JP2013155059A - Glass composition for dye-sensitized solar cell and material for the dye-sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve 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 in electrolyte resistance.SOLUTION: A glass composition for a dye-sensitized solar cell comprises, as a glass composition, 26-60 mol% VO, 20-48 mol% TeO, 6-35 mol% ZnO and 0.1-18 mol% BaO, calculated in terms of oxides. A material for a dye-sensitized solar cell comprises 50-100 vol% glass powder comprising the glass composition for a dye-sensitized solar cell and 0-50 vol% refractory filler.

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 that are suitable for coating, formation of partition walls for separating cells, and the like.

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

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 for 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.

  Also, if the softening point of the sealing material is too high, especially if it 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 are deformed during sealing. There is a fear. Accordingly, 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 500 ° C. or lower, particularly 450 ° C. or lower.

  Therefore, the present invention has been made in view of the above circumstances, and the technical problem thereof is a glass composition for dye-sensitized solar cells and a dye having low melting point characteristics and excellent electrolytic solution resistance. By providing a material for a sensitized solar cell, the long-term durability of the dye-sensitized solar cell is enhanced.

As a result of various studies, the present inventors have found that the above technical problem can be solved by introducing a predetermined amount of V ₂ O ₅ , TeO ₂ , ZnO, and BaO as essential components into the glass composition. This is proposed as the present invention. That is, the glass composition for dye-sensitized solar cells of the present invention has a glass composition of mol% in terms of the following oxides: V ₂ O ₅ 26 to 60%, TeO _{2 20 to} 48%, ZnO 6 to 35. %, BaO 0.1 to 18%.

The glass composition for a dye-sensitized solar cell of the present invention includes a predetermined amount of V ₂ O ₅ , TeO ₂ , ZnO, and BaO in the glass composition, and thus has a low melting point characteristic and has an electrolyte solution resistance. It is 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. In general, a glass having a low softening point tends to have low water resistance. However, the glass composition for dye-sensitized solar cell of the present invention contains a predetermined amount of V ₂ O ₅ , TeO ₂ , ZnO, and BaO in the glass composition, so that the water resistance is low even though the softening point is low. Is good.

  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.

The material for a dye-sensitized solar cell of the present invention includes a predetermined amount of V ₂ O ₅ , TeO ₂ , ZnO, and BaO in the glass composition of the glass powder, and thus has a low melting point property and is resistant to an electrolytic solution. (In particular, the weight loss when immersed in an iodine electrolyte at 70 ° C. for 2 weeks is 0.1 mg / cm ² or less) and the water resistance is 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.

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, the “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, 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 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.

  Fourth, the dye-sensitized solar cell material of the present invention has a softening point of 500 ° 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. When measured with a macro DTA apparatus, the softening point is the temperature (Ts) of the fourth 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.

It is the schematic which shows a softening point (Ts) when it measures with a macro type | mold 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, in description of the content range of each component,% display points out mol% except the case where 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 26 to 60%, preferably 28 to 50%. If the content of V ₂ O ₅ is too small, the viscosity (softening point and the like) of the glass increases, and the firing temperature (sealing temperature and the like) increases. On the other hand, when the content of V ₂ O ₅ is too large, glass becomes thermally unstable, and water resistance tends to decrease.

TeO ₂ is a component that lowers the softening point and increases water resistance, and its content is 20 to 48%, preferably 20 to 45%. When the content of TeO ₂ is too small, the viscosity of the glass increases, so that the firing temperature increases and the water resistance decreases. On the other hand, when the content of TeO ₂ is too large, the glass becomes thermally unstable, the glass tends to be devitrified at the time of melting or firing, and the thermal expansion coefficient is greatly increased. It becomes difficult to match the thermal expansion coefficient.

  ZnO is a component that thermally stabilizes the glass and increases water resistance, and its content is 6 to 35%, preferably 6 to 30%. If the ZnO content is too small, the glass becomes thermally unstable, and the glass tends to devitrify during melting or firing. On the other hand, when the content of ZnO is too large, the component balance of the glass composition is impaired, and on the contrary, the glass becomes thermally unstable and the viscosity of the glass increases, so that the firing temperature rises.

  BaO is a component that thermally stabilizes the glass and enhances water resistance, and its content is 0.1 to 18%, preferably 2 to 18%. When there is too 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, for example, the following components may be added to the glass composition.

P ₂ O ₅ is a component that forms a glass network, and the content thereof is preferably 0 to 20%, more preferably 0 to 10%. When the content of P ₂ O ₅ is too large, the glass viscosity is higher, the firing temperature increases, also the water resistance tends to decrease.

  SrO is a component that stabilizes the glass thermally and suppresses devitrification, and is a component that lowers the viscosity of the glass, and its content is preferably 0 to 20%, more preferably 0 to 0%. 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 thermally stabilizes the glass and suppresses devitrification, and is a component that increases water resistance, and its content is preferably 0 to 10%, more preferably 0 to 8%. It is. When there is too much content of CuO, since the viscosity of glass will become high, a calcination temperature will rise.

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

Bi ₂ O ₃ is a component for enhancing water resistance, its content is preferably 0-10%, more preferably 1 to 5%. If the content of Bi ₂ O ₃ is too large, the viscosity of the glass becomes too high, the firing temperature is increased easily.

In addition to the above components, other components such as CaO, MgO, B ₂ O ₃ , Fe ₂ O ₃ , and SiO ₂ may be added to the glass composition up to 10%.

  In addition, in order to improve electrolyte solution resistance, it is preferable not to contain PbO substantially. Here, “substantially does not contain PbO” refers to a case where the content of PbO in the glass composition is less than 1000 ppm (mass). In addition, if it is set as the aspect which does not contain PbO substantially, the recent environmental request | requirement can also be satisfy | filled.

In the dye-sensitized solar cell material of the present invention, the average particle diameter _{D 50} of the glass powder less than 15 [mu] m, particularly 1~10μm preferred. When regulating the average particle diameter D ₅₀ of the glass powder to less than 15 [mu] m, with the flowability of the sealing material increases, liable to narrow the sealing thickness, in such a case, the thermal expansion coefficient of the glass substrate and the sealing material Even if the difference is large, cracks or the like hardly occur in the glass substrate or the sealing portion.

  The material for a dye-sensitized solar cell of the present invention may be 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 becomes unnecessary, thereby reducing the manufacturing cost of the dye-sensitized solar cell material. 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 and 0 to 50% by volume of refractory filler, more preferably 50 to 95% by volume of glass powder and 5 to 50% by volume of refractory filler, and 50 to 90 volume of glass powder. %, Refractory filler 10 to 50% by volume is more preferred, glass powder 50 to 80% by volume, and refractory filler 20 to 50% by volume is particularly preferred. 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.

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. The cell gap of the dye-sensitized solar cell is very thin (for example, 50 μm or less). For this reason, if the maximum particle diameter of the refractory filler is too large, it becomes difficult to properly 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 500 ° C. or lower, particularly preferably 450 ° C. or lower. If the softening point is too high, the viscosity of the glass becomes high, so that the firing temperature (especially the sealing temperature) rises unreasonably, and the transparent electrode substrate and the counter electrode substrate are easily deformed during firing. Also, 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, It becomes difficult to form the porous oxide semiconductor layer, and 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 × 10 ^{−7 to} 120 × 10 ⁻⁷ / ° C., particularly preferably 75 × 10 ^{−7 to} 115 × 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 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 250 ° 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 glass powder contains 26 mol% or more of V ₂ O ₅ in the glass composition, the dye-sensitized solar cell material of the present invention can be subjected to 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 material for a dye-sensitized solar cell of the present invention seals a transparent electrode substrate and a counter electrode substrate using laser light, the glass powder may contain 30% mol or more of V ₂ O ₅ as a glass composition. preferable. In this way, the light energy of the laser light can be efficiently converted into thermal energy. In other words, since the glass can absorb the laser light accurately, only the part to be sealed can be locally heated accurately. . 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 electrolyte solution resistance, so that the barrier ribs can be broken for a long period of time. 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. Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 12) and comparative examples (sample No. 13). The following examples are merely illustrative. The present invention is not limited to the following examples.

  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, the molten glass was formed into a thin piece with a water-cooled roller. 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.

  Subsequently, the refractory filler (average particle diameter 10 μm) in the table was added and mixed. 1 to 11 and 13 were produced. In the table, “ZP” indicates zirconium phosphate, “ZWP” indicates zirconium tungstate phosphate, and “ZS” indicates zircon.

Subsequently, each 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 (thermal expansion coefficient: 85 × 10 ⁻⁷ / ° C.) so as to be 20 to 40 μm in thickness of 40 mm, dried in an electric furnace at 120 ° C. for 10 minutes, and then 350 to 420 ° C. Was baked for 10 minutes to obtain a sample for mass reduction evaluation.

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

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

  A thermal expansion coefficient is the value measured in the temperature range of 30-250 degreeC with the push rod type | formula thermal expansion coefficient measurement (TMA) apparatus. In addition, as a measurement sample, a sample in which each sample was densely sintered was used.

  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.

As is apparent from the table, sample No. In Nos. 1 to 12, the softening point was sufficiently low, and no mass loss after immersion in iodine electrolyte was observed. On the other hand, Sample No. Since 13 is lead glass, the mass loss was 0.32 mg / cm ² .

  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, covering a collecting electrode, and between cells. It is suitable for the formation of the partition wall for separating the substrate, and particularly suitable for sealing the transparent electrode substrate and the counter electrode substrate of the dye-sensitized solar cell.

Claims (6)

As a glass composition, which in mole percent terms of _{oxide, V 2 O 5 26~60%,} TeO 2 20~48%, ZnO 6~35%, characterized in that it contains 0.1 to 18% BaO A glass composition for a dye-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 500 ° C or lower.   It uses for sealing, The material for dye-sensitized solar cells as described in any one of Claims 2-4 characterized by the above-mentioned.   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.