JP2010280554A - Glass for dye-sensitized solar cell, and material for dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a dye-sensitized solar cell having high long-term reliability by creating a glass hard to be eroded in an iodine electrolyte, and a material using the same. <P>SOLUTION: In the glass for a dye-sensitized solar cell, the average ion radius of cations in a glass composition is ≤0.80 Å. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a glass for a dye-sensitized solar cell and a material for a dye-sensitized solar cell, and specifically to sealing of a transparent electrode substrate and a counter electrode substrate of a dye-sensitized solar cell and covering of a collecting electrode. The present invention relates to a suitable dye-sensitized solar cell glass and a dye-sensitized solar cell material.

  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. Under such circumstances, in recent years, a glass substrate has been used as a 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 iodine electrolyte from leaking 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 2004-292247 A

R. D. Shannon, “Revised effective radicals and systematic studies of intermediaries in halides and charcogenides”, Acta Cryst, 1976, A32, 751-767.

  In dye-sensitized solar cells, improvement of long-term durability is a problem for practical use. One of the causes of impairing the long-term durability is that the solar cell member (collecting electrode, sealing material, 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 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 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.

  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, since lead glass is easily eroded by iodine electrolyte, even when lead glass is used as a sealing material, the components of lead glass are eluted in iodine electrolyte by long-term use. The electrolytic solution deteriorates and the battery characteristics are deteriorated. 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 erosion of lead glass by iodine electrolyte.

  Therefore, the present invention has a technical problem of obtaining a dye-sensitized solar cell with high long-term reliability by creating a glass that is not easily eroded by iodine electrolyte and a material using the glass.

  As a result of various studies, the present inventors have found that the above technical problem can be solved by regulating the average ionic radius of the cation in the glass composition to a predetermined range, and propose as the present invention. is there. Here, as the “ion radius”, the value described in [Non-Patent Document 1] is used, and the ionic radius at the time of 6-coordination is used, except for the case where the structure is clear.

The erosion mechanism of glass is mainly because iodine ions (I ₃ ⁻ ) break the bond between cations and oxygen constituting the glass network structure. The glass for a dye-sensitized solar cell according to the present invention is characterized in that the average ionic radius of the cation in the glass composition is 0.80 mm or less. The smaller the ionic radius of the cation, the more the cation attracts oxygen. Increases, the distance between the two decreases, and the structure becomes dense. For this reason, iodine ions (I ₃ ⁻ ) having a large ion radius do not easily enter the glass structure, and as a result, it is difficult to break the bond between the cation and oxygen constituting the glass network structure.

Second, the glass for a dye-sensitized solar cell of the present invention has a value obtained by dividing [the average valence of cations in the glass composition] by [the square of the average ionic radius of cations in the glass composition]. 30 / Å ² or more. The strength of the electric field generated by the cation increases as the cation valence increases and the cation radius decreases, and is indicated by a value obtained by dividing the cation valence by the square of the ion radius. When the strength of the electric field generated by the cation increases, the cation attracts more oxygen, and the structure becomes dense, so that it becomes difficult for iodine ions (I ₃ ⁻ ) having a large ionic radius to enter. It becomes difficult to break the bond between the cation and oxygen constituting the structure.

Third, the glass for a dye-sensitized solar cell of the present invention has an average ionic radius of cations in the glass composition of 0.80 mm or less, and the [average valence of cations in the glass composition] is [glass composition]. and wherein the value obtained by dividing the square] of the average ionic radius in the cation is 4.30 / Å ² or more.

Fourth, the glass for a dye-sensitized solar cell of the present invention is characterized in that the mass loss when immersed in an iodine electrolyte at 25 ° C. for 2 weeks is 0.14 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. In addition, “mass loss” means that a glass substrate (glass substrate with a fired film baked at a temperature equal to or higher than the softening point of the glass powder) obtained by densely baking the glass powder made of the above glass into an iodine electrolytic solution in a sealed container. It is calculated by immersing and dividing the value obtained by subtracting the mass after two weeks from the mass before immersion 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 glass of the present invention preferably has a mass loss of 0.14 mg / cm ² or less when immersed in these iodine electrolytes at 25 ° C. for 2 weeks.

Fifth, the glass for a dye-sensitized solar cell of the present invention is characterized in that the mass loss when immersed in an iodine electrolyte at 25 ° C. for 2 weeks is 0.1 mg / cm ² or less.

Sixth, the glass for a dye-sensitized solar cell of the present invention has a thermal expansion coefficient of 65 to 120 × 10 ⁻⁷ / ° C.

  Seventh, 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 glass for a dye-sensitized solar cell and 0 to 50% by volume of a refractory filler powder. It is characterized by doing. Here, the dye-sensitized solar cell material of the present invention includes an embodiment composed only of glass powder made of the above-described dye-sensitized solar cell glass. In the dye-sensitized solar cell material of the present invention, the content of the refractory filler powder is preferably 10% by volume or less, 5% by volume or less, and particularly preferably 1% by volume or less, from the viewpoint of fluidity. It is more preferable not to contain the refractory filler powder (specifically, the content of the refractory filler powder is 0.5% by volume or less). In particular, when used for sealing, if the content of the refractory filler powder is reduced, the gap between the transparent electrode substrate and the counter electrode substrate can be easily narrowed and uniformized.

  Eighth, 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.

  Ninth, 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 glass tube is sealed with the material for the dye-sensitized solar cell of the present invention, leakage of liquid or the like hardly occurs.

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

  Eleventh, the dye-sensitized solar cell material of the present invention is characterized by being subjected to a sealing treatment with a laser beam.

In the glass for a dye-sensitized solar cell of the present invention, erosion by the iodine electrolyte is remarkably suppressed by regulating the average ionic radius of the cation in the glass composition to 0.80 mm or less. Further, dye-sensitized solar cell glass of the present invention, 25 ° C. iodine electrolyte 2 weeks immersed in the mass down to 0.14 mg / cm ² or less when, in particular to the 0.1 mg / cm ² or less Can do. As a result, the sealing, covering, and partition wall portions are less likely to be eroded by the iodine electrolyte solution, and deterioration of the iodine electrolyte solution and battery characteristics can be prevented over a long period of time.

It is data which shows the relationship between the average ionic radius of the cation in a glass composition, and the erosion amount by an iodine electrolyte. It is a schematic diagram which shows the softening point of glass when it measures with a macro type | mold DTA apparatus. It is data showing the relationship between the value obtained by dividing [the average valence of cations in the glass composition] by [the square of the average ionic radius of cations in the glass composition] and the amount of erosion by the iodine electrolyte.

In the glass for a dye-sensitized solar cell of the present invention, the average ionic radius of the cation in the glass composition is 0.80 cm or less, preferably 0.78 cm or less, more preferably 0.76 cm or less. When the average ionic radius of the cation in the glass composition is larger than 0.80 mm, the cation constituting the glass network structure has a small force to attract oxygen, and the distance between the cation and oxygen is increased so that the iodine ion (I ₃ ^-) enters, iodine ions (I ₃ ^- becomes by) likely to be cut binding cations and oxygen.

In the glass for a dye-sensitized solar cell of the present invention, the value obtained by dividing [the average valence of cations in the glass composition] by [the square of the average ionic radius of cations in the glass composition] is 4.30 / Å ^2. above, 4.40 / Å ² or more, particularly 4.50 / Å ² or more. And this value is 4.30 / Å ² less than the cation is a force to attract oxygen is small, the glass structure becomes sparse, iodine ions (I ₃ ^-) enters the glass network structure, the binding of cations and oxygen Becomes easier to cut.

In the glass for a dye-sensitized solar cell of the present invention, the average ionic radius of cations in the glass composition is 0.80 mm or less, and the [average valence of cations in the glass composition] is set to [cations in the glass composition]. to the average value obtained by dividing the square] ion radius 4.30 / Å ² or more, Si in the glass composition increases the content of elements such as Al, or Pb, Bi, Ba, etc. What is necessary is just to reduce content of the element.

The glass for dye-sensitized solar cells of the present invention includes Bi ₂ O ₃ —B ₂ O ₃ glass, SnO—P ₂ O ₅ glass, SiO ₂ —B ₂ O ₃ glass, and V ₂ O ₅ glass. Etc. can be used. Here, “to glass” refers to a glass containing 15 mol% or more of an explicit component as an essential component.

Bi ₂ O ₃ -B ₂ O ₃ based glass, a glass composition, in _{mol%, Bi 2 O 3 25~45%} , B 2 O 3 20~35%, ZnO 0~35%, SiO 2 + Al 2 O It is preferable to contain 0.5-15% of ₃ + ZrO ₂ . If it does in this way, thermal stability, a low melting-point characteristic, and the tolerance (electrolytic solution resistance) with respect to an iodine electrolyte solution can be made compatible at a high level. The reason for limiting the glass composition range as described above will be described below.

Bi ₂ O ₃ is a main component for lowering the softening point, and its content is preferably 25 to 45%, particularly preferably 30 to 40%. Among the components constituting the glass, Bi ³⁺ has a large ionic radius of 1.17 mm. Therefore, when the content of Bi ₂ O ₃ is small, the average ionic radius of the cation in the glass composition is small, and when the content of Bi ₂ O ₃ is large, the average ionic radius tends to be large. The value obtained by dividing the valency of ^{Bi 3+} in the square of the ionic radius is 2.19 / Å ^2. Therefore, when the content of Bi ₂ O ₃ is small, the value obtained by dividing [the average valence of the cation in the glass composition] by [the square of the average ionic radius of the cation in the glass composition] tends to increase, and the iodine ion It becomes difficult to receive erosion by. Furthermore, if the content of Bi ₂ O ₃ is small, the softening point becomes too high and it becomes difficult to seal at low temperatures. On the other hand, when the content of Bi ₂ O ₃ is large, the glass becomes thermally unstable, and the glass tends to devitrify during melting or firing.

B ₂ O ₃ is a component that forms a glass network of bismuth-based glass, and its content is preferably 20 to 35%, particularly preferably 23 to 30%. Among the components constituting the glass, B ³⁺ has a small ionic radius of 0.25 mm. Therefore, when the content of B ₂ O ₃ is small, the average ionic radius of the cation in the glass composition increases, and when the content of B ₂ O ₃ is large, the average ionic radius tends to decrease. ^The value obtained by dividing the valency by the square of the ionic radius of ^{B 3+} is 48.00 / Å ^2. Therefore, when the content of B ₂ O ₃ is large, the value obtained by dividing [the average valence of the cation in the glass composition] by [the square of the average ionic radius of the cation in the glass composition] becomes large, which is caused by iodine ions. Less susceptible to erosion. Further, when the content of B ₂ O ₃ is small, the glass becomes thermally unstable, and the glass is easily devitrified at the time of melting or firing. On the other hand, when the content of B ₂ O ₃ is too large, the viscosity is too high, it becomes difficult to seal at low temperatures.

ZnO is a component that suppresses devitrification during melting or firing, and its content is preferably 0 to 35%, more preferably 10 to 30%, and particularly preferably 20 to 30%. However, when there is too much content of ZnO, the component balance of a glass composition will be impaired and it will become easy to devitrify glass conversely. In addition, since the ionic radius of Zn ²⁺ is 0.74 Å and the value obtained by dividing the valence by the square of the ionic radius is 3.65 / Å ² , the object is to prevent erosion by the iodine electrolyte as much as possible. In this case, the content of ZnO is preferably small.

SiO ₂ + Al ₂ O ₃ is a component that hardly causes erosion by the iodine electrolyte, and its content is preferably 0.5 to 15%, particularly preferably 2 to 10%. When the content of SiO ₂ + Al ₂ O ₃ is small, the ionic radius of Si ^{4+ and} the ionic radius of Al ³⁺ are 0.40Å and 0.64Å, respectively, and the values obtained by dividing the valence by the square of the ionic radius are 25. Since it is 00 / Å ² and 6.68 / Å ² , the glass is easily eroded by the iodine electrolyte solution, and the deterioration of the iodine electrolyte solution and battery characteristics can be prevented for a long period of time. When the content of SiO ₂ + _Al 2 _{O 3} is large, too high softening point, it is difficult to seal at low temperatures.

SiO ₂ is a component that makes it difficult to cause erosion by the iodine electrolyte, and its content is preferably 0 to 15%, 0.1 to 10%, and particularly preferably 2 to 8%. When the content of SiO ₂ is large, the softening point becomes too high, and it becomes difficult to seal at a low temperature.

Al ₂ O ₃ is a component that makes it difficult to cause erosion by the iodine electrolyte, and its content is preferably 0 to 10%, particularly preferably 0.1 to 3.5%. When the content of Al ₂ O ₃ is large, too high softening point, it is difficult to seal at low temperatures.

  In the above glass composition range, in addition to the above components, for example, the following components can be contained in the glass composition up to 25% (preferably 20%, more preferably 15%, still more preferably 10%).

CuO is a component that suppresses devitrification during melting or firing, and its content is 0 to 10%, more preferably 0 to 7%. When there is too much content of CuO, since the ion radius of Cu < ²⁺ > is 0.87? And the value obtained by dividing the valence by the square of the ion radius is 2.64 /? ² , the resistance to electrolyte solution becomes poor. Moreover, when there is too much content of CuO, the component balance of a glass composition will be impaired, conversely, it will become easy to devitrify glass and fluidity | liquidity will be easy to be impaired. In particular, if the CuO content is restricted to 0.1 to 2%, the thermal stability can be remarkably enhanced.

Fe ₂ O ₃ is a component that suppresses devitrification during melting or firing, and its content is 0 to 5%, preferably 0 to 2%. When the content of Fe ₂ O ₃ is large, the ionic radius of Fe ³⁺ is 0.69Å, and the value obtained by dividing the valence by the square of the ionic radius is 6.30 / Å ² , which improves the resistance to electrolyte. Suruga, the content of Fe ₂ O ₃ is too large, is impaired balance of components glass composition, the glass tends to be devitrified reversed. Moreover, if the content of Fe ₂ O ₃ is restricted to 0.1 to 2%, the thermal stability can be remarkably improved.

  BaO, SrO, MgO, and CaO are components that suppress devitrification at the time of melting or firing, and these components can be contained in the glass composition up to 15% in total. If the total amount of these components is large, the softening point becomes too high and it becomes difficult to seal at low temperatures.

The content of BaO is preferably 0 to 10%, particularly preferably 0.1 to 8%. When the content of BaO is too large, the ionic radius of Ba ²⁺ is 1.49 Å, and the value obtained by dividing the valence by the square of the ionic radius is 0.90 / Å ² . Moreover, when there is too much content of BaO, the component balance of a glass composition will be impaired and it will become easy to devitrify glass conversely. Therefore, from the viewpoint of improving the thermal stability, the BaO content is preferably 1% or more.

Each content of SrO, MgO, and CaO is preferably 0 to 5%, particularly preferably 0 to 2%. The ionic radii of Sr ²⁺ , Mg ²⁺ and Ca ²⁺ are 1.32 Å, 0.86 Å and 1.14 そ れ ぞ れ, respectively, and the values obtained by dividing the valence by the square of the ionic radius are 1.15 / Å ² , respectively. 2.70 ^/ Å 2, which is 1.54 / Å ^2. Therefore, when there is much content of each component, electrolyte solution resistance will become scarce. Moreover, when there is too much content of each component, it will become easy to devitrify or phase-separate glass.

Sb ₂ O ₃ is a component for suppressing devitrification, and its content is preferably 0 to 5%, particularly preferably 0 to 2%. On the other hand, Sb ₂ O ₃ has an effect of stabilizing the network structure of the bismuth-based glass. If Sb ₂ O ₃ is appropriately added to the bismuth-based glass, when the content of Bi ₂ O ₃ is large, for example, Bi _{Even if} the content of ₂ O ₃ is 35% or more, the thermal stability is hardly lowered. However, when the content of Sb ₂ O ₃ is too large, is impaired balance of components glass composition, the glass is easily devitrified reversed. Ionic radius of sb ³⁺ is 0.90 Å, the value obtained by dividing the valency by the square of the ionic radius is 5.19 / Å ^2.

WO ₃ is a component for suppressing glass devitrification, and its content is preferably 0 to 10%, particularly preferably 0 to 4%. In WO ₃ , since the ionic radius of WO ⁶⁺ is 0.74Å, the average ionic radius of cations in the glass composition is slightly reduced, but the value obtained by dividing the valence by the square of the ionic radius is 15.61 / Å. ² is a component that improves the electrolytic solution resistance. However, when the content of WO ₃ is too large, is impaired balance of components glass composition, the glass tends to be devitrified reversed.

In ₂ O ₃ and Ga ₂ O ₃ are not essential components, but are components for suppressing devitrification, and the total content is preferably 0 to 5%, particularly preferably 0 to 3%. _However, when the total content of _{In 2 O 3, Ga 2 O} 3 is too large, is impaired balance of components glass composition, the glass tends to be devitrified reversed. In addition, the content of In ₂ O ₃ is preferably 0 to 1%, and the content of Ga ₂ O ₃ is preferably 0 to 0.5%. The ion radii of In ³⁺ and Ga ³⁺ are 0.94Å and 0.76Å, respectively, and the values obtained by dividing the valence by the square of the ion radius are 3.40 / Å ² and 5.19 / Å ² , respectively. is there.

The oxides of Li, Na, K, and Cs are components that lower the softening point. However, since they have an action of promoting devitrification at the time of melting, the total content is preferably 2% or less. The ionic radii of Li ⁺ , Na ⁺ , K ⁺ and Cs ⁺ are 0.90 そ れ ぞ れ, 1.16Å, 1.52Å and 1.81Å, respectively, and the values obtained by dividing the valence by the square of the ionic radius are respectively 1.23 / ２３ ² , 0.74 / Å ² , 0.43 / Å ² , and 0.31 / Å ² . Therefore, when there is too much content of each component, electrolyte solution resistance will become scarce.

MoO ₃ , La ₂ O ₃ , Y ₂ O _3, and Gd ₂ O ₃ are components that suppress phase separation at the time of melting. However, if the total amount thereof is more than 3%, the softening point becomes too high, and the temperature is low. It becomes difficult to seal with. The ionic radii of each component are 0.73０．７, 1.17Å, 1.04Å, and 1.08Å, respectively. Further, each 11.26 ^/ Å ² is a value obtained by dividing the valency by the square of the ionic ^{radius, 2.19 / Å 2, 2.77 /} Å 2, which is 2.57 / Å ^2.

CeO ₂ is a component that suppresses devitrification during melting or firing, and its content is preferably 0 to 5%, particularly preferably 0 to 2%. When the content of CeO ₂ is too large, the ionic radius of Ce ⁴⁺ is 1.15 価, and the value obtained by dividing the valence by the square of the ionic radius is 3.02 / Å ² , so that the electrolytic solution resistance becomes poor. . If the content of CeO ₂ is too large, lacking component balance of the glass composition, contrary to thermal stability is impaired, resulting in the glass is easily devitrified, the fluidity is easily impaired.

P ₂ O ₅ is a component that suppresses devitrification at the time of melting. However, if the amount of P ₂ O ₅ added is more than 1%, the glass tends to phase-separate at the time of melting.

  Moreover, even if it is another component, it can add to a glass composition to 10% (preferably 5%) in the range which does not impair a glass characteristic.

SiO ₂ -B ₂ O ₃ -based glass, as a glass composition, in _{mol%, SiO 2 20~50%, B} 2 O 3 15~35%, preferably contains 0 to 35% ZnO. In this way, thermal stability, low melting point characteristics, and electrolyte resistance can be achieved at a high level. The reason why the glass composition range is limited as described above will be described below.

SiO ₂ is a component that forms a glass network and hardly causes erosion by the iodine electrolyte, and its content is preferably 20 to 50%, particularly preferably 25 to 45%. When the content of SiO ₂ is large, the ionic radius of Si ⁴⁺ is 0.40Å, and the value obtained by dividing the valence by the square of the ionic radius is 25.00 / Å ² , so that the resistance to electrolytic solution is improved. If the content of SiO ₂ is small, glass becomes thermally unstable, the glass tends to be devitrified when melted or during sintering. On the other hand, when the content of SiO ₂ is large, the softening point becomes too high, and it becomes difficult to seal at a low temperature.

B ₂ O ₃ is a component that forms a glass network, and its content is preferably 15 to 35%, particularly preferably 20 to 30%. When the content of B ₂ O ₃ is small, the ionic radius of B ³⁺ is 0.25%, so that the average ionic radius of the cation in the glass composition increases, and when the content of B ₂ O ₃ is large, the average ion The radius tends to be small. ^The value of the valence divided by the square of the ionic radius of ^{B 3+} is 48.00 / Å ^2. Therefore, when the content of B ₂ O ₃ is large, a value obtained by dividing [average valence of cations in glass composition] by [square of average ionic radius of cations in glass composition] increases, and iodine ions Less susceptible to erosion. If the content of B ₂ O ₃ is less, glass becomes thermally unstable, the glass tends to be devitrified when melted or during sintering. On the other hand, if the content of B ₂ O ₃ is large, the viscosity is too high, it becomes difficult to seal at low temperatures.

ZnO is a component that suppresses devitrification during melting or firing, and its content is preferably 0 to 35%, more preferably 10 to 30%, and particularly preferably 20 to 30%. However, when there is too much content of ZnO, the component balance of a glass composition will be impaired and it will become easy to devitrify glass conversely. In addition, since the ionic radius of Zn ²⁺ is 0.74 Å and the value obtained by dividing the valence by the square of the ionic radius is 3.65 / Å ² , the object is to prevent erosion by iodine electrolyte as much as possible. In this case, the content of ZnO is preferably small.

_SnO-P 2 _{O 5} based glass, a glass composition, in mol%, SnO 35 to _70%, preferably contains _P 2 O 5 _18~50%. In this way, thermal stability, low melting point characteristics, and electrolyte resistance can be achieved at a high level. The reason for limiting the glass composition range as described above will be described below.

SnO is a component that lowers the melting point of glass and is an essential component. The content is preferably 35 to 70%, 40 to 65%, particularly 48 to 63%. In particular, if the SnO content is 40% or more, the fluidity is increased and the airtight reliability can be improved. If the content of SnO is small, the viscosity becomes too high and the sealing temperature may be unduly high. On the other hand, when there is much content of SnO, electrolyte solution resistance will become scarce and vitrification will become difficult. Ionic radius of Sn ²⁺ is 0.83A, the value obtained by dividing the valency by the square of the ionic radius is 2.90 / Å ^2.

P ₂ O ₅ is a glass-forming oxide and a component that makes it difficult to cause erosion by an iodine electrolyte, and is a component that lowers the melting point of glass, and its content is 18 to 50%, 20 to 20%. 35%, particularly 23 to 30% is preferable. When the content of P ₂ O ₅ is small, the ionic radius of P ⁵⁺ is 0.31 Å, and the value obtained by dividing the valence by the square of the ionic radius is 52.03 / Å ² , so that the resistance to electrolyte is poor. In addition, the thermal stability tends to decrease. On the other hand, when the high content of P ₂ O _5, water resistance is lowered and becomes difficult to ensure long-term reliability, electrolyte resistance is improved.

  In the glass composition range, in addition to the above components, for example, the following components can be contained up to 40% in the glass composition.

ZnO is an intermediate oxide and a component that stabilizes the glass. The content is preferably 0 to 30%, 0 to 20%, particularly preferably 3 to 15%. In particular, if the ZnO content is 3% or more, the thermal stability can be improved. On the other hand, if there is too much ZnO, the ionic radius of Zn ²⁺ is 0.74 Å, and the value obtained by dividing the valence by the square of the ionic radius is 3.65 / Å ^2. The component balance of the glass composition is impaired, and conversely, the thermal stability tends to decrease.

B ₂ O ₃ is a glass-forming oxide and is a component that stabilizes the glass. B ^{3+ has} an ionic radius of 0.25Å and a value obtained by dividing the valence by the square of the ionic radius is 48.00 / because it is Å ^2, or to enhance the electrolyte solution resistance, the content of 0-20%, especially 0-16% is preferred. If the content of B ₂ O ₃ is large, the viscosity is too high, the fluidity tends to decrease.

SiO ₂ is a glass-forming oxide, and is a component that stabilizes the glass. The ionic radius of Si ⁴⁺ is 0.40Ｓｉ, and the value obtained by dividing the valence by the square of the ionic radius is 25.00 / Å ^2. Therefore, it is a component that increases the resistance to electrolytic solution, and its content is preferably 0 to 15%, particularly preferably 0 to 5%. When the content of SiO ₂ is large, the softening point is increased and it is difficult to sealing at low temperatures.

Al ₂ O ₃ is an intermediate oxide, a component that stabilizes the glass, a component that lowers the thermal expansion coefficient, Al ^{3+ has} an ionic radius of 0.64Å, and a valence of 2 of the ionic radius. since a value obtained by dividing a power of it is 6.68 / Å ^2, or to enhance the electrolyte solution resistance, the content of 0-10%, especially 0-5% is preferred. When the content of Al ₂ O ₃ is large, softening point unduly increased, it becomes difficult to sealing at low temperatures.

In ₂ O ₃ is a component that enhances thermal stability, and its content is preferably 0 to 5%. When the content of In ₂ O ₃ is large, batch cost soars. Incidentally, the ionic radius of ^{In 3+} is 0.94 Å, the value obtained by dividing the valency by the square of the ionic radius is 3.40 / Å ^2.

Ta ₂ O ₅ is a component that enhances thermal stability, and its content is preferably 0 to 5%. When the content of Ta ₂ O ₅ is large, softening point unduly increased, it becomes difficult to sealing at low temperatures. The ion radius of ^{Ta 5+} is 0.88A, the value obtained by dividing the square of the valence ion radius is 6.48 / Å ^2.

La ₂ O ₃ is a component that enhances thermal stability and a component that improves weather resistance, and its content is preferably 0 to 15%, 0 to 10%, and particularly preferably 0 to 5%. When the content of La ₂ O ₃ is large, softening point unduly increased, it becomes difficult to sealing at low temperatures. The ion radius of ^{La 3+} is 1.17 Å, the value obtained by dividing the valency by the square of the ionic radius is 2.19 / Å ^2.

MoO ₃ is a component that enhances thermal stability, and its content is preferably 0 to 5%. When the content of MoO ₃ is large, softening point unduly increased, it becomes difficult to sealing at low temperatures. The ion radius of ^{Mo 6+} is 0.73A, the value obtained by dividing the square of the valence ion radius is 11.26 / Å ^2.

WO ₃ is a component that enhances thermal stability, and its content is preferably 0 to 5%. When the content of WO ₃ is large, the softening point is unreasonably raised and it becomes difficult to seal at a low temperature. Incidentally, WO ^_3, the ion radius of ^{W 6+} is 0.74A, the value obtained by dividing the square of the valence ion radius is 15.61 / Å ^2.

Li ₂ O is a component that lowers the melting point of glass, and its content is preferably 0 to 5%. When the content of Li ₂ O is large, the thermal stability tends to decrease, the Li ⁺ ion radius is 0.90０．９, and the value obtained by dividing the valence by the square of the ion radius is 1.23 / Å ^2. Therefore, the resistance to electrolytic solution becomes poor.

Na ₂ O is a component that lowers the melting point of glass, and its content is preferably 0 to 10%, particularly preferably 0 to 5%. When the content of Na ₂ O is large, the thermal stability tends to be lowered, and the ion radius of Na ⁺ is 1.16 Å, and the value obtained by dividing the valence by the square of the ionic radius is 0.74 / Å ^2. Therefore, the resistance to electrolytic solution becomes poor.

K ₂ O is a component that lowers the melting point of glass, and its content is preferably 0 to 5%. When the content of K ₂ O is large, the thermal stability tends to be lowered, the ion radius of K ⁺ is 1.52Å, and the value obtained by dividing the valence by the square of the ion radius is 0.43 / Å ^2. Therefore, the resistance to electrolytic solution becomes poor.

MgO is a component that enhances thermal stability, and its content is preferably 0 to 15%. If the content of MgO is too large, the balance of the composition of the glass composition is impaired, and conversely, the glass tends to be devitrified, and the ionic radius of Mg ²⁺ is 0.86%, and the valence is divided by the square of the ionic radius. since value is 2.70 / Å ^2, electrolyte resistance becomes poor.

BaO is a component that enhances thermal stability, and its content is preferably 0 to 10%. If the content of BaO is too large, the balance of the composition of the glass composition will be impaired, and conversely, the glass will be easily devitrified, and the ionic radius of Ba ²⁺ is 1.49%, and the valence is divided by the square of the ionic radius. since value is 0.90 / Å ^2, electrolyte resistance becomes poor.

F ₂ is a component for lowering the melting point of the glass, its content is preferably 0-5%. When the content of F ₂ is large, the thermal stability tends to decrease.

In consideration of the balance between thermal stability and low melting point characteristics, 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, MgO, The total amount of BaO and F ₂ is preferably 15% or less.

V ₂ O ₅ -P ₂ O ₅ based glass, a glass composition, in _{mol%, V 2 O 5 25~55%} , preferably contains _P 2 O 5 _15~45%. In this way, thermal stability, low melting point characteristics, and electrolyte resistance can be achieved at a high level. The reason for limiting the glass composition range as described above will be described below.

V ₂ O ₅ is a component that lowers the melting point of glass and is an essential component, and its content is preferably 25 to 55%, 28 to 53%, particularly preferably 30 to 50%. In particular, when the content of V ₂ O ₅ is 25% or more, the fluidity is increased and the airtight reliability can be improved. When the content of V ₂ O ₅ is ^less, the ionic radius of ^{V 5+} is 0.68A, since the value obtained by dividing the valency by the square of the ionic radius of 10.81 / Å ^2, is poor electrolyte resistance And the viscosity becomes too high, and the sealing temperature may be unduly high. On the other hand, when the content of V ₂ O ₅ is large, the electrolytic solution resistance is improved, but vitrification tends to be difficult.

P ₂ O ₅ is a glass-forming oxide and at the same time is 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 15 to 45%, 17 to 40%, especially 20-35% is preferred. When the content of P ₂ O ₅ is small, the ionic radius is 0.31 Å, and the value obtained by dividing the valence by the square of the ionic radius is 52.03 / Å ^2. Thermal stability tends to decrease. On the other hand, when the content of P ₂ O ₅ is large, the electrolytic solution resistance is improved, but the water resistance is lowered and it is difficult to ensure long-term reliability.

  In the glass composition range, in addition to the above components, for example, the following components can be contained up to 40% in the glass composition.

ZnO is an intermediate oxide and a component that stabilizes the glass. The content is preferably 0 to 30%, 0 to 20%, particularly preferably 3 to 15%. In particular, if the ZnO content is 3% or more, the thermal stability can be improved. On the other hand, if there is too much ZnO, the ionic radius of Zn ²⁺ is 0.74 Å, and the value obtained by dividing the valence by the square of the ionic radius is 3.65 / Å ^2. The component balance of the glass composition is impaired, and conversely, the thermal stability tends to decrease.

SrO is a component that enhances thermal stability, and its content is preferably 0 to 25%. If the SrO content is too large, the balance of the composition of the glass composition will be impaired, and conversely, the glass will be easily devitrified, and the ionic radius of Sr ²⁺ will be 1.32 mm, and the valence will be divided by the square of the ionic radius. since value is 1.15 / Å ^2, electrolyte resistance becomes poor.

BaO is a component that enhances thermal stability, and its content is preferably 0 to 30%. If the content of BaO is too large, the balance of the composition of the glass composition will be impaired, and conversely, the glass will be easily devitrified, and the ionic radius of Ba ²⁺ is 1.49%, and the valence is divided by the square of the ionic radius. since value is 0.90 / Å ^2, electrolyte resistance becomes poor.

CuO is a component that suppresses devitrification during melting or firing, and its content is preferably 0 to 25%, particularly preferably 0 to 20%. When there is too much content of CuO, since the ion radius of Cu < ²⁺ > is 0.87? And the value obtained by dividing the valence by the square of the ion radius is 2.64 /? ² , the resistance to electrolyte solution becomes poor. Moreover, when there is too much content of CuO, the component balance of a glass composition will be impaired, conversely, it will become easy to devitrify glass and fluidity | liquidity will be easy to be impaired.

  The glass for dye-sensitized solar cells of the present invention does not necessarily exclude the inclusion of PbO, but it does not substantially contain PbO from the environmental viewpoint and the viewpoint of preventing erosion by iodine electrolyte. Is preferred. Here, “substantially does not contain PbO” refers to a case where the content of PbO in the glass composition is 1000 ppm or less.

In the dye-sensitized solar glass battery of the present invention, decrease weight when immersed for two weeks in an iodine electrolyte solution of 25 ° C. is 0.14 mg / cm ² or less, 0.1 mg / cm ² or less, especially 0.05 mg / cm ² or less, and it is desirable that substantially no mass decrease. The smaller the mass loss, the more the iodine electrolyte and battery characteristics can be prevented from deteriorating 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 for a dye-sensitized solar cell of the present invention, the thermal expansion coefficient is less than 91 × 10 ⁻⁷ / ° C., less than 88 × 10 ⁻⁷ / ° C., less than 86 × 10 ⁻⁷ / ° C., particularly 84 × 10 ^−7. Less than / ° C is preferred. If the difference in thermal expansion coefficient between the glass for the dye-sensitized solar cell of the present invention and the glass substrate (for example, soda glass substrate) used for the transparent electrode substrate is too large, it is fired unless a refractory filler powder is added. Later, undue stress remains on the glass substrate, the sealing part, etc., and cracks are likely to occur in the glass substrate, the sealing part, etc., or the sealing part tends to peel off. Here, the “thermal expansion coefficient” refers to a value measured by a push rod type thermal expansion coefficient measuring apparatus (TMA apparatus).

  The dye-sensitized solar cell material of the present invention preferably contains substantially no refractory filler powder. 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. On the other hand, if the addition amount of the refractory filler powder is reduced, the fluidity, particularly the sealing property, of the dye-sensitized solar cell material can be improved. Therefore, the mixing ratio is 50-100 volume% of glass powder, 0-50 volume% of refractory filler powder, preferably 70-100 volume% of glass powder, 0-30 volume% of refractory filler powder, more preferably glass powder 95. -100% by volume, refractory filler powder 0-5% by volume, and for the reasons already described, it is desirable that the refractory filler powder is substantially not contained. 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 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.

The material of the refractory filler powder is not particularly limited, but is preferably a glass powder made of the dye-sensitized solar cell glass of the present invention and a material that does not easily react with the iodine electrolyte. Specifically, as refractory filler powder, zircon, zirconia, tin oxide, aluminum titanate, quartz, β-spodumene, mullite, titania, quartz glass, β-eucryptite, β-quartz, zirconium phosphate, phosphorus A compound having a basic structure of NZP type, such as zirconium tungstate, zirconium tungstate, willemite, [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 softening point of the sealing material is higher than the strain point of the glass substrate, the glass substrate is easily deformed in the sealing step. For this reason, a low melting point characteristic is requested | required of sealing material (glass used for sealing material). Therefore, in the dye-sensitized solar cell material of the present invention, the softening point is preferably 575 ° C. or less, more preferably 550 ° C. or less, and further preferably 535 ° C. or less. When the softening point is higher than 575 ° C., the viscosity becomes too high, the sealing temperature rises unreasonably, and the glass substrate tends to be deformed. In addition, when the dye-sensitized solar cell material and the porous oxide semiconductor layer are fired simultaneously, if the sealing temperature is too high, the fusion of the oxide semiconductor particles may proceed excessively. The surface area of the porous oxide semiconductor layer is reduced, making it difficult to adsorb the dye.

In the dye-sensitized solar cell material of the present invention, decrease weight when immersed for two weeks in an iodine electrolyte solution of 25 ° C. is 0.14 mg / cm ² or less, 0.1 mg / cm ² or less, especially 0.05 mg / cm ² or less, and it is desirable that substantially no mass decrease. The smaller the mass loss, the more the iodine electrolyte and battery characteristics can be prevented from deteriorating over a long period of time.

  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.

  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 are preferable because they 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 is preferable because it is highly viscous and has good solubility in 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 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 subjected to a sealing treatment with a laser beam. When laser light is used, the dye-sensitized solar cell material can be locally heated, and the transparent electrode substrate and the counter electrode substrate can be sealed after preventing thermal deterioration of components such as iodine electrolyte. it can. When the transparent electrode substrate and the counter electrode substrate are sealed using laser light, the dye-sensitized solar cell material of the present invention contains a transition metal oxide (for example, CuO, Fe ₂ O ₃ ) as a glass composition. The content is preferably 0.1% or more, 0.5% or more, 1.5% or more, 2% or more, and particularly preferably 3% or more. In this way, the light energy of the laser light can be efficiently converted into heat energy, in other words, the laser light can be absorbed accurately into the glass, so only the part to be sealed is heated locally. can do. Here, various laser beams can be used as the laser beam. In particular, 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, Preferably it is 750-1300 nm.

  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. Therefore, when using Ag for a current collection electrode, it is necessary to protect a current collection 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.

  The dye-sensitized solar cell material of the present invention can be used for forming partition walls. Generally, when a partition is formed in a dye-sensitized solar cell, the cell is filled with an iodine electrolyte. 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 temperatures and is less susceptible to erosion by iodine electrolytes, thus preventing the barrier ribs from breaking for a long period of time. can do.

  The present invention will be described in detail based on examples. Tables 1 to 4 show examples of the present invention (sample Nos. 1 to 22) and comparative examples (samples No. 23 to 26).

  Each sample described in the table was prepared as follows. First, a glass batch prepared by preparing raw materials such as various oxides and carbonates so as to have the glass composition in the table is prepared, and this is put into a platinum crucible or an alumina crucible and melted at 1000 to 1200 ° C. for 1 to 2 hours. did. Melting was performed in a nitrogen atmosphere for glass containing SnO and in an air atmosphere for the other glass. Next, a part of the molten glass was poured out as a TMA sample into a stainless steel mold, and the other molten glass was formed into a thin piece with a water-cooled roller. The sample for TMA 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.

Next, each glass powder and a vehicle (ethyl cellulose or polyethylene carbonate dissolved in α-terpineol or diethylpentanediol) were kneaded to obtain a paste. This was screen-printed on a soda glass substrate (coefficient of thermal expansion: 100 × 10 ⁻⁷ / ° C.) to a thickness of 40 to 80 μm with a diameter of 40 mm, dried in an electric furnace at 120 ° C. for 10 minutes, and then 500 to 550 ° C. Baking for 30 minutes gave a sample for mass reduction evaluation. In addition, baking was performed in the nitrogen atmosphere about the glass containing SnO, and the air atmosphere other than that.

  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 Tables 1-4.

  The thermal expansion coefficient was measured with a TMA apparatus. The thermal expansion coefficient was measured in a temperature range of 30 to 300 ° 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, the mass of the sample for evaluation of mass reduction and the surface area of the fired film in contact with the iodine electrolyte solution were measured, and then this sample was immersed in an iodine electrolyte solution in a glass sealed container, and the glass was placed in a thermostatic bath at 25 ° C. The value was obtained by dividing the value obtained by subtracting the mass of the sample after 2 weeks from the mass of the sample before immersion and leaving the mass of the sample before immersion by the surface area of the fired film. The iodine electrolyte used for evaluation of mass loss 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 is apparent from Tables 1 to 4, sample No. 1 to 22 had a thermal expansion coefficient of 64 to 124 × 10 ⁻⁷ / ° C. and a softening point of 348 to 535 ° C. Moreover, in any measurement sample for weight loss, the fired film was not peeled off and was in good contact with the glass substrate. Furthermore, sample no. 1 to 22 had a mass loss of 0.10 mg / cm ² or less, and were hardly eroded by the iodine electrolyte. On the other hand, sample No. Nos. 23 to 26 had a large mass loss and were easily eroded by the iodine electrolyte.

  The relationship between the average ionic radius of cations in the glass composition and the amount of erosion by iodine electrolyte was investigated.

  By the same method as Example 1, the mass loss with respect to iodine electrolyte solution was evaluated about various glasses. Next, the relationship between the average ionic radius of cations in the glass composition and the amount of erosion by the iodine electrolyte is plotted in FIG.

  As is apparent from FIG. 1, it can be seen that the smaller the average ionic radius of the cations in the glass composition, the smaller the amount of erosion by the iodine electrolyte.

  The relationship between the value obtained by dividing [the average valence of cations in the glass composition] by [the square of the average ionic radius of cations in the glass composition] and the amount of erosion by the iodine electrolyte was investigated.

  By the same method as Example 1, the mass loss with respect to iodine electrolyte solution was evaluated about various glasses. Next, FIG. 2 plots the relationship between the value obtained by dividing the average valence of cations in the glass composition by the square of the average ionic radius of cations and the amount of erosion by the iodine electrolyte.

  As can be seen from FIG. 2, the larger the value obtained by dividing the average valence of the cation in the glass composition by the square of the average ionic radius of the cation, the smaller the amount of erosion by the iodine electrolyte.

  The glass for a dye-sensitized solar cell and the material for a dye-sensitized solar cell of the present invention are used for sealing a transparent electrode substrate and a counter electrode substrate of a dye-sensitized solar cell, covering a collecting electrode, and partitioning cells. It is suitable for forming a partition wall.

Claims (11)

  A glass for a dye-sensitized solar cell, wherein an average ionic radius of cations in the glass composition is 0.80 mm or less. The value obtained by dividing [average valence of cations in glass composition] by [square of average ionic radius of cations in glass composition] is 4.30 /］ ² or more, Battery glass. The average ionic radius of cations in the glass composition is 0.80 mm or less, and the value obtained by dividing [the average valence of cations in the glass composition] by [the square of the average ionic radius of cations in the glass composition] is 4. .30 / Å ² or more, dye-sensitized solar cell glass. The glass for dye-sensitized solar cells according to any one of claims 1 to 3, wherein a mass loss when immersed in an iodine electrolyte at 25 ° C for 2 weeks is 0.14 mg / cm ² or less. The glass for dye-sensitized solar cells according to any one of claims 1 to 4, wherein a weight loss when immersed in an iodine electrolyte at 25 ° C for 2 weeks is 0.1 mg / cm ² or less. The coefficient of thermal expansion is 65 to 120 × 10 ⁻⁷ / ° C., The dye-sensitized solar cell glass according to claim 1.   Dye sensitization comprising: 50 to 100% by volume of a glass powder comprising the glass for a dye-sensitized solar cell according to any one of claims 1 to 6; and 0 to 50% by volume of a refractory filler powder. Sensitive solar cell material.   8. The dye-sensitized solar cell material according to claim 7, having a softening point of 550 ° C. or lower.   The dye-sensitized solar cell material according to claim 7 or 8, which is used for sealing.   The material for a dye-sensitized solar cell according to claim 7 or 8, which is used for covering a collecting electrode.   The material for a dye-sensitized solar cell according to claim 9, which is subjected to a sealing treatment with a laser beam.