JP2011086518A - Glass composition for dye-sensitized solar cell, and material for dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To raise long-term durability of a dye-sensitized solar cell by providing a glass composition for the dye-sensitized solar cell and a material for the dye-sensitized solar cell which have low melting-point characteristics and are excellent on electrolyte resistance and waterproof characteristics. <P>SOLUTION: The glass composition for the dye-sensitized solar cell contains 20-50% V<SB>2</SB>O<SB>5</SB>, 15-45% P<SB>2</SB>O<SB>5</SB>, 5-35% ZnO, and 15-40% BaO at mol% in terms of oxide as glass formation. Furthermore, the material for the dye-sensitized solar cell contains 50-100 vol.% of glass powder made of a glass composition for the dye-sensitized solar cell, and 0-50 vol.% of fireproof filler. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a glass composition for a dye-sensitized solar cell and a material for a dye-sensitized solar cell, specifically, sealing of a transparent electrode substrate and a counter electrode substrate of a dye-sensitized solar cell, The present invention relates to a glass composition for a dye-sensitized solar cell and a material for a dye-sensitized solar cell, which are suitable for forming a partition for partitioning between coating and cells.

  Dye-sensitized solar cells developed by Gretcher et al. Are expected to be the next-generation solar cells because they are less expensive than solar cells using silicon semiconductors and have abundant raw materials necessary for production. .

The dye-sensitized solar cell includes a transparent electrode substrate on which a transparent conductive film is formed, and a porous oxide semiconductor electrode composed of a porous oxide semiconductor layer (mainly a TiO ₂ layer) formed on the transparent electrode substrate, It is composed of a dye such as Ru dye adsorbed on the porous oxide semiconductor electrode, an iodine electrolyte containing iodine, a counter electrode substrate on which a catalyst film and a transparent conductive film are formed, and the like.

  A glass substrate, a plastic substrate, or the like is used as the transparent electrode substrate and the counter electrode substrate. When a plastic substrate is used as the transparent electrode substrate, the resistance value of the transparent electrode film increases, and the photoelectric conversion efficiency of the dye-sensitized solar cell decreases. On the other hand, when a glass substrate is used as the transparent electrode substrate, the resistance value of the transparent electrode film hardly increases, and the photoelectric conversion efficiency of the dye-sensitized solar cell can be maintained. Therefore, in recent years, a glass substrate has been used as the transparent electrode substrate.

  In the dye-sensitized solar cell, an iodine electrolyte is filled between the transparent electrode substrate and the counter electrode substrate. In order to prevent the leakage of iodine electrolyte from the dye-sensitized solar cell, it is necessary to seal the outer peripheral edges of the transparent electrode substrate and the counter electrode substrate. Moreover, in order to take out generated electrons efficiently, a collecting electrode (for example, Ag or the like is used) may be formed on the transparent electrode substrate. At this time, it is necessary to cover the current collecting electrode and prevent the current collecting electrode from being eroded by the iodine electrolyte. Furthermore, when a battery circuit is formed on a single glass substrate, a partition wall may be formed between the transparent electrode substrate and the counter electrode substrate.

Japanese Patent Laid-Open No. 1-220380 JP 2002-75472 A JP 2004-146425 A

  In dye-sensitized solar cells, improvement of long-term durability is a problem for practical use. As a cause of impairing the long-term durability, the solar cell member (sealing material, current collecting electrode, etc.) reacts with the iodine electrolyte, and the solar cell member and the iodine electrolyte are deteriorated. This tendency is particularly remarkable when a resin is used as the sealing material and an organic solvent such as acetonitrile is used as the iodine electrolyte. In this case, since the resin is eroded by the iodine electrolyte, the iodine electrolyte leaks from the dye-sensitized solar cell, and the battery characteristics are remarkably deteriorated. Similarly, when a resin is used for covering the collector electrode or forming the partition wall, the resin is eroded by the iodine electrolyte solution, so that the collector electrode is deteriorated or the partition wall is broken.

  If glass is used as the sealing material, this problem may be solved. For example, Patent Document 1 describes using glass as a sealing material. Patent Documents 2 and 3 describe the use of lead glass as a sealing material.

  However, lead glass cannot be said to have sufficient resistance (electrolytic solution resistance) to iodine electrolyte, and even when lead glass is used, the components of lead glass are eluted into the iodine electrolyte by long-term use. As a result, the iodine electrolyte solution deteriorates and the battery characteristics deteriorate. Further, even when lead glass is used for covering the current collecting electrode and forming the partition walls, deterioration of the current collecting electrodes and breakage of the partition walls occur due to long-term use. These phenomena are also caused by the insufficient resistance to electrolyte of lead glass.

Further, as the glass does not contain _{lead, V 2 O 5 -P 2 O} 5 -based glass has been studied intensively. However, V ₂ O ₅ -P ₂ O ₅ glass often has insufficient water resistance and is easily eroded by external moisture or the like, and iodine electrolyte leaks from a dye-sensitized solar cell after long-term use. In addition, battery characteristics may be significantly degraded.

  Furthermore, if the softening point of the sealing material is higher than the strain point of the transparent electrode substrate and the counter electrode substrate, high temperature firing is required for sealing, and the transparent electrode substrate and the counter electrode substrate may be deformed during sealing. Therefore, the sealing material (glass contained in the sealing material) is required to have a low melting point characteristic. Specifically, the sealing material is required to have a softening point of 550 ° C. or lower, particularly 500 ° C. or lower.

  Accordingly, the present invention provides a dye-sensitized solar cell glass composition and a dye-sensitized solar cell material having low melting point characteristics and excellent electrolyte solution resistance and water resistance. The technical challenge is to increase the long-term durability of sensitive solar cells.

As a result of various studies, the present inventor has found that the above technical problem can be solved by introducing a predetermined amount of V ₂ O ₅ , P ₂ O ₅ , ZnO and BaO as essential components into the glass composition. This is proposed as the present invention. That is, the dye-sensitized solar cell glass composition of the present invention has a glass composition, in mol% terms of _{oxide, V 2 O 5 20~50%,} P 2 O 5 15~45%, ZnO 5 It is characterized by containing -35% and BaO 15-40%.

In the glass composition for a dye-sensitized solar cell of the present invention, by introducing V ₂ O ₅ , P ₂ O ₅ , ZnO and BaO as essential components in the glass composition, and strictly regulating the content thereof, The low melting point characteristic can be secured and the resistance to electrolyte can be improved. In particular, the water resistance is remarkably enhanced by containing P ₂ O ₅ content of 45 mol% or less, ZnO content of 5 mol% or more and BaO content of 15 mol% or more in the glass composition. Can do. As a result, when the dye-sensitized solar cell glass composition of the present invention is used, the long-term durability of the dye-sensitized solar cell is increased. it can.

  Secondly, the material for a dye-sensitized solar cell of the present invention comprises 50 to 100% by volume of a glass powder composed of the above glass composition for a dye-sensitized solar cell and 0 to 50% by volume of a refractory filler. It is characterized by containing. In addition, the material for dye-sensitized solar cells of the present invention includes an embodiment constituted only by glass powder made of the above glass composition.

Third, the dye-sensitized solar cell material of the present invention is characterized in that the mass loss when immersed in an iodine electrolyte solution at 70 ° C. for 2 weeks is 0.1 mg / cm ² or less. Here, “iodine electrolyte” includes 0.1M lithium iodide, 0.05M iodine, 0.5M tert-butylpyridine, and 1,2-dimethyl-3-propylimidazolium iodide in acetonitrile. Use 6M dissolved. Further, “mass loss” means that a glass substrate (a glass substrate with a fired film) onto which a dye-sensitized solar cell material has been finely baked is immersed in an iodine electrolytic solution in a sealed container, and the mass before immersion is 2 The value obtained by subtracting the mass after the lapse of the week is calculated by dividing the value by the area of the fired film in contact with the iodine electrolyte. A glass substrate that is not eroded by the iodine electrolyte is used.

In general, the iodine electrolyte refers to a solution obtained by dissolving an iodine compound such as iodine, alkali metal iodide, imidazolium iodide, quaternary ammonium salt, etc. in an organic solvent. Some have 1 methoxybenzimidazole dissolved. As the solvent, nitrile solvents such as acetonitrile, methoxyacetonitrile, propionitrile, carbonate solvents such as ethylene carbonate and propylene carbonate, lactone solvents and the like are used. Even in the case of an iodine electrolytic solution composed of these compounds and solvents, the above problem that the glass is eroded by the iodine electrolytic solution may occur. Therefore, the dye-sensitized solar cell material of the present invention preferably has a mass loss of 0.1 mg / cm ² or less when immersed in these iodine electrolytes at 70 ° C. for 2 weeks.

  Fourthly, the dye-sensitized solar cell material of the present invention is characterized in that the softening point is 550 ° C. or lower. Here, the “softening point” refers to a value measured with a macro-type differential thermal analysis (DTA) apparatus, DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min. In addition, the softening point measured with the macro type | mold DTA apparatus points out the temperature (Ts) of the 4th bending point shown in FIG.

Fifth, the dye-sensitized solar cell material of the present invention is characterized by being used for sealing. Here, the sealing includes sealing of a glass tube in addition to sealing of the transparent electrode substrate and the counter electrode substrate.
In addition, after providing a plurality of openings in the transparent electrode substrate and the counter electrode substrate, and sealing the glass tube in each opening, the liquid containing the dye in the dye-sensitized solar cell through the glass tube Etc. may be circulated to adsorb the dye to the porous oxide semiconductor. In such a case, when the dye-sensitized solar cell material of the present invention is used, it is possible to prevent a liquid or the like from leaking from the glass tube.

  Sixth, the material for a dye-sensitized solar cell according to the present invention is used for coating a collecting electrode.

The glass composition for a dye-sensitized solar cell of the present invention contains a predetermined amount of V ₂ O ₅ , P ₂ O ₅ , ZnO and BaO in the glass composition. Good water resistance and water resistance. As a result, since the long-term durability of the dye-sensitized solar cell is improved, it is possible to prevent the battery characteristics from being deteriorated by long-term use. Similarly, the dye-sensitized solar cell material of the present invention includes a predetermined amount of V ₂ O ₅ , P ₂ O ₅ , ZnO and BaO in the glass composition of the glass powder, and thus has a low melting point characteristic, In addition, the electrolytic solution resistance (particularly, the weight loss when immersed in an iodine electrolytic solution at 70 ° C. for 2 weeks is 0.1 mg / cm ² or less) and the water resistance are good. As a result, since the long-term durability of the dye-sensitized solar cell is improved, it is possible to prevent the battery characteristics from being deteriorated by long-term use.

It is a schematic diagram which shows the softening point of the dye-sensitized solar cell material (glass powder) when measured with a macro DTA apparatus.

  The reason for limiting the glass composition range as described above in the dye-sensitized solar cell glass composition of the present invention will be described below. In addition, the following% display points out mol% unless there is particular notice.

V ₂ O ₅ is a component that forms a glass network and is a main component for lowering the softening point, and its content is 25 to 55%, preferably 28 to 50%, more preferably 30 to 45%. It is. When the content of V ₂ O ₅ is small, the viscosity of the glass increases, and the firing temperature (sealing temperature or the like) increases. On the other hand, when the content of V ₂ O ₅ is large, glass becomes thermally unstable, water resistance also decreases.

P ₂ O ₅ is a component for forming a glass network, the content is 15% to 45%, preferably 15 to 40%, more preferably 20-30%. When the content of P ₂ O ₅ is less, glass becomes thermally unstable, the glass tends to be devitrified when melted or during sintering. On the other hand, when the content of P ₂ O ₅ is large, too high the viscosity of the glass, also the water resistance is lowered.

  ZnO is a component that thermally stabilizes the glass and increases water resistance, and its content is 5 to 35%, preferably 10 to 30%, and more preferably 13 to 25%. When the content of ZnO is small, the glass becomes thermally unstable and the water resistance is lowered. On the other hand, when there is too much content of ZnO, the component balance of a glass composition will be impaired and glass will become thermally unstable conversely.

  BaO is a component that thermally stabilizes the glass and increases water resistance, and its content is 15 to 40%, preferably 15 to 30%, and more preferably 15 to 25%. When there is little content of BaO, water resistance will fall. On the other hand, when there is too much content of BaO, the component balance of a glass composition will be impaired and glass will become thermally unstable conversely.

  In addition to the above components, the following components can be added to the glass composition.

  SrO is a component that thermally stabilizes the glass and suppresses devitrification and lowers the viscosity of the glass, and its content is 0 to 20%, preferably 0 to 15%. . When there is too much content of SrO, the component balance of a glass composition will be impaired and glass will become thermally unstable conversely.

  CuO is a component that stabilizes the glass thermally and suppresses devitrification, and is a component that increases water resistance, and its content is 0 to 10%, preferably 0 to 8%. When the content of CuO is large, the viscosity of the glass increases, and the firing temperature increases.

Al ₂ O ₃ is a component that stabilizes the glass thermally and suppresses devitrification and is a component that increases water resistance, and its content is 0 to 10%, preferably 1 to 5%. is there. When the content of Al ₂ O ₃ is large, the viscosity of the glass becomes too high, the firing temperature increases.

Bi ₂ O ₃ is a component that improves water resistance, and its content is 0 to 10%, preferably 1 to 5%. The content of Bi ₂ O ₃ is large, the viscosity of the glass becomes too high, the firing temperature tends to increase.

In addition to the above _{ingredients, CaO, MgO, TeO 2,} B 2 O 3, Fe 2 O 3, the components of SiO ₂ or the like may be added to the glass composition to 10%.

In addition, in order to improve electrolyte solution resistance, it is preferable not to contain PbO substantially. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is 1000 ppm (mass) or less. In addition, if it is set as the aspect which does not contain PbO substantially, the recent environmental request | requirement can also be satisfied.

  It is preferable that the material for a dye-sensitized solar cell of the present invention is composed only of glass powder made of the above-described glass composition for a dye-sensitized solar cell. In this way, the cell gap of the solar cell can be made small and easy to be uniformed, and a mixing step of a refractory filler or the like is not required, so the manufacturing cost of the dye-sensitized solar cell material is reduced. be able to.

  The dye-sensitized solar cell material of the present invention may contain a refractory filler in order to improve the mechanical strength or lower the thermal expansion coefficient. The mixing ratio is preferably 50 to 100% by volume of glass powder, 0 to 50% by volume of refractory filler, particularly 65 to 100% by volume of glass powder, and 0 to 35% by volume of refractory filler. When the content of the refractory filler is more than 50% by volume, the ratio of the glass powder is relatively reduced, so that it is difficult to ensure desired fluidity. On the other hand, if the addition amount of the refractory filler is reduced, the fluidity, particularly the sealing property, of the dye-sensitized solar cell material can be improved. In consideration of fluidity, the content of the refractory filler is preferably 10% by volume or less, 5% by volume or less, and particularly preferably 1% by volume or less. As described above, it is desirable that the refractory filler is not substantially contained.

The refractory filler is not particularly limited, and various materials can be selected, but those that do not easily react with the glass powder or the electrolytic solution according to the present invention are preferable. Specifically, as a refractory filler, zircon, zirconia, tin oxide, aluminum titanate, quartz, β-spodumene, mullite, titania, quartz glass, β-eucryptite, β-quartz, zirconium phosphate, willemite, Cordierite, a compound having a basic structure of [AB ₂ (MO ₄ ) ₃ ],
A: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc. B: Zr, Ti, Sn, Nb, Al, Sc, Y etc. M: P, Si, W, Mo etc. Alternatively, these solid solutions can be used.

  When the refractory filler is included, the maximum particle size of the refractory filler is preferably 25 μm or less. Since the cell gap of the dye-sensitized solar cell is very thin (for example, 50 μm or less), if the particle size of the refractory filler is too large, it becomes difficult to seal the transparent electrode substrate and the counter electrode substrate. Here, the “maximum particle size” represents a particle size whose cumulative amount is 99% cumulative from the smaller particle size in a volume-based cumulative particle size distribution curve measured by a laser diffraction method.

In the dye-sensitized solar cell material of the present invention, the mass loss when immersed in an iodine electrolyte at 70 ° C. for 2 weeks is preferably 0.1 mg / cm ² or less, particularly preferably 0.05 mg / cm ² or less. It is desirable that there is no mass loss. If the mass loss is 0.1 mg / cm ² or less, it is possible to prevent erosion due to iodine electrolyte and deterioration of battery characteristics over a long period of time. Here, “substantially no weight loss” refers to a case where the weight loss is 0.01 mg / cm ² or less.

In the dye-sensitized solar cell material of the present invention, the softening point is preferably 550 ° C. or lower, particularly preferably 500 ° C. or lower. If the softening point is higher than 550 ° C., the viscosity of the glass becomes too high, and the firing temperature (especially the sealing temperature, etc.) rises unreasonably, and the transparent electrode substrate and the counter electrode substrate are easily deformed during firing. In addition, when forming the porous oxide semiconductor (mainly TiO ₂ ) layer and sealing the transparent electrode substrate and the counter electrode substrate at the same time, if the sealing temperature is too high, the fusion of the oxide particles proceeds and the porous As a result, it becomes difficult to simplify the manufacturing process of the dye-sensitized solar cell.

In the dye-sensitized solar cell material of the present invention, the thermal expansion coefficient is preferably 60 to 120 × 10 ⁻⁷ / ° C., particularly preferably 65 to 110 × 10 ⁻⁷ / ° C. If the difference in thermal expansion coefficient between the dye-sensitized solar cell material and soda glass used for the transparent electrode substrate or the counter electrode substrate is large, unreasonable stress will remain on both after firing, and cracks and peeling will easily occur. Become. Here, the “thermal expansion coefficient” refers to a value measured in a temperature range of 30 to 300 ° C. by a push rod type thermal expansion coefficient measurement (TMA) apparatus.

  The dye-sensitized solar cell material of the present invention may be used as it is in powder form, but is easy to handle when it is uniformly kneaded with a vehicle and processed into a paste. The vehicle mainly consists of a solvent and a resin. The resin is added for the purpose of adjusting the viscosity of the paste. Moreover, surfactant, a thickener, etc. can also be added as needed. The produced paste is applied onto the glass substrate using an applicator such as a dispenser or a screen printer.

  As the resin, acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used. In particular, acrylic acid esters and nitrocellulose have good thermal decomposability.

  As the solvent, N, N′-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyllactone (γ-BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triethylene glycol Propylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO), N-me -2-pyrrolidone and the like can be used. In particular, α-terpineol has high viscosity and good solubility for resins and the like.

  The dye-sensitized solar cell material of the present invention is preferably used for sealing, and particularly preferably used for sealing a transparent electrode substrate and a counter electrode substrate. Since the dye-sensitized solar cell material of the present invention has low melting point characteristics and good electrolytic solution resistance and water resistance, the long-term durability of the dye-sensitized solar cell is improved, and the long-term By using this, it is possible to prevent the battery characteristics from deteriorating.

Since the dye-sensitized solar cell material of the present invention contains 20% or more of V ₂ O ₅ in the glass composition of the glass powder, it can be subjected to a sealing treatment with a laser beam. When laser light is used, the dye-sensitized solar cell material can be locally heated, so that the transparent electrode substrate and the counter electrode substrate can be sealed while preventing thermal deterioration of the constituent members such as iodine electrolyte. When the transparent electrode substrate and the counter electrode substrate are sealed using a laser beam, the dye-sensitized solar cell material of the present invention has a glass composition of glass powder of V ₂ O ₅ of 30% or more, particularly 40% or more. It is preferable to contain. If regulated in this way, the light energy of the laser light can be efficiently converted into thermal energy, in other words, the glass can absorb the laser light accurately, so that only the part to be sealed can be locally heated accurately. it can. Various laser beams can be used as the laser beam, but a semiconductor laser, a YAG laser, a CO ₂ laser, an excimer laser, an infrared laser, and the like are preferable in terms of easy handling. Moreover, in order to make a glass absorb a laser beam exactly, it is preferable that a laser beam has an emission center wavelength of 500-1600 nm, especially 750-1300 nm.

  The dye-sensitized solar cell material of the present invention may contain a spacer such as glass beads. If it does in this way, when using for sealing of a transparent electrode substrate and a counter electrode substrate, the cell gap of a solar cell can be made uniform.

  The dye-sensitized solar cell material of the present invention is preferably used for coating the current collecting electrode. Generally, Ag is used for the current collecting electrode. However, Ag has the property of being easily eroded by iodine electrolyte. For this reason, when using Ag for a current collection electrode, it is necessary to coat | cover the surface which contact | connects an iodine electrolyte solution. Therefore, when the material for a dye-sensitized solar cell of the present invention is used, a dense coating layer can be formed at low temperature and the resistance to electrolytic solution is good, so that Ag can be protected over a long period of time. it can.

  The dye-sensitized solar cell material of the present invention can be used for forming partition walls. Since the dye-sensitized solar cell material of the present invention has a low melting point property, it can form dense barrier ribs at low temperature and has good resistance to electrolyte solution. Can be prevented. In general, the cell formed by the partition walls is filled with an iodine electrolyte.

  The present invention will be described in detail based on examples. Table 1 shows Examples (Sample Nos. 1 to 4) and Comparative Examples (Sample Nos. 5 to 8) of the present invention.

  Each sample described in the table was prepared as follows. First, a glass batch in which raw materials such as various oxides and carbonates were prepared so as to have the glass composition in the table was prepared, and this was put in a platinum crucible and melted at 1000 to 1200 ° C. for 1 to 2 hours. Next, a part of the molten glass was poured into a stainless steel mold as a sample for water resistance evaluation, and the other molten glass was formed into a flake shape with a water-cooled roller. The sample for water resistance evaluation was subjected to a predetermined slow cooling (annealing) treatment after molding. Finally, the glass flakes were pulverized with a ball mill and passed through a sieve having an opening of 75 μm to obtain glass powders having an average particle diameter of about 10 μm. Sample No. No. 8 is obtained by adding and mixing the refractory fillers (lead titanate, average particle diameter 10 μm) in the table at the ratio in the table.

Next, each glass powder (sample No. 8 is a mixed powder) and a vehicle (ethyl cellulose dissolved in α-terpineol) were kneaded to obtain a paste. This was screen-printed on a soda glass substrate (coefficient of thermal expansion: 90 × 10 ⁻⁷ / ° C.) to a thickness of 20 to 40 μm with a diameter of 40 mm, dried in an electric furnace at 120 ° C. for 10 minutes, and then 430 to 610 ° C. Was baked for 10 minutes to obtain a sample for mass reduction evaluation.

  Using the above samples, the softening point, electrolytic solution resistance and water resistance were evaluated. The results are shown in Table 1.

  The softening point was determined by a macro type DTA apparatus. The measurement was performed in air, and the rate of temperature increase was 10 ° C./min.

  Electrolytic solution resistance was evaluated as follows. First, the mass of the fired film and the surface area of the fired film in contact with the iodine electrolyte solution were measured for the sample for evaluation of mass reduction. Next, after immersing this sample in an iodine electrolyte solution in a glass sealed container, the glass sealed container is allowed to stand in a constant temperature bath at 70 ° C., and the sample after two weeks has passed from the mass of the sample before immersion. The value obtained by subtracting the mass of the fired film was divided by the surface area of the fired film to calculate the weight loss of the fired film when immersed in the iodine electrolyte, and the resistance to the electrolyte was evaluated. The iodine electrolyte was 0.1M lithium iodide, 0.05M iodine, 0.5M tert-butylpyridine, and 0.6M 1,2-dimethyl-3-propylimidazolium iodide to acetonitrile. Used.

  The water resistance was evaluated as follows. First, the mass of the bulk water resistance evaluation sample was measured. Next, this sample was immersed in pure water at 80 ° C. for 3 hours, and the mass after the immersion was measured. Note that the sample after the immersion was sufficiently dried after washing. Finally, the case where there was no mass loss was evaluated as “◯”, and the case where there was a mass loss was evaluated as “x”.

As is clear from Table 1, sample No. Nos. 1 to 4 had a softening point of 414 to 479 ° C., no mass loss was observed after immersion in iodine electrolyte solution, and water resistance was also good. On the other hand, sample No. No. ₅ had a small amount of V ₂ O ₅ in the glass composition and a large amount of P ₂ O _5, so the softening point was as high as 590 ° C. and the water resistance was poor. Sample No. Since No. 6 did not contain ZnO in the glass composition, the water resistance was poor. Sample No. Since No. 7 contained only 10 mol% of BaO in the glass composition, the water resistance was poor. Sample No. Since No. 8 is lead glass, the weight loss was 0.32 mg / cm ² and the water resistance was also poor.

  The glass composition for a dye-sensitized solar cell and the material for a dye-sensitized solar cell according to the present invention are provided by sealing a transparent electrode substrate and a counter electrode substrate of a dye-sensitized solar cell, covering a collector electrode, and between cells. It is suitable for forming partition walls for partitioning, and particularly suitable for sealing a transparent electrode substrate and a counter electrode substrate of a dye-sensitized solar cell.

Claims (6)

As a glass composition, it contains 20 to 50% of V ₂ O ₅ , 15 to 45% of P ₂ O _{5, 5 to} 35% of ZnO, and 15 to 40% of BaO in terms of the following oxide equivalent mol%. A glass composition for a sensitized solar cell.   A dye-sensitized solar cell comprising 50 to 100% by volume of a glass powder comprising the glass composition for a dye-sensitized solar cell according to claim 1 and 0 to 50% by volume of a refractory filler. Materials. The material for a dye-sensitized solar cell according to claim 2, wherein a weight loss when immersed in an iodine electrolyte at 70 ° C for 2 weeks is 0.1 mg / cm ² or less.   The material for a dye-sensitized solar cell according to claim 2 or 3, wherein the softening point is 550 ° C or lower.   The dye-sensitized solar cell material according to any one of claims 2 to 4, wherein the material is used for sealing.   The material for a dye-sensitized solar cell according to any one of claims 2 to 4, wherein the material is used for coating a collecting electrode.

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