JP5369353B2 - Electrode provided with electrode protection partition and dye-sensitized solar cell provided with the electrode - Google Patents

Abstract

To provide a technique, in manufacturing dye-sensitized solar cells, for preventing degradations in their photovoltaic performance and durability due to sealant-derived electrode contamination.A photoelectrode characterized in that an electrode-protection partition wall is formed along a circumference of an oxide semiconductor layer formed on a transparent conductive substrate and a position for forming a partition wall made of a sealant is reserved outside the electrode-protection partition wall; or a counter electrode comprising an electrode-protection partition wall, characterized in that the electrode-protection partition wall is so positioned on the counter electrode that, when the partition wall is laminated to a photoelectrode via a sealant, the electrode-protection partition wall assumes a position over a region of the photoelectrode between the sealant partition wall and an oxide semiconductor layer; and a dye-sensitized solar cell comprising either of the aforementioned electrodes.

Description

  The present invention relates to an electrode suitable for a dye-sensitized solar cell and a dye-sensitized solar cell provided with the electrode.

  Dye-sensitized solar cells have attracted widespread attention worldwide since they are less expensive than Si-based solar cells.

  In a dye-sensitized solar cell, a transparent conductive substrate is used as a substrate. However, since the resistance value of the transparent conductive substrate itself is limited, an appropriate module design is required. When modularizing dye-sensitized solar cells, the current collector material, sealing technology, and patterning occupy important elements, which greatly affect module performance and durability.

  In order to realize high performance of the module, it is necessary to make the pattern dense, and therefore it is desirable that the distance between the sealing portion and the electrode portion is narrow.

JP 2006-261090 A

  However, if the sealing material and the electrode part are adjacent, (i) electrode contamination due to the flow of the sealing material due to the pressure treatment at the time of bonding the counter electrode, and contamination due to low molecular weight substances contained in the sealing material, etc. are problematic. (Ii) the low molecular weight material [for example, various monomers and solvents for appropriately dispersing the monomer that is a raw material of the polymer (resin) or the resin monomer or imparting viscosity suitable for screen printing] As a result of research conducted by the present inventors, it has been found as a new finding that the contamination form due to the contamination varies greatly depending on the composition and use method of the sealing material.

  Therefore, it is an object of the present invention to provide a technique for preventing a decrease in power generation performance and a decrease in durability due to electrode contamination derived from the sealing material as described above based on such new knowledge.

  According to a first aspect of the present invention, a partition wall for electrode protection is formed along the periphery of an oxide semiconductor layer formed on a transparent conductive substrate, and a partition wall made of a sealing material is disposed outside the partition wall for electrode protection. This is a photoelectrode characterized in that a predetermined site is secured.

  A second aspect of the present invention is a counter electrode provided with an electrode protection partition, and the electrode protection partition is bonded to the photoelectrode with an encapsulant and the sealing material partition and the oxide semiconductor. The counter electrode is characterized in that it is disposed on the counter electrode so as to be positioned above the photoelectrode region between the layers.

  3rd aspect of this invention is a dye-sensitized solar cell provided with the photoelectrode of said 1st aspect.

  4th aspect of this invention is a dye-sensitized solar cell provided with the counter electrode of said 2nd aspect.

  According to a fifth aspect of the present invention, there is provided a dye sensitizing method characterized in that a partition wall made of a sealing material is formed outside the electrode protection partition wall of the photoelectrode of the first aspect, and then a counter electrode is bonded. It is a manufacturing method of a solar cell.

  The sixth aspect of the present invention is the method for producing a dye-sensitized solar cell by forming a partition wall made of a sealing material on a photoelectrode and then bonding the counter electrode together. When the counter electrode having the electrode protection partition wall is used and the photoelectrode and the counter electrode are bonded together, the electrode protection partition wall is positioned above the photoelectrode region between the partition wall of the sealing material and the oxide semiconductor layer. Thus, a method of manufacturing a dye-sensitized solar cell, wherein the partition wall of the sealing material is formed on a photoelectrode.

  By using the photoelectrode or counter electrode provided with the electrode protecting partition wall of the present invention, the electrode protecting partition wall is interposed between the oxide semiconductor layer on the photoelectrode and the partition wall of the sealing material, thereby providing a sealing material. It is possible to prevent a decrease in power generation performance and durability due to electrode contamination derived from the origin.

FIG. 1A is a schematic view showing a cross section of a photoelectrode provided with an electrode protection partition and a counter electrode. This corresponds to the first aspect of the present invention. FIG. 1B is a schematic view showing a cross section of a photoelectrode and a counter electrode provided with an electrode protection partition. This corresponds to the second aspect of the present invention. FIG. 2 shows a printed pattern including an electrode protection partition. In this figure, in addition to the electrode protection partition, an insulating layer for protecting the current collecting wiring is also shown. FIG. 3 is a diagram showing a production procedure of a photoelectrode for producing a dye-sensitized battery indicated by test numbers 1 to 4 in Example 2.

1. About the first aspect of the present invention In the first aspect of the present invention, an electrode protection partition is formed along the periphery of the oxide semiconductor layer formed on the transparent conductive substrate, and the electrode protection partition is formed outside the electrode protection partition. Further, a photoelectrode characterized in that a partition arrangement planned portion made of a sealing material is secured is an object.

(A) Electrode protection partition wall The electrode protection partition wall is a partition wall formed along the periphery of the oxide semiconductor layer, and the flow of the sealing material itself by the pressure treatment at the time of bonding the counter electrode, or sealing It is a partition for preventing contamination of the electrode by low molecular weight substances contained in the material [see FIG. 1A].

  In addition to the partition made of a sealing material for separating the photoelectrode and the counter electrode, it is novel to provide such an electrode protection partition as far as the inventors of the present application know. For example, Patent Document 1 discloses that a spacer material may be included in a resin or rubber used as a sealing material for sealing a peripheral portion between substrates (Patent Document 1, paragraph numbers 0051 to 0052). Is intended to be used for the purpose of adjusting the interval between the substrates, and the purpose is completely different. The sealing material referred to in Patent Document 1 corresponds to the partition wall made of the sealing material referred to in the present invention. The spacer mentioned in the above is considered to be one particle component in the sealing material, whereas the electrode protecting partition wall of the present invention is not one particle in the composition but is located outside the partition wall made of the sealing material. Therefore, the positional relationship is also different.

  The electrode protection barrier ribs are formed along the periphery of the oxide semiconductor layer. However, the electrode protection barrier ribs can be formed continuously so as to cover the entire periphery. For example, it may be a slit-shaped partition wall (see the slit-shaped electrode protection partition wall of Example 2). However, it is preferable to cover the entire periphery as much as possible because the electrode can be more effectively protected.

  As a material for the electrode protection partition, at least the surface thereof is preferably composed of an insulating material such as glass, ceramics, or a resin such as a rubber-like resin. From the viewpoint of protecting the semiconductor layer, glass frit and resin are more preferable.

  As the shape of the partition wall for electrode protection, it can be said that the higher the height, the better. However, at least 20% of the distance between the electrodes within a range not exceeding the distance between the electrodes is due to contamination due to the flow of the sealing material. It is preferable from the viewpoint of protecting the oxide semiconductor layer, and more preferably 30% or more of the distance between the electrodes.

  Furthermore, from the viewpoint of more effectively dealing with electrode contamination due to low molecular weight substances contained in the sealing material, the electrode protection partition is made of rubber-like resin, and the height slightly exceeding the distance between the electrodes ( For example, when the protective partition is formed at 1.0 to 2.0 times and the two electrodes are bonded to each other, it is preferable to act as a packing that makes the space between the electrodes airtight.

  The width of the partition wall for electrode protection is preferably as narrow as possible in terms of obtaining an effective power generation area, preferably 0.3 mm or less, more preferably 0.2 mm or less.

  The electrode protection partition is formed along the periphery of the oxide semiconductor layer of the photoelectrode (see FIG. 1A). The smaller the distance from the oxide semiconductor layer of the electrode protection partition, the more effective power generation is. Although it is preferable in terms of increasing the area, in the case of forming by a printing technique such as screen printing, it is usually preferable to leave an interval of about 0.2 mm due to restrictions from the viewpoint of printing accuracy.

  Further, as already described, a partition arrangement planned portion made of a sealing material is secured outside the electrode protection partition. The smaller the distance to the partitioning arrangement planned site made of the sealing material, the better in terms of increasing the effective power generation area, and it is preferable to form the distance substantially zero. Further, the electrode protection partition wall may partially overlap with the partition wall made of a sealing material.

  The electrode protection partition can be easily produced by applying a screen printing method or the like. In particular, it can be more easily produced by simultaneous printing with an insulating layer as described later.

(B) The photoelectrode of the present invention includes components that are usually used, such as a transparent conductive substrate, an oxide semiconductor layer, and a spectral sensitizing dye, as components other than the electrode protection partition.

(A) Transparent conductive substrate As the transparent conductive substrate, titanium oxide, zinc oxide (which may be doped with antimony or aluminum), indium oxide (tin) as a transparent conductive film on a transparent substrate such as transparent glass or transparent resin film Alternatively, those formed with a film of tin oxide (which may be doped with antimony or fluorine) may be preferably used.

(B) Oxide semiconductor layer A layer formed on the transparent conductive substrate and made of a metal oxide semiconductor film. As the metal oxide semiconductor, known porous materials such as titanium oxide, zinc oxide, tin oxide, tin-doped indium oxide, zirconium oxide, and magnesium oxide can be used. Spin coating, spraying, dipping Can be formed on the transparent conductive substrate by a method, a screen printing method, a doctor blade method, an ink jet method, etc., but from the viewpoint of ease of operation, a spin coating method, a spray method, a dipping method are screens from the viewpoint of mass production. The printing method is preferred.

(C) Spectral sensitizing dye As the spectral sensitizing dye, various metal complexes and organic dyes having absorption in the visible region and / or the infrared light region can be used. A method in which an oxide semiconductor thin film such as titanium is immersed in a dye solution at a predetermined temperature (dipping method, roller method, air knife method, etc.) or a method in which a dye solution is applied to the surface of an oxide semiconductor layer (wire bar method, application method) The metal oxide semiconductor film is adsorbed by a spin method, a spray method, an offset printing method, a screen printing method, or the like.

(D) Others It is preferable that current collecting wiring is applied to the photoelectrode in an arbitrary pattern. The terminal portion can be easily manufactured by using a printing technique such as screen printing as a part of the current collecting wiring pattern. Further, the current collecting wiring is preferably covered with an insulating layer in order to protect it from the electrolyte. As the insulating layer, glass frit or resin can be used, and among these, glass frit is preferable in terms of durability and insulation.

2. About the second aspect of the present invention The second aspect of the present invention is a counter electrode provided with an electrode protection partition, which is sealed when the electrode protection partition is bonded to the photoelectrode with a sealing material. A counter electrode that is disposed on the counter electrode so as to be positioned above the photoelectrode region between the partition wall of the stopper and the oxide semiconductor layer is an object.

(A) Electrode-protecting partition wall The electrode-protecting partition wall in this embodiment is also included in the flow of the sealing material itself by the pressure treatment at the time of bonding the counter electrode, or the sealing material, as in the electrode protection partition wall in the first embodiment. This is a partition wall for preventing contamination of the electrode by low molecular weight substances, etc., and is basically the same as that described in the electrode protection partition wall of the first aspect.

  However, it differs in that it is arranged not on the photoelectrode but on the counter electrode as in the first aspect of the present invention. That is, the electrode protection partition wall in this embodiment is positioned on the counter electrode so as to be positioned above the photoelectrode region between the partition wall of the sealing material and the oxide semiconductor layer when being bonded to the photoelectrode with the sealing material. Placed in. In other words, in this embodiment, the electrode protection partition is disposed in a portion corresponding to the counter electrode portion located immediately above the electrode protection partition disposed on the photoelectrode in the first embodiment [see FIG. 1B. ].

(B) Counter electrode The counter electrode of the present invention is not particularly limited as long as it has corrosion resistance to the corrosive component in the electrolyte to be sealed between the counter electrode and the photoelectrode, but titanium, stainless steel, conductive Glass etc. are illustrated, and among these, titanium is more preferable from the viewpoint of electrical conductivity and thermal expansion.

3. Third and fifth aspects of the present invention The third aspect of the present invention is directed to a dye-sensitized solar cell provided with the photoelectrode of the first aspect, and the fifth aspect of the present invention is the above-described first aspect. The present invention is directed to a method for producing a dye-sensitized solar cell, in which a partition wall made of a sealing material is formed outside an electrode protection partition wall of a photoelectrode according to one aspect, and then a counter electrode is bonded.

  By having an electrode protection partition in the photoelectrode, contamination by the sealing material itself or low molecular weight substances contained in the sealing material is reduced, and a dye-sensitized solar cell with little deterioration in performance such as conversion efficiency is obtained. Can do.

  First, a partition wall of a sealing material is formed on the transparent conductive substrate on which the photoelectrode of the first aspect is formed. It can be easily formed by using a printing technique such as screen printing. The sealing material is not particularly limited as long as it has corrosion resistance against the corrosive component in the electrolyte, but thermoplastic resin, thermosetting resin, ultraviolet curable resin, electron beam curable resin, metal, rubber, etc. As an example, at least the surface needs to be electrically insulating, and when the sealing material is conductive, the surface is covered with an electrically insulating material such as various resins or rubber.

  Subsequently, a photoelectrode and a counter electrode are bonded together through the sealing material. At this time, care should be taken so that the electrodes are arranged in parallel by applying a uniform pressure.

  When using a photocurable resin as the sealing material, the sealing material is cured by light irradiation (ultraviolet irradiation) from the photoelectrode side.

A constant distance is maintained between the photoelectrode and the counter electrode via the partition wall of the sealing material, but the electrolyte is sealed here. Examples of the electrolyte include an electrolytic solution containing a redox electrolyte such as an I ₃ ⁻ / I ⁻ system, a Br ₃ ⁻ / Br ⁻ system, and a quinone / hydroquinone system.

4). About 4th and 6th aspect of this invention The 4th aspect of this invention is directed to the dye-sensitized solar cell provided with the counter electrode of said 2nd aspect, and the 6th aspect of this invention is a photoelectrode. In the method for producing a dye-sensitized solar cell by forming a partition wall made of a sealing material on the substrate and then bonding the counter electrode, the counter electrode having the electrode protection partition wall of the second aspect is used as the counter electrode, When the electrode and the counter electrode are bonded together, the partition wall of the sealing material is placed on the photoelectrode so that the partition wall for electrode protection is positioned above the photoelectrode region between the partition wall of the sealing material and the oxide semiconductor layer. The present invention is directed to a method for producing a dye-sensitized solar cell.

  By having an electrode protection partition at the counter electrode, contamination by the sealing material itself or low molecular weight substances contained in the sealing material is reduced, and a dye-sensitized solar cell with little deterioration in performance such as conversion efficiency can be obtained. it can.

  Regarding the manufacturing method of the sixth aspect, the above item 3. In the description of the fifth aspect of the present invention, the counter electrode provided with the partition wall for electrode protection according to the second aspect of the present invention is used as the counter electrode, and the electrode for protecting the electrode according to the first aspect of the present invention is used in principle. What is necessary is just to replace with the photoelectrode which does not have the partition wall for electrode protection instead of the photoelectrode provided with the partition wall.

  However, also in the embodiment of the present invention, the photoelectrode of the first embodiment of the present invention may be used together as the photoelectrode when the following conditions are satisfied.

    i) The total height of the electrode protection partition wall of the counter electrode and the electrode protection partition wall of the photoelectrode does not exceed the distance between the electrodes, and when the counter electrode is bonded to the photoelectrode through the partition wall of the sealing material, When the barriers for protecting both electrodes do not collide with each other and do not hinder the bonding.

    ii) Structure in which the electrode protection partition walls are alternately arranged when the counter electrode partition walls and the electrode protection partition walls of the photoelectrode are bonded to the photoelectrode via the sealing material partition walls. If it does not become a hindrance to pasting.

iii) One or both of the partition walls for protecting both electrodes are made of rubber-like resin, and even if the total height slightly exceeds the distance between the electrodes, the counter electrode is attached to the photoelectrode via the partition wall of the sealing material. If it is not an obstacle to match,
iv) In other cases where there is no obstacle to the bonding when the counter electrode is bonded to the photoelectrode via the partition wall of the sealing material.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to these.

The typical example of preparation of the dye-sensitized solar cell by this invention is shown below.
1. Production of photoelectrode-Formation of titanium oxide layer Using a screen printer (MT-320TV manufactured by Microtech), a titanium oxide paste (catalyst conversion PST-18NR) having a primary particle size of 20 to 30 µm is 120 mm x 120 mm. Screen printing was performed on a conductive glass substrate (FTO conductive film, manufactured by Nippon Sheet Glass) and dried. This process was repeated until a predetermined film thickness was obtained, and then a titanium oxide paste (catalyst conversion PST400C) having a particle size of about 400 μm was screen-printed and dried. Thereafter, the substrate was transferred to a muffle furnace (FUW252PA manufactured by Advantech) and baked at 500 ° C. for 30 minutes to form a titanium oxide layer. The thickness of the titanium oxide after firing was about 12 μm.

-Formation of current collecting grid Next, silver paste was applied onto the substrate in a grid by screen printing, dried at 160 ° C for 12 minutes, and then fired in a muffle furnace at 500 ° C for 30 minutes to obtain current collecting wiring. It was.

  The current collecting grid may be formed before the titanium oxide layer is formed.

・ Simultaneous formation of current collector grid protection layer (insulating layer) and electrode protection barrier (see Fig. 2)
Next, a glass frit paste is applied on the substrate by screen printing, so that the electrode protection partition wall having a width of 0.2 mm and a height of 0.01 mm around the insulating layer and the oxide semiconductor layer of the current collecting grid. Were simultaneously formed, dried at 160 ° C. for 12 minutes, and then baked in a muffle furnace at 500 ° C. for 30 minutes. FIG. 2 shows the print pattern used.

  The insulating layer and the electrode protection partition may be formed before the titanium oxide layer is formed.

-Dye adsorption Next, the substrate on which the insulating layer was formed was immersed in a ruthenium organic complex dye solution and allowed to stand for 16 hours to adsorb the dye to the titanium oxide layer.

b. Production of counter electrode-Outline shape machining of titanium plate A 0.2 mm thick pure titanium plate was cut into a prescribed shape (120 mm x 120 mm) by wire electric discharge machining.

-Formation of platinum catalyst layer Next, a platinum catalyst layer was formed on the titanium plate by electroplating.

c. Assembly-Sealing material application | coating The ultraviolet curable resin for sealing was apply | coated by screen printing on each photoelectrode.

-Bonding Next, the counter electrode was disposed so as to face the photoelectrode in the up and down direction, and bonded to face each other.

-Curing of encapsulant Next, ultraviolet rays were irradiated from the photoelectrode side (3000 mJ / cm ² , ECS-601G-3 manufactured by iGraphic) to cure the encapsulant (distance between electrodes: about 30 μm).

-Electrolyte solution injection | pouring Then, electrolyte solution was inject | poured from the electrolyte solution injection hole of the module using the vacuum injection apparatus (LC-35 by Ayumi Industry).

-Sealing of injection | pouring hole Then, electrolyte solution injection | pouring hole was sealed using ultraviolet curable resin.

  d. The photoelectrode of the obtained dye-sensitized solar cell was protected by the electrode protection partition wall, and contamination due to the flow of the sealing material itself was not observed.

  Below, it demonstrates about the bad influence of the sealing material with respect to the performance of a dye-sensitized solar cell, and the point which can influence this influence by this invention.

A. Preparation of dye-sensitized solar cell for evaluation The following procedures (1), (2), (3), (4-1), (5-1) or (1), (2), (3), (4 -2) By producing dye-sensitized solar cells having test numbers 1 to 4 in (5-2) and comparing their performance, the effect on the battery performance due to the presence or absence of the sealing material, and the electrode protection of the present invention The effect of partition walls on battery performance was evaluated.

  In FIG. 3, the relationship between the preparation procedure of a photoelectrode and the dye-sensitized solar cell of the said test numbers 1-4 is shown.

(1) Titanium oxide paste [Product name: PST-18NR, PST-400C, manufactured by Catalytic Chemical Co., Ltd.] on a transparent conductive substrate [glass plate with SnO ₂ film, 20 mm × 120 mm × 4 mm, manufactured by Nippon Sheet Glass Co., Ltd.] Was applied in an area of (5 mm × 96.4 mm = 4.82 cm ² ) and dried at 150 ° C. for 10 minutes. As a result, a titanium oxide film having a thickness of about 13 μm [a value after baking at 500 ° C. after forming the partition walls for electrode protection in (2) below] was formed.

  Twelve such transparent conductive substrates on which a titanium oxide layer was formed were produced [see FIG. 3A].

  (2) Next, an electrode protection partition wall made of glass frit (product name glass paste 1115A2 paste, manufactured by Asahi Glass Co., Ltd.) was formed around the titanium oxide layer produced above, and then fired at 500 ° C. for 20 minutes ( Simultaneous firing of titanium oxide and glass frit). A screen printing method was used to form the partition walls.

    As the electrode protection barrier ribs, six glass frit barrier ribs are continuously formed around the electrodes (continuous electrode protection barrier ribs), and glass frit barrier ribs are intermittently formed around the electrodes. 6 sheets of slits (slit electrode protection partition walls) were prepared.

    The continuous electrode protection partition has an inner side on the transparent conductive substrate separated by 0.2 mm from each side of the titanium oxide film, a width of 1 mm, and a height of about 25 μm. Further, the length of the long side (between the outer side and the outer side) was 98.8 mm, and the length of the short side (between the outer side and the outer side) was 7.4 mm [see FIG. 3B].

    The shape of the slit-shaped electrode protection partition is such that five long-side partitions are removed so as to leave four isolated 6-mm partitions for each of the two long-side portions of the continuous electrode protection partition. It corresponds to the shape. The separation between the partition including the short side and the isolated partition was 13 mm, and the adjacent spacing between the four isolated partitions was 13 mm (see FIG. 3E).

  (3) Next, each of the transparent conductive substrates on which the titanium oxide film and the electrode protection partition walls were formed as described above was transferred to the dye [N719: cis-bis (isothiocyanato) -bis (2,2′-bipyridine-4, 4′-carboxylate) ruthenium (II) bis (tetra-n-butylammonium)] in an acetonitrile / t-butanol solution containing 0.3 mM in concentration at 25 ° C. for 18 hours to form a titanium oxide film. The dye was adsorbed, washed with acetonitrile, and then dried with an air blower to obtain 6 photoelectrodes each having a continuous electrode protection partition and 6 photoelectrodes having a slit electrode protection partition.

  (4-1) Among the photoelectrodes on which the dye has been adsorbed, sealing is made of an ultraviolet curable resin for each of three photoelectrodes having a continuous electrode protection partition and three photoelectrodes having a slit electrode protection partition. The partition walls of the material were screen-printed [see FIG. 3 (c) for photoelectrodes having continuous electrode protection partition walls, and FIG. 3 (f) for photoelectrodes having slit electrode protection partitions], and the gap between the electrodes was about 40 μm. The counter electrode (titanium plate with platinum, 110 × 15 × 0.2 mm) was bonded so that the ultraviolet rays (high pressure mercury lamp, orc handy UV300, model: orc HSL-300 / B-FM) were applied at 1 ° C. for 10 minutes. Irradiation was performed to cure the encapsulant, and each cell was obtained.

  It was confirmed that the encapsulant material itself was made with care so as not to flow into the titanium oxide film, and that it did not actually flow in.

  (5-1) Next, for each cell obtained in (4-1), an electrolytic solution (0.1 M guanidine dithiocyanate, 0.1 M iodine, 0.5 M t-butylpyridine, 0.6M dimethylpropylimidazolium iodide, solvent: 3-methoxypropionitrile) was injected, and then the injection port was irradiated with ultraviolet curable resin at 1 ° C. for 3 minutes with ultraviolet light (high pressure mercury lamp, orc handy). UV300, model: orc HSL-300 / B-FM) and sealed.

  Among the obtained dye-sensitized solar cells, three having a continuous electrode protection partition were designated as test number 2, and three having a slit-like electrode protection partition were designated as test number 4 (see FIG. 3).

  (4-2) On the other hand, among the photoelectrodes on which the dye is adsorbed, the remaining three photoelectrodes each having a continuous electrode protection partition and a photoelectrode having a slit electrode protection partition Resin sheet having a height of about 40 μm in the outer region of the protective partition [Himiran (trademark), because the shape and size are used instead of the partition of the sealing material, the same as the partition of the sealing material The shape and size were used], and both electrodes were fixed with clips together with the counter electrode. The resin sheet was used as a substitute for the partition wall of the sealing material described in (4-1) above, and similarly used to perform the function of insulating both electrodes. Therefore, it is arranged to be the same as the position of the partition wall of the sealing material in the above (4-1) [Photo electrode having continuous electrode protection partition wall FIG. 3 (d), having slit electrode protection partition wall] For the photoelectrode, see the portion surrounded by the broken line in FIG.

  (5-2) Next, an electrolytic solution [same as described in (5-1) above] was injected into each cell obtained in (4-2) from the gap between the two electrodes using the capillary phenomenon. .

  Among the obtained control dye-sensitized solar cells, three having a continuous electrode protection partition were designated as test number 1, and three having a slit-like electrode protection partition were designated as test number 3.

B. Evaluation A. above. Performance evaluation was performed on the dye-sensitized solar cells (test numbers 1 to 4) produced as described above, and the results shown in Table 1 below were obtained.

  In the table, Voc means open circuit voltage, Jsc means short circuit current density, and FF means fill factor. The size referred to as the cell size means a titanium oxide coating area (96.4 mm × 5 mm).

  Moreover, the photoelectric conversion efficiency in a table | surface was measured on condition of the following.

That is, with a solar simulator (manufactured by Yamashita Denso Co., Ltd.), AM (air mass, atmospheric mass) 1.5, 100 mW / cm ² of simulated sunlight is irradiated, and short circuit current density, open circuit voltage, and fill factor (FF) are measured. The photoelectric conversion efficiency was calculated based on the following calculation formula (Formula 1).
(Formula 1)
Photoelectric conversion efficiency (%) =
100 × [(Short-circuit current density × Open circuit voltage × Curve factor) / (Irradiated solar energy)]
From the results of Table 1 above, it can be seen that the following has been demonstrated.

  a. By comparing Test No. 1 and Test No. 2 or Test No. 3 and Test No. 4, the photoelectric conversion efficiencies of the dye-sensitized solar cells of Test No. 1 and Test No. 3 that do not use the sealing material are respectively It turns out that it is higher than the photoelectric conversion efficiency of the dye-sensitized solar cell of the test number 2 and the test number 4 which uses the corresponding sealing material.

  This has shown that the photoelectric conversion efficiency fell by using the sealing material.

  This decrease is presumed that the gas emission component from the resin used as the sealing material had an adverse effect on the cell performance.

  b. By comparing test number 2 and test number 4, test number 2 using the continuous electrode protection partition tends to have higher photoelectric conversion efficiency than test number 4 using the slit electrode protection partition. I understand that there is.

  This has shown that the photoelectric conversion efficiency of a battery can be improved by providing an electrode protection partition.

  c. Although test number 2 has a continuous electrode protection partition, it is slightly lower than the photoelectric conversion efficiency of test number 1 that does not use the corresponding sealing material, and there is room for further improving the electrode protection effect. It shows that there is.

  For this purpose, for example, the height of the used continuous electrode protection partition wall (in Test Nos. 1 and 2, the distance between the electrodes is about 40 μm, and a height of about 25 μm corresponding to about 65% is adopted. The height of the resin is increased to a height closer to the distance between the electrodes, or instead of the glass frit used in this example, the elasticity of a rubber-like resin having an electrolytic solution resistance and a low gas emission during curing. By using a material as an electrode protection partition and setting its height slightly larger than the distance between the electrodes, when the two poles are bonded together, the space between the electrodes is made to act as an airtight structure. Thus, it is considered that the photoelectric conversion efficiency can be further improved by better blocking between the photoelectrode and the partition wall of the sealing material.

  By using the photoelectrode or counter electrode provided with the electrode protection partition wall of the present invention, it is possible to prevent contamination of the electrode when the photoelectrode and the counter electrode are sealed with the partition wall of the sealing material, so that the performance resulting from the manufacturing process This is advantageous for the production of a dye-sensitized solar cell that does not deteriorate.

Claims (10)

A photoelectrode for a dye-sensitized solar cell obtained by sealing a photoelectrode and a counter electrode with a partition made of a sealing material,
A partition wall for electrode protection is formed along the periphery of the oxide semiconductor layer formed on the transparent conductive substrate, and a partition arrangement planned portion made of a sealing material is secured outside the partition wall for electrode protection, A photoelectrode, wherein the height of the partition wall for electrode protection is less than the interelectrode distance between the counter electrode and the photoelectrode when bonded to the counter electrode, and is at least 20% or more of the interelectrode distance. 2. The photoelectrode according to claim 1, wherein the electrode protection partition is formed as a partition that is continuous over the entire circumference of the oxide semiconductor layer.   The photoelectrode according to claim 1, wherein at least a surface of the partition wall for electrode protection is formed of an insulating material. A counter electrode for a dye-sensitized solar cell obtained by sealing a photoelectrode and a counter electrode with a partition wall made of a sealing material,
An electrode protection partition is provided, and the electrode protection partition is positioned above the photoelectrode region between the partition wall of the sealing material and the oxide semiconductor layer when bonded to the photoelectrode by the sealing material. And the height of the partition wall for electrode protection is less than the interelectrode distance between the photoelectrode and the counterelectrode when bonded to the photoelectrode, and at least 20 of the interelectrode distance. % As a counter electrode. The counter electrode according to claim 4 , wherein the electrode protection partition is formed as a partition that is continuous over the entire circumference of the oxide semiconductor layer. The counter electrode according to claim 4 , wherein at least a surface of the partition wall for electrode protection is formed of an insulating material. According to claim 1, dye-sensitized solar cell having an optical electrode according to any of the three. Claim 4, 5, 6 dye-sensitized solar cell having a counter electrode according to any one of. A dye-sensitized solar cell comprising: a partition wall made of a sealing material formed outside the electrode protection partition wall of the photoelectrode according to any one of claims 1, 2, and 3 ; Production method. In the method for manufacturing a dye-sensitized solar cell by forming a partition wall made of a sealing material on a photoelectrode and then bonding the counter electrode, the electrode protection according to any one of claims 4 , 5 and 6 as a counter electrode. When the counter electrode provided with the barrier rib is used and the photoelectrode and the counter electrode are bonded together, the electrode protective barrier is positioned above the photoelectrode region between the barrier rib of the sealing material and the oxide semiconductor layer. A method for producing a dye-sensitized solar cell, comprising forming a partition wall of the sealing material on a photoelectrode.

Images