JP5095148B2 - Working electrode substrate and photoelectric conversion element - Google Patents

Description

  The present invention relates to an electrode substrate used for a photoelectric conversion element such as a dye-sensitized solar cell, and more particularly, to reduce the weight while maintaining the substrate strength, and to construct a large-area element having better power generation characteristics. The present invention relates to an electrode substrate and a photoelectric conversion element.

  Dye-sensitized solar cells are attracting attention as photoelectric conversion elements that can be obtained at low cost and have high photoelectric conversion efficiency, and have been proposed by a group of Gretzel et al. In Switzerland (for example, see Patent Documents 1 and 2 and Non-Patent Document 1). .

  As a general structure of this dye-sensitized solar cell, as shown in FIG. 5, titanium dioxide or the like is usually formed on a transparent conductive electrode substrate composed of a working electrode base material 102 and a transparent conductive layer 104. Forming a porous oxide semiconductor layer (hereinafter also referred to as a “porous film”) 105 made of a fine oxide semiconductor fine particle as a working electrode 108, on the other hand, a counter electrode substrate coated with a conductive layer 107 such as platinum 103 as a counter electrode 109, and a photosensitizing dye is supported on the porous film 105 of the working electrode 108, and oxidation is performed between the working electrode 108 and the counter electrode 109 and at least part of the porous film 105. The electrolyte 106 containing a reducing pair is filled. In this type of dye-sensitized solar cell 101, oxide semiconductor fine particles are sensitized by a photosensitizing dye that absorbs incident light such as sunlight (indicated as hν in FIG. 5), and converts light energy into electric power. It functions as a photoelectric conversion element.

By the way, as the transparent conductive electrode substrate used here, a transparent conductive layer 104 such as ITO or FTO is previously coated on the surface of the working electrode base material 102 made of glass by a technique such as vapor deposition, CVD, or sputtering. Is common.
However, when a large-sized module having a practical size is constructed using glass as the working electrode base material 102, there are disadvantages such as a risk of breaking and a heavy substrate weight. Further, although it is possible to reduce the thickness of the glass for weight reduction, it is extremely disadvantageous in terms of the substrate strength and is not necessarily a suitable measure.
On the other hand, it is conceivable to change the working electrode base material 102 to one made of plastic. In that case, although a good effect can be expected for problems such as substrate strength and weight reduction, the heat resistant temperature is reduced to glass. Compared with this, the heat resistance is problematic, and the firing process of the semiconductor porous film is severely restricted, making it difficult to obtain good device output.
Japanese Patent No. 2664194 JP 2001-160427 A M. Graetzel et al., Nature (UK), 1991, No. 353, p. 737

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a working electrode substrate that can maintain substrate strength and good power generation characteristics and can be reduced in weight.
Moreover, an object of this invention is to provide the photoelectric conversion element which can make large area and weight reduction compatible.

The working electrode substrate according to claim 1 of the present invention is a working electrode substrate having a porous oxide semiconductor layer on the surface of which a sensitizing dye is supported via a transparent conductive layer on a transparent substrate, The transparent substrate has a first substrate located on the porous oxide semiconductor layer side and at least one or more second substrates arranged to overlap the first substrate, and the second group The material includes a substrate having a specific gravity smaller than that of the first substrate , the first substrate is a glass plate, and a substrate having a specific gravity smaller than the first substrate is a plastic material, the total thickness of the smaller specific gravity substrate than the first substrate is characterized 5-20 Baidea Rukoto thickness of the first substrate.
The working electrode substrate according to claim 2 of the present invention is the substrate for working electrode according to claim 1, wherein the specific gravity of the base material having a specific gravity smaller than that of the first base material is ½ or less of the specific gravity of the first base material. It is characterized by.
A working electrode substrate according to a third aspect of the present invention is the working electrode substrate according to the first or second aspect , wherein a plurality of the first base materials are arranged two-dimensionally on the second base material. to.
The working electrode substrate according to claim 4 of the present invention is characterized in that, in any one of claims 1 to 3, a projected area of the second base material is larger than a projected area of the first base material. To do.
The working electrode substrate according to claim 5 of the present invention is the working electrode substrate according to any one of claims 1 to 4, wherein the first base material is disposed so as to overlap the second base material via a transparent adhesive layer. It is characterized by being.
The working electrode substrate according to claim 6 of the present invention is characterized in that, in claim 5, the second base material is permeable to light in the ultraviolet region.
A photoelectric conversion element according to claim 7 of the present invention is opposed to the working electrode substrate according to any one of claims 1 to 6 and the porous oxide semiconductor layer included in the working electrode substrate. It is comprised from the arrange | positioned counter electrode board | substrate and the electrolyte layer pinched | interposed into at least one part between the said working electrode board | substrate and the said counter electrode board | substrate.

  In the working electrode substrate according to the present invention, a transparent base material having a porous oxide semiconductor layer having a sensitizing dye supported on the surface via a transparent conductive layer is located on the porous oxide semiconductor layer side. A base material and at least one second base material disposed on the first base material, wherein the second base material includes a base material having a specific gravity smaller than that of the first base material. It has a configuration. Therefore, it is possible to reduce the overall weight by including a base material having a small specific gravity, and by appropriately selecting the materials of the first base material and the second base material that are arranged in a superimposed manner, the substrate strength and good power generation are achieved. The characteristics can be maintained.

  In addition, the photoelectric conversion element using the working electrode substrate according to the present invention is such that the transparent base material having a porous oxide semiconductor layer having a sensitizing dye supported on the surface via a transparent conductive layer is the porous oxide. The first base material located on the semiconductor layer side and at least one or more second base material arranged to overlap the first base material, the second base material is more than the first base material A working electrode substrate including a base material having a small specific gravity, a counter electrode substrate disposed opposite to a porous oxide semiconductor layer included in the working electrode substrate, the working electrode substrate, and the counter electrode And an electrolyte layer sandwiched between at least part of the substrate. Therefore, it is possible to obtain a photoelectric conversion element that can achieve both an increase in area and a reduction in weight.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing the structure of a photoelectric conversion element using the working electrode substrate of the present invention.
As shown in FIG. 1, the photoelectric conversion element 1 of the present invention has a working electrode (on the side where light is incident) on an electrode substrate composed of a working electrode substrate 2, a transparent conductive layer 4, and a porous oxide semiconductor layer 5. Window electrode) substrate 8, while electrode substrate composed of counter electrode base material 3 and conductive layer 7 is used as counter electrode substrate 9, and working electrode substrate 8 and counter electrode substrate 9 including the inside of porous oxide semiconductor layer 5 The electrolyte layer 6 is filled in at least a part of the gap.

  The working electrode substrate 2 is a transparent substrate including the transparent conductive layer 4 and the porous oxide semiconductor layer 5 used for the power generation layer, and at least the surface of the transparent conductive layer 4 made of a conductive material is formed. It is comprised from 2 or more types of layers which have the 1st base material 21 which has the electroconductivity which conducts electricity, and the at least 1 or more 2nd base material 22 distribute | arranged and piled up on this 1st base material. Further, the second base material 22 includes a base material having a specific gravity smaller than that of the first base material 21. Thereby, weight reduction can be achieved. In addition, the surface here means the surface which forms the transparent conductive layer 4 grade | etc., Among substrate surfaces, and is arrange | positioned facing the conductive layer 7 which acts as a counter electrode.

The first base material 21 is resistant to the case where a structure including a baking step is formed at the time of film formation, such as the porous oxide semiconductor layer 5 of the dye-sensitized solar cell, on the substrate on which the transparent conductive layer 4 is formed. Heat resistance is required. Examples of the first substrate 21 include glass plates such as soda lime glass, white plate glass, borosilicate glass, quartz glass, high strain point glass, and crystallized glass. Thereby, there is no restriction | limiting in the baking process of a semiconductor porous film, and a favorable element can be obtained.
Moreover, it is desirable that the first base material 21 is a thin plate so as to contribute to weight reduction of the working electrode base material 2. Therefore, it is bonded to the second base material 22 containing a base material having a specific gravity smaller than that of the first base material 21 to form a laminate, and the substrate strength and good power generation characteristics are maintained while reducing the weight. Can be planned.
Further, as shown in FIG. 2, for example, the first base material 21 includes a cell unit C in which a power generation layer composed of a transparent conductive layer 4 and a porous oxide semiconductor layer 5 is formed on a second base material 22. A plurality (four in the illustrated example) may be arranged two-dimensionally. Thereby, it is possible to obtain a photoelectric conversion element that achieves both an increase in area and a reduction in weight set to an arbitrary element output.

The second base material 22 is preferably made of a material that compensates for the strength of the first base material 21 having a small thickness and has a specific gravity lower than that of the first base material 21. As this 2nd base material 22, plastic materials, such as an acrylic resin, a polystyrene, a polycarbonate (PC), a cycloolefin polymer, a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), can be used, for example.
The projected area of the second substrate is preferably equal to or larger than the projected area of the first substrate. As a result, a plurality of the first base materials 21 can be arranged on the second base material 22, and the surplus area can be freely used, for example, by applying current collecting wiring.

As long as the working electrode base material 2 is a transparent member with high light transmittance, in addition to the first base material 21 and the second base material 22, an adhesive (adhesive) layer, a UV cut layer, an antireflection film, etc. It may be configured to include one or more. Therefore, the second base material 22 is not limited to one configured, and can be a laminated structure including at least one material that can be reduced in weight compared to the first base material 21.
At this time, the layers including the first base material 21 and the second base material 22 are laminated and bonded together by an arbitrary method such as adhesion (adhesion), pressure bonding, and fusion via an adhesive or pressure-sensitive adhesive. Therefore, when the first base material 21 and the second base material 22 are bonded to each other through the transparent adhesive layer, the laminate can be strongly produced without impairing light transmittance.
Moreover, as shown in FIG. 1, the total thickness L2 of the base material contained in the second base material 22 and having a specific gravity smaller than that of the first base material 21 is configured to be thicker than the thickness L1 of the first base material. And desirable. Thereby, further weight reduction can be achieved.

Furthermore, the second base material 22 is preferably made of a material that is transparent to light in the ultraviolet region. In the present invention, “having transparency with respect to light in the ultraviolet region” is defined as having a light transmittance at a wavelength of 365 nm of at least 70% of a transmittance at a wavelength of 550 nm.
When the 2nd base material 22 shows sufficient transmittance | permeability with respect to the light of an ultraviolet region, when bonding the 1st base material 21 and the 2nd base material 22, an ultraviolet curing transparent adhesive is applied. be able to.
As the second base material 22 made of a material that is transmissive to light in the ultraviolet region, in addition to various glass substrates, highly transmissive acrylic plates, cycloolefin polymers, PET [ poly (ethylene terephthalate)], PEN [poly (ethylene naphthalate)], and the like, but are not particularly limited.

In addition, when bonding the 1st base material 21 and the 2nd base material 22, it can replace with an ultraviolet curing transparent adhesive, and can also employ | adopt the adhesive agent and adhesive which are illustrated next.
Specific examples of the former include arbitrary adhesives such as a two-component mixed system, a visible light curing system, and a thermosetting system. The material of such an adhesive is not particularly limited, such as acrylic or epoxy, but is preferably colorless and transparent and excellent in light transmittance. In order to keep the light transmittance of the base material high, for example, by applying a two-component mixed adhesive that exhibits sufficient transmittance even for light in a wide wavelength range including the ultraviolet region, a glass single unit is used. The same level of transparency as when using one substrate can be secured.
A specific example of the latter is a so-called double-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive is disposed on both sides of the sheet. Also in this case, for the purpose of keeping the light transmittance of the base material high, it is desirable that the sheet or the pressure-sensitive adhesive is colorless and transparent and has excellent light transmittance.

  The transparent conductive layer 4 is a conductive film having a high light transmittance made of a conductive material formed on the first base material 21. As the transparent conductive layer 4, for example, a transparent conductive material such as tin-added indium oxide (ITO), fluorine-added tin oxide (FTO), tin-added antimony oxide (ATO) or various metal materials alone or fluorine-added oxide is used. It can be used in combination with multiple types such as tin / tin-added indium oxide (FTO / ITO) composite film, but it is not particularly limited and fits the purpose of use in terms of light transmittance and conductivity Choose what you want. In addition, in order to give a conductive auxiliary (current collecting) effect, it is made of a material selected from silver, platinum, copper, nickel, gold, aluminum, carbon, conductive polymer, etc. within a range that does not significantly impair the light transmittance. A metal wiring or the like may be added. Then, the working electrode (window electrode) substrate 8 is formed by forming the porous oxide semiconductor layer 5 on the working electrode substrate 2 via the transparent conductive layer 4.

There are no particular limitations on the material and formation method of the porous oxide semiconductor layer 5, for example, titanium dioxide (TiO ₂ ), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO). ), Niobium oxide (Nb ₂ O ₅ ), manganese oxide (MnO ₂ ), magnesium oxide (MgO), etc., alone or in combination of two or more types, oxide semiconductor particles having an average particle diameter of 1 nm to 1000 nm are mainly used. It is a porous thin film as a component, and can be obtained from commercially available fine particles or a colloidal solution obtained by a sol-gel method.
As a method for forming a porous film, for example, colloidal solutions and dispersions (including additives as necessary), various coating methods such as screen printing, inkjet printing, roll coating, doctor blade, spin coating, spray coating, etc. In addition to coating by using, electrophoretic electrodeposition of fine particles may be applied. The porous oxide semiconductor layer 5 carries a sensitizing dye.

  As the sensitizing dye, for example, a ruthenium complex containing a bipyridine structure, a terpyridine structure or the like as a ligand, a metal-containing complex such as porphyrin or phthalocyanine, and an organic dye such as a derivative such as eosin, rhodamine, merocyanine, or coumarin are used. A suitable one can be selected without particular limitation depending on the intended use and the semiconductor porous membrane to be used.

  On the other hand, the substrate 3 for the counter electrode is provided with the conductive layer 7 used for the counter electrode, and metal, glass, plastic, or the like can be used. On these substrates, various carbon materials, conductive polymers, platinum, etc. are formed by wet or dry methods (sputtering or vapor deposition), or platinum films are formed by heat treatment of chloroplatinate. Can be used as a counter electrode. In particular, when the substrate is an insulating material such as glass or plastic, a layer that imparts conductivity to the substrate, such as a transparent conductive layer, may be separately formed on the surface of the substrate.

  For the conductive layer 7, for example, platinum, chemically stable carbon, conductive polymer, or the like can be used. As for the method for forming the conductive layer 7, for example, when it is made of platinum, a vacuum film-forming method such as a sputtering method or a vapor deposition method, a wet film-forming method in which a platinum-containing solution such as a chloroplatinic acid solution is applied to the substrate surface and then heat treatment is applied. Can be used.

As the electrolyte layer 6, for example, an organic solvent containing a redox pair, an ionic liquid (room temperature molten salt), or the like can be used.
The redox couple is not particularly limited. For example, a redox couple obtained by adding iodine / iodide ions, bromine / bromide ions, or the like can be selected. Quaternized imidazolium salts, tetrabutylammonium salts and the like can be used alone or in combination) and iodine can be added alone or in combination.
In addition, although there is no particular limitation on the organic solvent, examples thereof include acetonitrile, methoxyacetonitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, and γ-butyrolactone.
Further, as the ionic liquid, for example, a room temperature comprising a cation such as an imidazolium ion or a pyridinium ion and an anion such as an iodide ion, a bistrifluoromethanesulfonylimide ion, a dicyanoamide ion, or a thiocyanate ion. Molten salt can be selected.

In addition, such an electrolyte layer 6 is a suspicious solid that suppresses fluidity by introducing a suitable gelling agent such as a high molecular gelling agent, a low molecular gelling agent, various nanoparticles, and carbon nanotubes, and a filler. A so-called gel electrolyte may be used.
Various additives such as lithium salt and 4-tert-butylpyridine may be further added to the electrolyte layer 6 as necessary.

Steps such as loading of the sensitizing dye, injection of the electrolyte layer 6, and lamination of the counter electrode substrate 9 can be provided at any timing before and after the bonding of the first base material 21 and the second base material 22. When incorporating the said process before bonding with the 2nd base material 22, in order to supplement the intensity | strength of the 1st base material 21 during handling, it is more preferable to use by temporarily sticking a support substrate.
For the bonding, for example, an arbitrary adhesive or pressure-sensitive adhesive such as a two-component mixed system, a UV curing system, a visible light curing system, or a thermosetting system can be used. The material is not particularly limited, such as acrylic or epoxy, but is more preferably colorless and transparent and excellent in light transmittance. Moreover, you may bond together using a double-sided adhesive sheet.

Next, an example of a method for producing a photoelectric conversion element according to the present invention will be described.
First, in order to constitute the working electrode base material 2, a glass plate (hereinafter denoted by reference numeral 21) is used as the first base material 21, and a plastic plate (hereinafter denoted by reference numeral 22) is used as the second base material 22. Prepare each.
When the working electrode substrate 8 is applied to a dye-sensitized solar cell as a photoelectric conversion element, particularly when used as a porous semiconductor electrode, the transparent conductive layer 4, the current collecting grid, and the corrosion prevention layer ( Insulating layer), porous oxide semiconductor layer 5 and the like are formed as necessary, and after passing through a baking step, they can be manufactured by bonding to each layer including the plastic plate 22. Therefore, the working electrode substrate 8 may be configured to include one or more UV cut layers, antireflection films, and the like.

  As a method for forming the transparent conductive layer 4, a known method may be used depending on the material of the transparent conductive layer 4, for example, a sputtering method, a CVD method (vapor phase growth method), an SPD method (spray pyrolysis deposition). Method), a vapor deposition method, etc., to form a thin film made of an oxide semiconductor such as FTO or FTO / ITO. Thereby, an electroconductive board | substrate is comprised. If the transparent conductive layer 4 is too thick, the light transmittance is inferior. On the other hand, if the transparent conductive layer 4 is too thin, the conductivity is inferior, so that both the light transmittance and the conductivity are taken into consideration. The film is formed to a thickness of about 2 μm.

Subsequently, the working electrode substrate (window-side electrode) 8 is formed by forming the porous oxide semiconductor layer 5 on the transparent conductive layer 4. As a method for forming the porous oxide semiconductor layer 5, for example, a titanium dioxide (TiO ₂ ) powder is mixed with a dispersion medium to prepare a paste, and this is used for a screen printing method, an ink jet printing method, a roll coating method, a doctor, etc. It is applied onto a conductive substrate by a blade method, a spin coating method or the like, and is baked. The porous oxide semiconductor layer 5 is usually formed as a thin film having a thickness of about 1 μm to 50 μm. Thus, a conductive substrate (electrode substrate) is formed, and sunlight (denoted as hν in FIG. 1) enters the photoelectric conversion element 1 through the electrode substrate.
Then, the substrate on which the porous oxide semiconductor layer 5 is formed is dipped in the dye solution, whereby the porous oxide semiconductor layer 5 carries the dye.

  On the other hand, for example, a transparent conductive glass plate is prepared as the counter electrode substrate 3, and the counter electrode substrate 9 is configured by providing the conductive layer 7 made of platinum thereon. As a method for forming the conductive layer 7, for example, a sputtering method or the like can be used.

  Then, the porous oxide semiconductor layer 5 of the working electrode substrate 8 and the conductive layer 7 of the counter electrode substrate 9 are arranged to face each other, and an electrolyte layer is formed on at least a part between both substrates including the inside of the porous oxide semiconductor layer 5. 6 is filled with an electrolytic solution and sealed to provide a photoelectric conversion element (dye-sensitized solar cell) 1 using the working electrode substrate 8 according to the present invention.

  As described above, according to the present embodiment, it is possible to maintain strength and maintain good power generation characteristics and to reduce the weight as compared with the case where glass alone is used as the working electrode substrate. Therefore, even when a photoelectric conversion element is constructed, both an increase in area and a reduction in weight can be achieved, and an excellent element output can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
First, the working electrode base material has a first base material and at least one or more second base materials arranged on the first base material, and the second base material includes the first base material. By including a base material having a specific gravity smaller than that of the material, it is possible to reduce the weight while maintaining strength, and to confirm that a large-area photoelectric conversion element having good power generation characteristics can be constructed, A first base material shown in Table 1, a second base material shown in Table 2, and a bonding adhesive shown in Table 3 were prepared.

  As shown in Table 1, the first substrate is a glass plate that has heat resistance and is not subject to restrictions in the firing process of the semiconductor porous membrane, and can maintain strength while reducing weight. In order to confirm, two types with different thicknesses were prepared.

  As shown in Table 2, as the second base material, four kinds of plastic materials such as an acrylic plate, a polycarbonate (PC) plate, a cycloolefin polymer, and a PEN sheet having a specific gravity about half that of the first base material are used. Prepared and prepared two types of acrylic plates with different dimensions in order to confirm that a large area photoelectric conversion element can be constructed.

Next, a photoelectrode layer for a photoelectric conversion element (dye-sensitized solar cell) was formed on the first substrate.
First, an FTO film was formed on one surface of the first substrate by the SPD method or the CVD method.
Next, four strip-shaped silver circuits having a circuit width of 300 μm and a film thickness of 10 μm were formed in parallel on the first base material on which the FTO film was formed by screen printing. Moreover, the silver layer was formed also in the peripheral part. A silver paste having a volume resistivity after sintering of 3 × 10 ⁻⁶ Ω · cm was used as a printing silver paste.
Subsequently, a low melting point glass paste was printed by screen printing on the circuit forming portion so as to completely cover the silver circuit with a width of 800 μm, and this was fired using a hot air circulation oven to form a shielding layer.
Furthermore, a paste containing TiO ₂ nanoparticles was applied onto the first substrate by screen printing, dried, and then fired at a temperature of 500 ° C. for 60 minutes to form a porous oxide semiconductor film.
Thereafter, the first substrate was immersed in an acetonitrile / t-butanol solution of ruthenium bipyridine complex (N719 dye) for at least 24 hours to carry the dye to obtain a photoelectrode. The dye was supported before or after the first base material and the second base material were bonded together.

And after forming current collection wiring and a porous oxide semiconductor film, the 1st base material and the 2nd base material in which the photoelectrode layer was formed were bonded together using the transparent adhesive. The combinations of the materials are as shown in Table 4. Moreover, the kind of the 1st base material shown in Table 4, the 2nd base material, and the adhesive agent for bonding is described by the number shown in Table 1, Table 2, and Table 3 mentioned above, respectively.
In Example 6, the first base material and the second base material were bonded together with a UV cut film interposed between both base materials instead of directly. Moreover, in Example 10, it bonded together on the 2nd base material in the state which arranged the 1st base material in tile shape.

And when the produced bonded substrate is compared with a high strain point glass substrate (manufactured by Central Glass Co., Ltd.) having a thickness of 2.8 mm and a specific gravity of 2.7, the specific gravity of the second base material is 1/2 or less. For this reason, the specific gravity of the substrate can be greatly reduced and the weight can be reduced.
In addition, when the first base material used in Example 9 is only the first base material and the vicinity of the end is held by hand, the bending due to its own weight has greatly cracked, but it is bonded to the second base material. After that, even if it was held in the same manner, it did not cause bending that would cause cracking, and the strength could be maintained.

  Therefore, it has a first base material and at least one or more second base materials arranged on the first base material, and the second base material has a specific gravity smaller than that of the first base material. It was confirmed that the working electrode base material including the material can reduce the weight while maintaining the strength of the substrate. Moreover, even when the total thickness of the base material having a small specific gravity in the second base material is thicker than the thickness of the first base material, the weight can be reduced while maintaining the strength.

  Next, a change in light transmittance due to bonding of the first base material and the second base material was confirmed. The light transmittance is confirmed by bonding the first base material before forming the conductive layer and the second base material, and the visible light transmittance at a wavelength of 550 nm is 10% that of the second substrate alone. The case where it decreased more than was evaluated as x, and the case where the decrease remained below 10% was evaluated as ◯. The results are shown in Table 5.

  As is apparent from Table 5, it was confirmed that good transmittance can be maintained in any case. Therefore, it can be expected that good power generation characteristics are maintained.

Next, photoelectric conversion elements (dye-sensitized solar cells) were prepared using the substrates of Examples 1 to 10, and the photoelectric conversion characteristics were measured. In this case, 1-hexyl-3-methylimidazolium iodide and iodine were mixed at a molar ratio of 10: 1 in the electrolytic solution, and further 0.1M lithium iodide (LiI) and 0.5M 4 A liquid electrolyte to which -tert-butylpyridine was added was used. A pseudo solid electrolyte obtained by adding 5 wt% silica powder to the liquid electrolyte and removing excess liquid components by centrifugation was also used. Moreover, the titanium sheet which sputter-formed the platinum layer was used as a counter electrode.
Then, the electrolyte is spread on the photoelectrode, the counter electrode sheet is overlaid on the photoelectrode, the electrolyte that protrudes to the periphery is wiped off, sealed with UV curable resin, and lead wires are arranged on both the photoelectrode and the counter electrode. Then, it was housed in a cell case to obtain a test element.
Furthermore, in Example 10, the element 6 cell created based on the board | substrate first was wired in series, and the characteristic was evaluated. At this time, a quasi-solid electrolyte was used as the electrolyte.

  Moreover, the element of the same size was produced as a comparative example using the polyethylene terephthalate (PET) board | substrate which provided the tin addition indium oxide (ITO) layer on the single side | surface. In this case, since a sintered type silver wiring cannot be applied, a resin binder type silver paste was used, and an acrylic resin paste was also used for the shielding layer. The titanium oxide porous membrane was obtained by applying a paste containing nanoparticles and then drying at 120 ° C. The other constituent materials were the same as described above. Furthermore, the same photoelectrode (window side electrode) was produced using the above-mentioned high strain point glass substrate, and the result when this was applied to a solar cell was defined as Comparative Example 2.

The power generation characteristics were evaluated by irradiating simulated sunlight with AM 1.5 and 100 mW / cm ² . The measurement results are shown in Table 6.

From Table 6, the following points became clear.
(1) The photoelectric conversion elements using the electrodes according to the present invention (Examples 17 to 25) can ensure good characteristics at the same level as when a conventional glass substrate is used (Comparative Example 2).
(2) On the other hand, in Comparative Example 1, the output was low because the firing of the TiO ₂ layer was insufficient.
The open circuit voltage in the case of a single cell (Examples 17 to 25) is about 0.6 to 0.7 V, whereas the open circuit voltage in the case of connecting a plurality of cells in series (Example 26) is Since it was 4 V or more, it was confirmed that according to the present invention, a high-voltage type device could be easily manufactured.
Furthermore, it is possible to increase the amount of current if the element cells are connected in parallel. A plurality of first substrates are arranged two-dimensionally on the second substrate, that is, on the second substrate. It was found that an arbitrary element output can be set by adjusting the number of first base materials arranged on the substrate and the connection method.

  Therefore, when the working electrode (electrode) substrate of the present invention is used, it is possible to reduce the weight while maintaining the strength of the substrate and good power generation characteristics when compared with those using glass alone as a base material. is there. In addition, since the projected area of the second substrate is larger than the projected area of the first substrate, a plurality of photoelectrode layers can be formed substantially on a single substrate. Thus, it was confirmed that an arbitrary module in series or parallel can be easily produced and a photoelectric conversion element capable of achieving both a large area and a light weight can be constructed.

  Below, in order to confirm that the photoelectric conversion element using the 2nd base material which has the transmittance | permeability with respect to the light of an ultraviolet region can aim at the increase in photoelectric conversion efficiency, the 1st base material shown in Table 7, Table 8 The second base material shown in FIG. 5 and the bonding adhesive shown in Table 9 were prepared.

  As shown in Table 7, the first substrate is a glass plate that has heat resistance according to the previous Examples 1 to 10 and is not restricted in the firing process of the semiconductor porous film, One type was used, which was confirmed to maintain strength while reducing weight.

  As shown in Table 8, as the second substrate, three types of plastic materials such as an acrylic plate, a cycloolefin polymer, and a general-purpose acrylic plate having a specific gravity about half that of the first substrate were prepared.

Next, a photoelectrode layer for a photoelectric conversion element (dye-sensitized solar cell) was formed on the first substrate.
First, an FTO film was formed on one surface of the first substrate by the SPD method.
Next, four strip-shaped silver circuits having a circuit width of 300 μm and a film thickness of 10 μm were formed in parallel on the first base material on which the FTO film was formed by screen printing. Moreover, the silver layer was formed also in the peripheral part. A silver paste having a volume resistivity after sintering of 3 × 10 ⁻⁶ Ω · cm was used as a printing silver paste.
Subsequently, a low melting point glass paste was printed by screen printing on the circuit forming portion so as to completely cover the silver circuit with a width of 800 μm, and this was fired using a hot air circulation oven to form a shielding layer.
Furthermore, a paste containing TiO ₂ nanoparticles was applied onto the first substrate by screen printing, dried, and then fired at a temperature of 500 ° C. for 60 minutes to form a porous oxide semiconductor film.
Thereafter, the first substrate was immersed in an acetonitrile / t-butanol solution of N719 dye for 24 hours or more to carry the dye, thereby obtaining a photoelectrode.

  And after forming current collection wiring and a porous oxide semiconductor film, the 1st base material and the 2nd base material in which the photoelectrode layer was formed were bonded together using the transparent adhesive. The combination of each material is as shown in Table 10. Moreover, the kind of the 1st base material shown in Table 10, the 2nd base material, and the adhesive agent for bonding is described by the number shown in Table 7, Table 8, and Table 9 mentioned above, respectively.

The light transmittance in the wavelength range of 200 nm to 900 nm was observed for the substrates (photoelectrode layers were not formed) bonded together in combinations of the examples and comparative examples shown in Table 10. The result is shown in FIG. In addition, in FIG. 3, the result of the glass plate for a comparison (1 mm thickness soda glass plate) was shown collectively with the result of Example 31, 33, 34, 36 and Comparative Examples 31 and 32.
In the short wavelength region (here, the wavelength region is smaller than 400 nm), the substrates after bonding in the respective examples shown in FIG. 3 are not inferior to the glass plate for comparison or have better transmission characteristics. I understood that. On the other hand, in each comparative example shown in FIG. 3, it was confirmed that the transmittance sharply decreased from the vicinity of 400 nm on the low wavelength side.
In the case of Examples 32 and 35, it was possible to easily bond the substrates using a UV curable adhesive, but in the case of Comparative Example 33, the second substrate absorbed the irradiation light. Therefore, the curing of the adhesive was very slow, and yellowing and warping of the base material occurred as the irradiation amount increased. (Because a power generation layer is formed on the glass surface side, it cannot be used as an ultraviolet incident surface. .)

Next, photoelectric conversion elements (dye-sensitized solar cells) were prepared using the substrates of Examples 31, 32, 34, and 35 and Comparative Examples 31 and 32 described above, and the photoelectric conversion characteristics thereof were measured. Here, the produced photoelectric conversion elements are referred to as Examples 41, 42, 44, and 45 and Comparative Examples 41 and 42 in this order. When producing the above photoelectric conversion element, the electrolyte is mixed with 1-hexyl-3-methylimidazolium iodide and iodine at a molar ratio of 10: 1, and further 0.1 M lithium iodide (LiI). ) And 0.5M 4-tert-butylpyridine were used. A pseudo solid electrolyte obtained by adding 5 wt% silica powder to the liquid electrolyte and removing excess liquid components by centrifugation was also used. Moreover, the titanium sheet which sputter-formed the platinum layer was used as a counter electrode.
Then, the electrolyte is spread on the photoelectrode, the counter electrode sheet is overlaid on the photoelectrode, the electrolyte that protrudes to the periphery is wiped off, sealed with UV curable resin, and lead wires are arranged on both the photoelectrode and the counter electrode. Then, it was housed in a cell case to obtain a test element.

  For comparison, an element of the same size was fabricated using a glass plate (1 mm thick) provided with a fluorine-added tin oxide (FTO) film on one side. At that time, the manufacturing conditions other than the substrate were the same as those in Examples 31, 32, 34, and 35 and Comparative Examples 31 and 32 described above.

The power generation characteristics were evaluated by irradiating simulated sunlight with AM 1.5 and 100 mW / cm ² .
FIG. 4 is a graph showing the measurement results of the external quantum efficiency (IPCE: Incident Photon-to-Current conversion Efficiency) of a photoelectric conversion element manufactured using each substrate. For the evaluation here, a simple cell having a power generation area of 8 mm square was fabricated and used by combining the substrates shown in Table 10.
As shown in FIG. 4, in Examples (41, 42, 44, 45), photoelectric conversion characteristics similar to those obtained when using a glass plate were obtained, whereas in Comparative Example 41, the lower wavelength side was obtained. It was found that the light of the can not be used effectively. Although not shown here, it was confirmed that the result of Comparative Example 42 was the same as that of Comparative Example 41.

  Table 11 shows the short circuit current value of the photoelectric conversion element manufactured using each substrate of Table 10, and shows the short circuit current value observed in the photoelectric conversion element using the glass plate (Comparative Example 43: liquid electrolyte system) as 1 As a standardized numerical value.

From Table 11, the following points became clear.
(1) The short-circuit current observed in each example was at least 0.96, which was a value close to or exceeding 1.0. From this result, it was confirmed that the photoelectric conversion element according to the present invention is at the same level as when a glass plate is applied.
(2) On the other hand, since the short circuit current of Comparative Examples 41 and 42 remains in the range of 0.72 to 0.91, the short circuit current is reduced as compared with the case where the glass plate is applied, which is not good. It became clear.
The present inventors have determined that the difference between the above (1) and (2) reflects whether or not incident light on the short wavelength side can be used effectively.

  Therefore, when the working electrode (window electrode) substrate of the present invention is used, the weight can be reduced while maintaining the substrate strength and good power generation characteristics, compared with those using glass alone as a base material. It is possible to provide a photoelectric conversion element that can effectively use incident light on the wavelength side.

It is sectional drawing which shows an example of the photoelectric conversion element using the board | substrate for working electrodes which concerns on this invention. It is a perspective view which shows another example of the board | substrate for working electrodes which concerns on this invention. It is a graph which shows the light transmittance of the board | substrate after bonding. It is a graph which shows the external quantum efficiency (IPCE) of a photoelectric conversion element. It is sectional drawing which shows an example of the photoelectric conversion element using the conventional board | substrate for working electrodes.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoelectric conversion element (dye-sensitized solar cell), 2 base material for working electrodes, 3 base materials for counter electrodes, 4 transparent conductive layer, 5 porous oxide semiconductor layer, 6 electrolyte layer, 7 conductive layer, 8 working electrode ( Window electrode) substrate, 9 counter electrode substrate, 21 first base material, 22 second base material.

Claims (7)

A substrate for a working electrode having a porous oxide semiconductor layer having a sensitizing dye supported on the surface via a transparent conductive layer on a transparent substrate,
The transparent substrate has a first substrate located on the porous oxide semiconductor layer side and at least one or more second substrates arranged to overlap the first substrate, and the second group The material includes a substrate having a specific gravity smaller than that of the first substrate ,
The first substrate is a glass plate, the substrate having a specific gravity smaller than that of the first substrate is a plastic material,
The total thickness of the first substrate specific gravity than a small substrate, a working electrode substrate according to claim 5-20 Baidea Rukoto thickness of the first substrate. 2. The working electrode substrate according to claim 1, wherein the specific gravity of the base material having a specific gravity smaller than that of the first base material is ½ or less of the specific gravity of the first base material. Said first substrate, said plurality on the second substrate, a working electrode substrate according to claim 1 or 2, characterized in that it is arranged two-dimensionally.  4. The working electrode substrate according to claim 1, wherein a projected area of the second base material is equal to or larger than a projected area of the first base material. 5.  5. The working electrode substrate according to claim 1, wherein the first base material is disposed so as to overlap the second base material with a transparent adhesive layer interposed therebetween.  The working electrode substrate according to claim 5, wherein the second base material is transparent to light in an ultraviolet region. The working electrode substrate according to any one of claims 1 to 6,
A counter electrode substrate disposed opposite to the porous oxide semiconductor layer of the working electrode substrate;
A photoelectric conversion element comprising: an electrolyte layer sandwiched between at least a part between the working electrode substrate and the counter electrode substrate.

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