is formed, a semiconductor layer 4 is formed on the surface of the conductive film 3, and a dye is supported thereon to be a photoelectrode 5 . The support of the dye to the semiconductor layer 4 can be performed, for example, by spray application. Moreover, you may use the roll-shaped resin base material in which the electrically conductive film 3 was previously formed in one plate|board surface of the resin base material P1.

Furthermore, the resin base material P2 wound in roll shape is taken out, for example in one direction and the opposite direction from the upper side of the 1st electrode substrate 2, and the conductive film 7 is formed into a film on the one plate surface. Thus, the counter electrode 8 is formed. Thereafter, the plate surface of the counter electrode 8 is inverted and the conductive film 7 is opposed to the conductive film 3 to extend in the same direction as the photoelectrode 5 .

(I) <Electrolyte batch process>

As shown in FIG. 2 , in the electrolyte arrangement step, the electrolyte 11 is dropped on the surface of the semiconductor layer 4 of the photoelectrode 5 withdrawn. At this time, the total capacity of the electrolytic solution 11 is made smaller than the volume of the internal space S of the solar cell 1A while sufficiently covering the surface of the semiconductor layer 4 .

(II) sealing material placement process

3 and 4, in the sealing material arrangement step, the sealing material 10 is sandwiched between the semiconductor layer 4 at the positions of the outer end portions 2p and 2p spaced apart from the outer end portion of the semiconductor layer 4 place the At this time, the sealing material 10 may be disposed on the wiring 20 after arranging the wiring 20 having a large cross-sectional area at the end for collecting current, and the wiring 20 may be embedded in the sealing material 10 .

In addition, the electrolyte disposing process and the sealing material disposing process do not matter which one is performed first.

(III) lamination process

In the lamination process, as shown in FIG. 4 , the photoelectrode 5 and the counter electrode 8 are guided to overlap with rollers R and R, and the semiconductor layer 4 and the conductive film 7 are opposed to each other. The electrode 5 and the counter electrode 8 are laminated.

(IV) <Electrolyte drawing process>

The electrolytic stretching process is performed substantially simultaneously with the above-described lamination process. Specifically, the photoelectrode 5 and the counter electrode 8 guided to overlap each other in the lamination process are overlapped, and at the same time as shown in FIG. 5, the outer surface 2b of the first electrode substrate 2 is and the rollers R and R from both of the outer surface 6b of the second electrode substrate 6 . Here, as the roller R, for example, the surface layer portion R1 thereof is formed of a material such as elastically deformable rubber, elastically deformed by a pressing force equal to or greater than a predetermined pressure, and elastically returned with a pressing force equal to or less than a predetermined pressure. use what you have

Then, since the sealing material 10 has a predetermined thickness (height in the vertical direction) dimension and is hardly elastically deformed, a pressing force greater than or equal to a predetermined pressure is applied to the surface layer portion R1 of the rollers R and R, and the surface layer portion R1 is elastically deformed. Accordingly, at the outer ends 2p and 6p where the sealing material 10 is disposed, the thickness dimension of the sealing material 10 is maintained approximately to extend the first electrode substrate 2 and the second electrode substrate 6 in parallel. .

On the other hand, inside the sealing material 10, since the resin base materials P1 and P2 have flexibility, the 1st electrode board|substrate 2 and the 2nd electrode board|substrate 6 advance between the rollers R, R. In the process, a pressing force less than a predetermined pressure is relatively applied to the rollers R and R. Accordingly, the surface layer portion R1 of the rollers R and R deforms (ie, tilts) the first electrode substrate 2 and the second electrode substrate 6 in a direction to approach each other to form the space expanding wall portion 15 . do. As a result, in the first electrode substrate 2 and the second electrode substrate 6, as shown in FIG. 5, a space expansion wall portion having inclined surfaces 15a and 15a that expand and open to each other in the vicinity of the sealing material 10 ( 15 and 15 are formed, and the enlarged space E in which the internal space S is enlarged is formed by the space enlarged wall parts 15 and 15. As shown in FIG. Also, as shown in FIG. 1 , in the region X1 , the first electrode substrate 2 and the second electrode substrate 6 are parallel to each other with a separation distance L1 that is slightly larger than the thickness of the semiconductor layer 4 . prolong it

Also, at this time, as shown in FIG. 4 , the electrolyte 11 dropped at a predetermined interval is gradually stretched in the advancing direction as the photoelectrode 5 and the counter electrode 8 move between the rollers R and R. It is coated on the entire semiconductor layer 4 while closely adhering to the first electrode substrate 2 and the second electrode substrate 6 while excluding air with surface tension on the surface and vicinity of the semiconductor layer 4 .

In addition, the electrolyte 11 is a total volume smaller than the volume of the interior space S formed by the first electrode substrate 2 , the second electrode substrate 6 , and the sealing material 10 , and the voids formed in the semiconductor layer 4 . loaded by capacity. Accordingly, the stretched electrolyte 11 stops in the middle of the enlarged space E formed by the space enlarged wall portion 15 , and hardly penetrates into the enlarged space E and stays in the vicinity of the semiconductor layer 4 . As a result, the sealing material 10 and the electrolyte solution 11 are separated, and the non-contact portion N (see FIG. 1 ) in which the electrolyte solution 11 does not contact the sealing material 10 is formed.

(V) <Sealing process>

After the electrolytic stretching step, in the sealing step, the photoelectrode 5 and the counter electrode 8 are adhered by heating the portion where the sealing material 10 is disposed, and as shown in FIG. 4 , the photoelectrode 5 is opposed to the photoelectrode 5 . In the direction intersecting the conveyance direction (arrow L1 direction) of the electrode 8, it adhere|attaches by the ultrasonic welding apparatus 50, and 1 A of solar cells shown in FIG. 1 are obtained.

As described above, according to the solar cell 1A shown in FIG. 1 , the electrolyte 11 is disposed between the first electrode substrate 2 and the second electrode substrate 6 in the region X1 in the expanded space E. While keeping it in close contact with it so that it does not flow, it is separated as much as possible so as to form a non-contact portion N of the electrolyte 11 in the sealing material 10 . Therefore, the effect that the electrolytic solution 11 can suppress the deterioration of the sealing material 10 as much as possible, thereby providing the solar cell 1A which can maintain high performance over a long period of time is acquired.

In addition, in the conventional solar cell, since the resin substrates P1 and P2 were formed of a flat plate-like material, considering that the electron transport resistance by the electrolyte 11 may increase, the resin substrates P1 and P2 ) was suppressed to tens of micrometers or less. In other words, since there was a problem that the performance of the battery significantly decreased when the gap between the resin substrates P1 and P2 was widened, conventionally, the distance between the resin substrates P1 and P2 was limited to about 30 μm. . Accordingly, the wiring member or the like inserted between the resin substrates P1 and P2 was also limited to a range accommodated in the distance between the resin substrates P1 and P2.

On the other hand, according to the solar cell 1A, as shown in FIG. 1 , while forming the region X1 where the electrolyte 11 is disposed as thin as possible, the outer ends 2p and 6p where the sealing material 10 is disposed. The separation distance L2 may be adopted to be 20 times or more larger than the distance L1 between the first electrode substrate 2 and the second electrode substrate 6 in the region X1 (however, in FIG. 1 ). is a schematic diagram, so the distance of L2 is not indicated to be 20 times or more of the distance of L1), the current collecting wiring 20 with a large cross-sectional area in the enlarged space E in the sealing material 10 or adjacent to the sealing material 10 can be placed. Therefore, the effect that it can be set as the high-quality solar cell 1A with reduced resistance of the wiring 20 is acquired.

Further, the cross-sectional shape of the wiring 20 is long and thin, and thick in the direction between the first electrode substrate 2 and the second electrode substrate 6, and the direction intersecting it (the sealing materials 10 and 10). direction) so as to be thinner. Therefore, it is easy to be embedded in the sealing material 10, and the area used as the effective area for power generation in the semiconductor layer 4 can be taken as wide as possible, and the effect that the photoelectric conversion efficiency can be raised as much as possible is acquired.

Further, by making the thickness (height in the vertical direction) of the sealing material 10 as large as possible and making the thickness 200 µm or less, the power generation in the semiconductor layer 4 due to an increase in dead space around the sealing material 10 The effect of being able to prevent causing a fall of an effective area is acquired.

In the solar cell 1A, a semiconductor layer 4 having low conductivity is interposed in a portion where the conductive film 3 and the conductive film 7 are adjacent to each other, and a first electrode substrate 2 is provided in other portions. and the second electrode substrate 6 are bent in a direction to be spaced apart from each other and formed in a direction to be gradually spaced apart. Therefore, the effect that the solar cell 1A with a low possibility of a short circuit can be obtained is acquired even if it does not interpose the separator containing a nonwoven fabric etc. between the electrically conductive film 3 and the electrically conductive film 7 .

Moreover, the effect that it can be set as 1 A of low-cost solar cells which abbreviate|omitted the cost required for a separator and the process of interposing a separator is acquired. In addition, the separator may be interposed between the photoelectrode 5 and the counter electrode 8 .

Moreover, since the electrolyte solution 11 filled in the internal space S can be made to a minimum, the effect that 1 A of solar cells which suppressed the manufacturing cost can be provided is acquired.

Moreover, in the manufacturing method of the solar cell 1A of this invention of the said embodiment, as shown in FIG. 4, before sealing between the photoelectrode 5 and the counter electrode 8, the electrolyte solution ( 11) is dropped, and thereafter, the photoelectrode 5 and the counter electrode 8 are joined together. In addition, the electrolyte solution 11 used at that time does not overflow from the internal space S. Therefore, in the production of the solar cell 1A, it is not necessary to place the bonded photoelectrode 5 and the counter electrode 8 in a vacuum atmosphere, and the photoelectrode 5 and the counter electrode 8 are bonded together. Since there is no immersion in the electrolytic solution 11 in the solar cell 1A, the operation of wiping the electrolytic solution 11 on the outer surface of the solar cell 1A can be omitted. Therefore, the effect that the solar cell 1A can be manufactured by simplifying a manufacturing process without using expensive vacuum equipment is acquired.

Moreover, according to the manufacturing method of the solar cell 1A of the said embodiment, the lamination|stacking process and the electrolyte solution extending|stretching process can be performed simultaneously, pressing the photoelectrode 5 and the counter electrode 8 with rollers R and R. .

Further, in this method, while sending each manufacturing process in one direction, the outer ends 2p and 6p extending in the longitudinal direction (arrow L direction) are adhered by the sealing materials 10, 10... to the sealing material 10 . The sealing in the intersecting direction can be sealed and cut by performing ultrasonic welding or the like at an arbitrary position from the tip of the solar cell 1A. That is, by forming the photoelectrode 5 and the counter electrode 8 in a band shape and conveying the photoelectrode 5 in the longitudinal direction while manufacturing the solar cell 1A, so-called Roll to Roll manufacturing, the photoelectrode ( 5) The advantageous effect that the solar cell 1A can be manufactured extremely simply, efficiently and quickly without considering the bonding position of the counter electrode 8 is acquired.

In addition, in the said embodiment, although 1 A of solar cells were set as the structure using the resin base material P1, P2 which has flexibility for both the 1st electrode substrate 2 and the 2nd electrode substrate 6, this invention is not limited to the configuration of this embodiment. That is, as shown in FIG. 6 , even if a resin substrate having flexibility is applied only to either one of the first electrode substrate 2 and the second electrode substrate 6 , the expanded space E and the sealing material 10 are A non-contact portion N may be formed. Accordingly, approximately the same actions, functions and effects as those described above are obtained.

In addition, in the said embodiment and its modification, although the semiconductor layer 4 is a structure formed into a film so that it may not contact the sealing material 10, this invention is not limited to such a structure. That is, the semiconductor layer 4 may be arranged so as to be in contact with the sealing material 10 , as long as the electrolyte 11 is disposed at a distance from the sealing material 10 through the expanded space E .

Moreover, in the said embodiment, although the wiring 20 has the structure embedded in the sealing material 10, this wiring 20 may be arrange|positioned in the expanded space E. As shown in FIG. Even when the wiring 20 is disposed in the enlarged space E, the resistance of the wiring 20 is increased by increasing the thickness of the wiring 20 in the direction between the first electrode substrate 2 and the second electrode substrate 6 . The effective area for power generation of the semiconductor layer 4 (that is, the surface area of the semiconductor layer 4 in a plan view) is increased as much as possible by reducing the thickness of the semiconductor layer 4 and reducing the thickness in the direction between the sealing materials 10 and 10. The effect that can be obtained is obtained.

Further, in the above embodiment, the present invention has been described using an example in which the electrolytic solution 11 is disposed between the photoelectrode 5 and the counter electrode 8. However, the present invention is suitable even if a gel or solid electrolyte is used. can be carried out In the case of using a gel or solid electrolyte, a gel or solid electrolyte is disposed on the semiconductor layer 4, and after that, the photoelectrode 5 and the counter electrode 8 are laminated, followed by heating and pressurization. Thus, the gel or solid electrolyte may be permeated into the semiconductor layer 4 .

Further, in the above embodiment, the outer ends intersecting the outer ends 2p and 6p on which the sealing materials 10 and 10 are disposed are sealed by ultrasonic welding, but it is properly sealed by a sealing method other than ultrasonic welding. it may be

In addition, although the above embodiment described the configuration in which the semiconductor layers 4 are arranged in two rows in the width direction of the first electrode substrate 2 and formed into a film as an example, the configuration of the present invention is not limited to such a configuration, The semiconductor layer 4 may be formed into a film in one row or three or more rows.

1A: Solar cell (photoelectric conversion element)
2: first electrode substrate
3: conductive film
4: semiconductor layer
5: photoelectrode
6: second electrode substrate
7: conductive film
8: counter electrode
11: electrolyte (electrolyte)
15: space expansion wall
15a: slope
E: magnification space
L1, L2: spacing dimension
N: non-contact part
X1: region where the semiconductor layer is formed

Claims (11)

A counter electrode comprising a photoelectrode in which a semiconductor layer is formed on a first electrode substrate, a second electrode substrate facing the first electrode substrate, a sealing material sealing between the photoelectrode and the counter electrode; An electrolyte disposed on the inside,
At least one of the first electrode substrate and the second electrode substrate is provided with a space expanding wall portion that enlarges the distance between the surfaces of the first electrode substrate and the second electrode substrate facing each other, and the sealing material to form an enlarged space on the inner side of the
The electrolyte is maintained between the first electrode substrate and the second electrode substrate inside the enlarged space,
A photoelectric conversion element, wherein a non-contact portion not in contact with the electrolyte is formed in the sealing material. The photoelectric device according to claim 1, wherein a wiring arranged on at least one electrode substrate selected from the group consisting of a first electrode substrate and a second electrode substrate is provided in the expanded space or the sealing material. conversion element. The photoelectric conversion element according to claim 1 or 2, wherein the space expanding wall portion has an inclined surface that gradually enlarges the separation dimension toward the sealing material. The difference between the thickness dimension of the sealing material and 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 30 µm or more and 200 µm A photoelectric conversion element characterized by the following. The photoelectric conversion element according to claim 2, wherein a height of the sealing material in a vertical direction is larger than a height of the wiring in a vertical direction. The photoelectric conversion element according to claim 1 or 2, wherein a volume of the enlarged space is greater than 1/3 of a volume of the electrolyte. The photoelectric conversion element according to claim 1 or 2, wherein a sealing material deterioration preventing member is provided between the electrolyte and the sealing material. An electrolyte disposing process of disposing an electrolyte in a semiconductor layer on a first electrode substrate provided in the photoelectrode;
a sealing material arrangement 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;
a lamination process of laminating a counter electrode provided with a second electrode substrate on the photoelectrode;
The photoelectrode and the counter electrode are pressed, and the electrolyte is held between the first electrode substrate and the second electrode substrate while arranging the semiconductor layer, and the first electrode substrate in the vicinity of the sealing material; an electrolyte stretching step of forming a space expanding wall portion that enlarges the separation dimension of the second electrode substrate and forming a non-contact portion not in contact with the electrolyte in the sealing material;
A sealing process of sealing the photoelectrode and the counter electrode
A method for manufacturing a photoelectric conversion element comprising: The method for manufacturing a photoelectric conversion element according to claim 8, wherein the lamination step, the electrolyte stretching step, and the sealing step are simultaneously performed by pressing the photoelectrode and the counter electrode. The said space expansion wall part uses a flexible resin base material for at least one of the said 1st electrode board|substrate and the said 2nd electrode board|substrate, The said photoelectrode and the said counter electrode are pressurized according to claim 8 or 9. A method for manufacturing a photoelectric conversion element, characterized in that it is formed by deforming the flexible resin substrate when performing the process. The method for manufacturing a photoelectric conversion element according to claim 8, wherein the pressing is performed using an elastically deformable roller.

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