JP2010042960A - Glass composition for dye-sensitized solar cell and material for dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell having high long-term reliability by inventing a glass composition which is hardly eroded by an iodine electrolyte solution and has low-melting point characteristics, and by inventing a material using the glass composition. <P>SOLUTION: The glass composition for a dye-sensitized solar cell includes as a glass composition 35-70% of SnO and 18-50% of P<SB>2</SB>O<SB>5</SB>, in terms of mol%. <P>COPYRIGHT: (C)2010,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, formation of partition walls, and The present invention relates to a glass composition for a dye-sensitized solar cell and a material for a dye-sensitized solar cell that are suitable for covering a collecting electrode.

  The dye-sensitized solar cell developed by Gretcher et al. Is expected to be a next-generation solar cell because it is less expensive than solar cells using silicon semiconductors and has 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 comprises 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.

By the way, the dye-sensitized solar cell is filled with an iodine electrolytic solution between the transparent electrode substrate and the counter electrode substrate. In order to prevent leakage of the 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

  For dye-sensitized solar cells, improvement of long-term reliability is an issue for practical use. As a cause of impairing the long-term reliability, the solar cell member and the iodine electrolyte solution are reacted, and the solar cell member and the iodine electrolyte solution 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 electrolytic solution, the iodine electrolytic solution leaks from the solar cell, and the battery characteristics are remarkably deteriorated. Similarly, when a resin is used for forming the partition walls or covering the collector electrode, the resin is eroded by the iodine electrolyte solution, so that the partition walls are broken and the collector electrode is deteriorated.

  In view of such circumstances, a method in which no resin is used for the sealing material has been proposed. For example, Patent Document 1 describes that the outer peripheral edges of a transparent electrode substrate and a counter electrode substrate are sealed with glass. Patent Documents 2 and 3 describe sealing the outer peripheral edges of the transparent electrode substrate and the counter electrode substrate with lead glass.

  However, even when lead glass is used as the sealing material, lead glass is easily eroded by the iodine electrolyte, and as a result, the components of the lead glass are eluted into the iodine electrolyte due to long-term use. The electrolytic solution deteriorates and the battery characteristics are deteriorated. Even when lead glass is used for the formation of the partition walls or the covering of the current collecting electrodes, the partition walls are broken or the current collecting electrodes are deteriorated by long-term use. These phenomena are also caused by the erosion of lead glass by iodine electrolyte.

  If the softening point of the sealing material is higher than the strain point of the glass substrate, the glass substrate is deformed in the sealing step. Therefore, the sealing material (glass used for the sealing material) is required to have a low melting point characteristic, for example, a softening point of 550 ° C. or lower, preferably 500 ° C. or lower.

  Therefore, the present invention provides a technology for obtaining a dye-sensitized solar cell with high long-term reliability by creating a glass composition and a material using the glass composition that are hardly eroded by iodine electrolyte and have low melting point characteristics. As an objective.

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 SnO and P ₂ O ₅ as essential components in the glass composition, and proposes the present invention. Is. That is, the glass composition for dye-sensitized solar cells of the present invention is characterized by containing SnO 35 to 70% and P ₂ O ₅ 18 to 50% in terms of glass composition. In addition, when SnO and P ₂ O ₅ are introduced into the glass composition in predetermined amounts, the mechanism that makes the glass difficult to be eroded by the iodine electrolyte is unknown at present, and is currently under intensive investigation.

Secondly, the dye-sensitized solar cell glass composition of the present invention, further, as a glass composition, in _{mol%, 0~30% ZnO, B 2} O 3 0~20%, SiO 2 0~10% , Al ₂ O _{3 is} contained in an amount of 0 to 10%.

Third, the dye-sensitized solar cell glass composition of the present invention, further, as a glass composition, in _{mol%, In 2 O 3 0~5%} , Ta 2 O 5 0~5%, La 2 O _{3 0~15%, MoO 3 0~5%} , WO 3 0~15%, Li 2 O 0~5%, Na 2 O 0~10%, K 2 O 0~5%, 0~15% MgO, BaO _0%, characterized by containing F 2 0 to 5%.

Fourth, the glass composition for a dye-sensitized solar cell of the present invention is characterized in that the mass loss when immersed in an iodine electrolyte solution at 25 ° C. for 2 weeks is 0.1 mg / cm ² or less. . Here, the iodine electrolyte used for the calculation of mass loss includes 0.1M lithium iodide, 0.05M iodine, 0.5M tert-butylpyridine, and 1,2-dimethyl-3-propylimidazo in acetonitrile. A solution in which 0.6M of lithium iodide is dissolved is used. Further, “mass loss” means that a glass substrate (a glass substrate with a fired film) on which the glass powder made of the glass composition is finely baked is immersed in an iodine electrolytic solution in a sealed container, and 2% from the mass before immersion. 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. Note that a glass substrate that is not eroded by the iodine electrolyte is used.

In general, an iodine electrolytic solution refers to an iodine compound such as iodine, alkali metal iodide, imidazolium iodide, quaternary ammonium salt or the like dissolved in an organic solvent. Some have dissolved pyridine, 1 methoxybenzimidazole and the like. 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 glass composition for a dye-sensitized solar cell of the present invention has a mass loss when immersed for 2 weeks at 25 ° C. in an iodine electrolyte solution in which the glass is actually in contact with the dye-sensitized solar cell. It is preferably 0.1 mg / cm ² or less.

Fifth, the glass composition for a dye-sensitized solar cell of the present invention has a thermal expansion coefficient of 65 to 120 × 10 ⁻⁷ / ° C. Here, the “thermal expansion coefficient” refers to a value measured in a temperature range of 30 to 250 ° C. by a push rod type thermal expansion coefficient measurement (TMA) apparatus.

  Sixth, the material for a dye-sensitized solar cell of the present invention contains 50 to 100% by volume of a glass powder made of the above-described glass composition for a dye-sensitized solar cell, and 0 to 50% by volume of a refractory filler powder. It is characterized by doing. In addition, the dye-sensitized solar cell material of the present invention does not contain a refractory filler powder, and includes an embodiment composed only of glass powder made of the above glass composition.

  Seventh, the dye-sensitized solar cell material of the present invention has a softening point of 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.

  Eighth, the dye-sensitized solar cell material of the present invention is characterized by being used for sealing.

  Ninth, the dye-sensitized solar cell material of the present invention is characterized in that it is used for protecting a collecting electrode.

The glass composition for a dye-sensitized solar cell of the present invention contains a predetermined amount of SnO and P ₂ O ₅ in the glass composition, so that erosion by the iodine electrolyte hardly occurs and the iodine electrolyte at 25 ° C. As a result of the mass loss of 0.1 mg / cm ² or less when soaked in 2 weeks, the solar cell member and the iodine electrolyte are less likely to deteriorate over a long period of time, and the partition wall breakage and the collector electrode deterioration are prevented. can do.

  The reason why the glass composition range is limited 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.

  SnO is a component that lowers the melting point of glass and is an essential component. Its content is 35 to 70%, preferably 40 to 65%, more preferably 55 to 63%. In particular, if the SnO content is 40% or more, the fluidity of the glass can be improved, and the airtight reliability can be improved. If the SnO content is less than 30%, the viscosity of the glass becomes too high, and the sealing temperature may be unduly high. On the other hand, if the SnO content is more than 70%, vitrification tends to be difficult.

P ₂ O ₅ is a glass-forming oxide and a component that makes it difficult to cause erosion by the iodine electrolyte, and is a component that lowers the melting point of the glass, and its content is 18 to 50%, preferably It is 23 to 40%, more preferably 25 to 35%. When the content of P ₂ O ₅ is less than 18%, the thermal stability of the glass tends to be lowered. On the other hand, if the content of P ₂ O ₅ is more than 50%, the water resistance of the glass is lowered and it is difficult to ensure long-term reliability.

  In addition to the above components, the glass composition for dye-sensitized solar cells of the present invention can contain up to 40% of the following components in the glass composition.

  ZnO is an intermediate oxide and a component that stabilizes the glass. Its content is 0-30%, preferably 0-20%, more preferably 3-15%. In particular, if the ZnO content is 3% or more, the thermal stability of the glass can be enhanced. On the other hand, when ZnO is more than 30%, the thermal stability of the glass tends to be lowered.

B ₂ O ₃ is a glass-forming oxide and a component that stabilizes the glass. Its content is 0 to 20%, preferably 0 to 16%. When the content of B ₂ O ₃ is greater than 20%, too high the viscosity of the glass, the flow resistance of the glass tends to decrease.

SiO ₂ is a glass-forming oxide and is a component that stabilizes the glass. Its content is 0-15%, preferably 0-5%. If the content of SiO ₂ is more than 15%, the softening temperature of the glass rises and it becomes difficult to seal at a low temperature.

Al ₂ O ₃ is an intermediate oxide, a component that stabilizes the glass, and a component that lowers the thermal expansion coefficient of the glass, and its content is 0 to 10%, preferably 0 to 5%. is there. When the content of Al ₂ O ₃ is more than 10%, the glass softening temperature is unduly increased, it becomes difficult to sealing at low temperatures.

In ₂ O ₃ is a component that improves the thermal stability of the glass, and its content is 0 to 5%. When the content of In ₂ O ₃ is more than 5%, the batch cost increases.

Ta ₂ O ₅ is a component that improves the thermal stability of the glass, and its content is 0 to 5%. When the content of Ta ₂ O ₅ is more than 5%, the glass softening temperature is unduly increased, it becomes difficult to sealing at low temperatures.

La ₂ O ₃ is a component that improves the thermal stability of glass and a component that improves the weather resistance of glass, and its content is 0 to 15%, preferably 0 to 10%, more preferably. 0 to 5%. When the content of La ₂ O ₃ is more than 15%, the glass softening temperature is unduly increased, it becomes difficult to sealing at low temperatures.

MoO ₃ is a component that improves the thermal stability of the glass, and its content is 0 to 5%. When the content of MoO ₃ is more than 5%, the softening temperature of the glass is unduly raised, and it becomes difficult to seal at a low temperature.

WO ₃ is a component that improves the thermal stability of the glass, and its content is 0 to 5%. If the content of WO ₃ is more than 5%, the softening temperature of the glass will unduly rise and it will be difficult to seal at low temperatures.

Li ₂ O is a component that lowers the melting point of glass, and its content is 0 to 5%. The content of Li 2 _O is more than 5%, the thermal stability of the glass tends to decrease.

Na ₂ O is a component that lowers the melting point of glass, and its content is 0 to 10%, preferably 0 to 5%. When the content of Na 2 _O is greater than 10%, thermal stability of the glass tends to decrease.

K ₂ O is a component that lowers the melting point of glass, and its content is 0 to 5%. When the content of K 2 _O is more than 5%, the thermal stability of the glass tends to decrease.

  MgO is a component that improves the thermal stability of the glass, and its content is 0 to 15%. When the content of MgO is more than 15%, the component balance of the glass composition is impaired, and conversely, the glass is easily devitrified.

  BaO is a component that improves the thermal stability of the glass, and its content is 0 to 10%. When the content of BaO is more than 10%, the component balance of the glass composition is impaired, and conversely, the glass is easily devitrified.

F ₂ is a component to lower the melting point of the glass, the content thereof is 0 to 5%. When the content of F ₂ is greater than 5%, the thermal stability of the glass tends to decrease.

In consideration of the balance of thermal stability and low melting point characteristics of glass, In ₂ O ₃ , Ta ₂ O ₅ , La ₂ O ₃ , MoO ₃ , WO ₃ , Li ₂ O, Na ₂ O, K ₂ O, The total amount of MgO, BaO and F ₂ is preferably 15% or less.

  In addition, it is preferable that the glass composition for dye-sensitized solar cells of this invention does not contain PbO substantially from an environmental viewpoint and the viewpoint which prevents the corrosion by an iodine electrolyte solution. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is 1000 ppm (mass) or less.

In the glass composition for a dye-sensitized solar cell of the present invention, the mass loss when immersed in an iodine electrolyte at 25 ° C. for 2 weeks is 0.1 mg / cm ² or less, preferably 0.05 mg / cm ² or less. A state where there is substantially no weight loss is more preferable. If the mass loss when immersed in an iodine electrolyte at 25 ° C. for 2 weeks is 0.1 mg / cm ² or less, it is possible to prevent deterioration of the iodine electrolyte and 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 glass composition for a dye-sensitized solar cell of the present invention, the thermal expansion coefficient is preferably 65 to 120 × 10 ⁻⁷ / ° C., more preferably 80 to 110 × 10 ⁻⁷ / ° C. If the difference in thermal expansion coefficient between the glass composition for a dye-sensitized solar cell of the present invention and a glass substrate (for example, soda glass substrate) used for a transparent electrode substrate or the like is too large, the glass substrate or sealing site after firing. Unreasonable stress remains, and cracks are likely to occur in the glass substrate, the sealing part, etc., or the sealing part is easily peeled off.

  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 smaller and more uniform, and the mixing process of the refractory filler powder or the like is not required, thereby reducing the manufacturing cost of the dye-sensitized solar cell material. can do.

  The dye-sensitized solar cell material of the present invention may contain a refractory filler powder in order to improve the mechanical strength or lower the thermal expansion coefficient, and the mixing amount thereof is 50 to 100 volume of glass powder. %, Refractory filler powder 0 to 50% by volume, preferably 65 to 100% by volume of glass powder, and 0 to 35% by volume of refractory filler powder. When there is more content of a refractory filler powder than 50 volume%, the ratio of glass powder will become comparatively too low, and it will become difficult to obtain desired fluidity | liquidity.

  Since the cell gap of a dye-sensitized solar cell is generally very small as 50 μm or less, if the particle size of the refractory filler powder is too large, protrusions are locally generated at the sealing site. It becomes difficult to make the gap uniform. In order to prevent such a situation, the maximum particle size of the refractory filler powder is preferably 25 μm or less, and more preferably 15 μm or less. Here, the “maximum particle diameter” refers to a value measured by a laser diffraction method, and refers to a particle diameter with an integrated particle diameter of 99% (volume).

The material of the refractory filler powder is not particularly limited, but it is preferable that the refractory filler powder does not easily react with the glass powder and the iodine electrolyte solution made of the dye-sensitized solar cell glass composition of the present invention. Specifically, as refractory filler powder, zircon, zirconia, tin oxide, aluminum titanate, quartz, β-spodumene, cordierite, mullite, titania, quartz glass, β-eucryptite, β-quartz, phosphorus Zirconium oxide, zirconium tungstate phosphate, zirconium tungstate, willemite, 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.

In the dye-sensitized solar cell material of the present invention, the softening point is preferably 550 ° C. or lower, 500 ° C. or lower, particularly 450 ° C. or lower. When the softening point is higher than 550 ° C., the viscosity of the glass becomes too high, the sealing temperature is unduly increased, and the glass substrate is likely to be deformed. Even in the case of co-firing with a porous oxide semiconductor (mainly TiO ₂ ) layer, if the sealing temperature is too high, fusion with oxide particles proceeds and it becomes difficult to form a porous layer.

  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 includes a solvent and a resin, and 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 using an applicator such as a dispenser or a screen printer.

The resin binder preferably has a low decomposition temperature and a small amount of residue after firing, and it is preferable that the SnO—P ₂ O ₅ glass is not easily altered. Specifically, nitrocellulose, polyethylene glycol derivatives, and polyethylene carbonate are used. Is preferred.

The solvent preferably has a low boiling point (for example, a boiling point of 300 ° C. or lower) and a small amount of residue after firing, and does not alter the SnO—P ₂ O ₅ glass, specifically, toluene, N , N′-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl carbonate, butyl carbitol acetate (BCA), isoamyl acetate, propylene carbonate, N-methyl-2-pyrrolidone acetonitrile , Dimethyl sulfoxide, acetone, methyl ethyl ketone and the like are preferable. Moreover, it is preferable to use a higher alcohol as a solvent. The higher alcohol can be made into a paste without adding a resin binder to the vehicle because the solvent itself has viscosity. When the resin binder is not added to the vehicle, tin in the SnO—P ₂ O ₅ glass is difficult to be oxidized from divalent to tetravalent, and as a result, the glass is hardly deteriorated during firing. As the higher alcohol, isoicosyl alcohol can be used from isohexyl alcohol represented by CnC _{2n + 1} OH (n = 8 to 20). When the molecular weight of the higher alcohol is increased to isodecyl alcohol (n = 10) or more, it becomes easy to ensure an appropriate viscosity when mixed with the dye-sensitized solar cell material. Further, if the molecular weight of the higher alcohol is made to be less than isohexadecyl alcohol (n = 16), the amount of residue after firing can be reduced. Considering the above points, isotridecyl alcohol is most preferable as a higher alcohol because it has a good balance between viscosity and residual amount. Furthermore, pentanediol and its derivatives, specifically diethylpentanediol (C ₉ H ₂₀ O ₂ ) are also excellent in viscosity and can be used as a solvent.

  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 a low melting point property and is not easily eroded by iodine electrolyte solution, the iodine electrolyte solution is less likely to leak through long-term use, thereby extending the life of the solar cell. Can be planned. Further, when used for sealing the transparent electrode substrate and the counter electrode substrate, a spacer such as glass beads may be added to the dye-sensitized solar cell material of the present invention in order to make the cell gap of the solar cell 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, but Ag is easily eroded by the iodine electrolyte. Due to this, when Ag is used for the current collecting electrode, it is necessary to protect the current collecting electrode. Since the dye-sensitized solar cell material of the present invention has a low melting point characteristic, it can form a dense coating layer at low temperature and is not easily eroded by iodine electrolyte solution. Can be protected. Moreover, the dye-sensitized solar cell material of the present invention can also be used to form partition walls.

  The present invention will be described in detail based on examples. Table 1 shows examples of the present invention (samples A to G) and a comparative example (sample H).

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 into an alumina crucible. Samples A, B, D, E, F, and H were covered with an alumina crucible and melted in the atmosphere at 900 ° C. for 2 hours. Sample C was melted at 900 ° C. for 2 hours while bubbling the molten glass with N ₂ gas at a flow rate of 1 L / min after flowing N ₂ gas at a flow rate of 3 L / min in the electric furnace. Sample G was melted at 900 ° C. for 2 hours while bubbling the molten glass with N ₂ gas at a flow rate of 1 L / min after flowing N ₂ gas at a flow rate of 3 L / min in the electric furnace, and then melted. While maintaining the temperature, the pressure was reduced to 50 Torr, and the reduced pressure state was maintained for 1 hour to remove gas components remaining in the molten glass. Next, a part of the molten glass was poured into a stainless steel mold as a sample for measuring the coefficient of thermal expansion, and the other molten glass was formed into a thin piece with a water-cooled roller. The sample for measuring the thermal expansion coefficient was subjected to a predetermined slow cooling (annealing) treatment after molding. Finally, the glass flakes were pulverized by a ball mill and passed through a sieve having an opening of 25 μm to obtain glass powders having an average particle diameter D ₅₀ of about 5 μm.

  Next, each glass powder and a vehicle made of pentanediol and propanediol were kneaded to form a paste. The obtained paste was screen-printed on a soda glass substrate so as to have a diameter of 40 mm and a thickness of 40 to 80 μm, dried in an electric furnace at 120 ° C. for 10 minutes, and then at the temperature and the atmosphere shown in the table for 30 minutes It baked and it was set as the sample for a measurement of the mass loss with respect to an iodine electrolyte solution.

  Using the above samples, the thermal expansion coefficient, softening point, and mass loss with respect to iodine electrolyte were evaluated. The results are shown in Table 1.

  The thermal expansion coefficient was measured by a push rod type thermal expansion coefficient measuring device in a temperature range of 30 to 250 ° C.

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

  The weight loss was calculated as follows. First, after measuring the mass of the measurement sample and the surface area of the fired film in contact with the iodine electrolyte, the measurement sample is immersed in an iodine electrolyte in a glass sealed container, and the glass sealed container is placed in a thermostatic bath at 25 ° C. Was allowed to stand. Next, the mass reduction was calculated by dividing the value obtained by subtracting the mass of the measurement sample after two weeks from the mass of the measurement sample before immersion by the surface area of the fired film. The iodine electrolyte used for the above measurement was 0.1M lithium iodide, 0.05M iodine, 0.5M tert-butylpyridine, and 1,2-dimethyl-3-propylimidazolium iodide with respect to acetonitrile. What added 0.6M was used.

As apparent from Table 1, the samples A to G had an expansion coefficient of 71 to 118 × 10 ⁻⁷ / ° C. and a softening point of 375 to 440 ° C. Moreover, in any sample, the fired film was not peeled off and was in good contact with the glass substrate. Furthermore, samples A to G were not able to confirm mass loss and were not easily eroded by iodine electrolyte. On the other hand, since the sample H used lead glass, the mass loss was 0.32 mg / cm ² and was eroded by the iodine electrolyte.

  The glass composition for a dye-sensitized solar cell and the material for a dye-sensitized solar cell according to the present invention include sealing a transparent electrode substrate and a counter electrode substrate of a dye-sensitized solar cell, forming a partition wall, and covering a collecting electrode. It is suitable for etc.

It is a schematic diagram which shows the softening point of glass when it measures with a macro type | mold DTA apparatus.

Claims (9)

A glass composition for a dye-sensitized solar cell, comprising, as a glass composition, mol%, SnO 35 to 70% and P ₂ O ₅ 18 to 50%. Further, as a glass composition, in _{mol%, 0~30% ZnO, B 2} O 3 0~20%, SiO 2 0~10%, claim, characterized in that it contains _Al 2 O 3 _0~10% 1 The glass composition for dye-sensitized solar cells as described in 1 above. Further, as a glass composition, in _{mol%, In 2 O 3 0~5%} , Ta 2 O 5 0~5%, La 2 O 3 0~15%, MoO 3 0~5%, WO 3 0~15% , Li ₂ O 0-5%, Na ₂ O 0-10%, K ₂ O 0-5%, MgO 0-15%, BaO 0-10%, F ₂ 0-5% The glass composition for dye-sensitized solar cells according to claim 1 or 2. The glass composition for a dye-sensitized solar cell according to any one of claims 1 to 3, wherein a weight loss when immersed in an iodine electrolyte at 25 ° C for 2 weeks is 0.1 mg / cm ² or less. object. The coefficient of thermal expansion is 65 to 120 × 10 ⁻⁷ / ° C., The glass composition for a dye-sensitized solar cell according to claim 1.   A dye comprising 50 to 100% by volume of a glass powder comprising the glass composition for a dye-sensitized solar cell according to any one of claims 1 to 5, and 0 to 50% by volume of a refractory filler powder. Material for sensitized solar cells.   The material for a dye-sensitized solar cell according to claim 6, wherein the softening point is 550 ° C or lower.   The dye-sensitized solar cell material according to claim 6 or 7, which is used for sealing.   The material for a dye-sensitized solar cell according to claim 6 or 7, which is used for protecting a collecting electrode.