WO2014010553A1 - Sealing material for dye-sensitized solar cells - Google Patents

Sealing material for dye-sensitized solar cells Download PDF

Info

Publication number
WO2014010553A1
WO2014010553A1 PCT/JP2013/068638 JP2013068638W WO2014010553A1 WO 2014010553 A1 WO2014010553 A1 WO 2014010553A1 JP 2013068638 W JP2013068638 W JP 2013068638W WO 2014010553 A1 WO2014010553 A1 WO 2014010553A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
sealing material
dye
sensitized solar
content
Prior art date
Application number
PCT/JP2013/068638
Other languages
French (fr)
Japanese (ja)
Inventor
朋子 榎本
Original Assignee
日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Publication of WO2014010553A1 publication Critical patent/WO2014010553A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a sealing material for a dye-sensitized solar cell, and specifically relates to a sealing material for a dye-sensitized solar cell suitable for sealing treatment with laser light (hereinafter referred to as laser sealing).
  • 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 because there are 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, An organic dye such as a 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 or a plastic substrate is used for the transparent electrode substrate and the counter electrode substrate.
  • 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.
  • 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, glass substrates have been used as transparent electrode substrates and counter electrode substrates.
  • an iodine electrolyte is filled between the transparent electrode substrate and the counter electrode substrate.
  • the challenge to commercialization of soot dye-sensitized solar cells is to improve long-term durability.
  • the solar cell member or iodine electrolyte is deteriorated by the reaction between the solar cell member (sealing material, etc.) and the iodine electrolyte, or moisture enters the inside due to low airtightness.
  • an iodine electrolyte solution deteriorates. 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.
  • 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.
  • 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 electrolyte solution deteriorates and the battery characteristics are deteriorated.
  • the glass powder used for the sealing material generally has a softening point of 300 ° C or higher. For this reason, when sealing glass substrates with said sealing material, it is necessary to throw the whole dye-sensitized solar cell into an electric furnace, and to bake at the temperature more than the softening point of glass powder.
  • iodine electrolytes and organic dyes used in dye-sensitized solar cells have only heat resistance of about 120 to 130 ° C. When sealing glass substrates together by this method, iodine electrolytes are It volatilizes or the organic dye is thermally degraded.
  • Patent Documents 4 and 5 describe a method of sealing a front glass substrate and a rear glass substrate of a field emission display by irradiating a sealing material with laser light.
  • Patent Documents 4 and 5 do not specifically describe a glass system suitable for this method, and even if a conventional sealing material is irradiated with laser light, the light energy of the laser light is reduced at the sealing site. It was difficult to efficiently convert to heat energy. Therefore, in order to seal glass substrates together using a conventional sealing material, it is necessary to increase the output of the laser beam. As a result, an unreasonable thermal history is applied to organic pigments and the battery characteristics are degraded. There was a fear.
  • the present invention improves the long-term reliability of dye-sensitized solar cells by creating a sealing material for dye-sensitized solar cells that is highly resistant to iodine electrolyte and suitable for laser sealing. Is a technical issue.
  • the sealing material for a dye-sensitized solar cell of the present invention is a sealing material for a dye-sensitized solar cell containing at least a bismuth-based glass powder, and the bismuth-based glass powder has a mol% as a glass composition.
  • the sealing material for dye-sensitized solar cells of the present invention can include not only an embodiment composed of only bismuth-based glass powder but also a composite material of bismuth-based glass powder and refractory filler powder, for example.
  • the thermal stability is prevented from lowering and the glass is reduced.
  • the melting point can be reached.
  • the content of B 2 O 3 is regulated to 20 to 40 mol%, the thermal stability can be enhanced while maintaining the low melting point characteristics.
  • the ZnO content is restricted to 0 to 20 mol%, the thermal stability can be improved.
  • the content of SiO 2 is regulated to 11 mol% or more, the glass is less likely to be eroded by the iodine electrolyte. Moreover, if the content of SiO 2 is regulated to 32 mol% or less, it is easy to prevent a situation where the softening point is unduly increased. Further, if the content of Al 2 O 3 + ZrO 2 is restricted to 0 to 20 mol%, it becomes easy to prevent the glass from devitrifying when irradiated with laser light.
  • the CuO content is regulated to 5 mol% or more, the light energy of the laser light is efficiently converted into thermal energy. As a result, the glass substrates can be properly sealed with each other while preventing volatilization of the iodine electrolyte and deterioration of the organic pigment.
  • the sealing material is locally heated with laser light, the temperature at a location 1 mm away from the heating location is 100 ° C. or less, and the volatilization of the electrolytic solution and the deterioration of the organic dye can be prevented.
  • content of CuO is controlled to 20% or less, the situation where glass devitrifies at the time of laser light irradiation can be prevented.
  • the sealing material for dye-sensitized solar cell of the present invention does not substantially contain PbO.
  • substantially does not contain PbO refers to a case where the content of PbO in the sealing material is less than 1000 ppm. In this way, environmental demands in recent years can be satisfied.
  • the sealing material for dye-sensitized solar cells of the present invention has a mass loss of 0.1 mg / cm 2 or less when immersed in an iodine electrolytic solution at 70 ° C. for 2 weeks.
  • iodine electrolyte includes 0.1M lithium iodide, 0.05M iodine, 0.5M 4-tert-butylpyridine, and 1,2-dimethyl-3-propylimidazolium iodide in acetonitrile. Use a solution of 0.6M id.
  • mass loss means that a glass substrate (glass substrate with a fired film) on which a dye-sensitized solar cell sealing material is baked densely is immersed in an iodine electrolyte solution in a sealed container, and the mass before immersion Is calculated by dividing the value obtained by subtracting the mass after two weeks from 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.
  • the sealing material for dye-sensitized solar cell of the present invention further contains a refractory filler powder and the content thereof is 0 to 70% by volume.
  • the thermal expansion coefficient of the sealing material can be adjusted so as to closely match the thermal expansion coefficient of the glass substrate.
  • the content of the refractory filler powder is more preferably 50% by volume or less, more preferably 30% by volume or less, and most preferably 10% by volume or less from the viewpoint of ensuring fluidity. Further, when the content of the refractory filler powder is reduced, the gap between the transparent electrode substrate and the counter electrode substrate is easily narrowed and made uniform.
  • the dye-sensitized solar cell sealing material of the present invention is preferably used for laser sealing.
  • the sealing material is locally heated, it is easy to prevent volatilization of the iodine electrolyte and deterioration of the organic dye.
  • Various lasers can be used as a laser light source.
  • 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.
  • the emission center wavelength of the laser light is preferably 500 to 1600 nm, particularly preferably 750 to 1300 nm.
  • Bi 2 O 3 is a main component for lowering the softening point, and its content is 25 to 35% (excluding 35.0%), preferably 29 to 34%, more preferably 30 to 33. %.
  • the content of Bi 2 O 3 is less than 25%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.
  • the Bi 2 O 3 content is 35.0% or more, the glass becomes thermally unstable, and the glass tends to devitrify during melting or laser irradiation.
  • B 2 O 3 is a component that forms a glass network of bismuth-based glass, and its content is 20 to 40%, preferably 25 to 35%, more preferably 28 to 33%.
  • the content of B 2 O 3 is less than 20%, the glass becomes thermally unstable, and the glass is easily devitrified during melting or laser irradiation.
  • the content of B 2 O 3 is more than 40%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.
  • SiO 2 is a component that makes it difficult for glass to be eroded by the iodine electrolyte. Its content is 11 to 32%, preferably 18 to 30%, more preferably 21 to 30%. If the content of SiO 2 is less than 11%, the glass is easily eroded by the iodine electrolyte solution, and the deterioration of the iodine electrolyte solution and battery characteristics proceeds. On the other hand, if the content of SiO 2 is more than 32%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.
  • CuO is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass easily, and devitrification during melting or laser irradiation. It is a component which suppresses. Its content is 5 to 20%, preferably 5 to 15%, more preferably 8 to 15%. When the content of CuO is more than 20%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified and the fluidity of the sealing material is easily impaired. If the CuO content is less than 5%, the light absorption characteristics are lowered, and the glass is difficult to soften even when irradiated with laser light.
  • ZnO is a component that decreases the coefficient of thermal expansion while suppressing devitrification during melting or laser irradiation, and its content is 0 to 20%, preferably 5 to 15%.
  • the content of ZnO is more than 20%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  • Al 2 O 3 + ZrO 2 is a component that makes it difficult for glass to be eroded by the iodine electrolyte. Its content is 0 to 20%, preferably 1 to 10%. If the content of Al 2 O 3 + ZrO 2 is more than 20%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.
  • Fe 2 O 3 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass, and also when melted or irradiated with laser Is a component that suppresses devitrification, and its content is preferably 0 to 5%, particularly preferably 0.1 to 3%.
  • the content of Fe 2 O 3 is more than 5%, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.
  • BaO, SrO, MgO, and CaO are components that enhance the thermal stability, and the total content of these components is preferably 10% or less, particularly preferably 5% or less. If the total amount of these components is too large, the softening point becomes too high, and the glass becomes difficult to soften even when irradiated with laser light.
  • the content of BaO is preferably 0 to 10%, more preferably 0 to 7%.
  • the content of BaO is preferably 0 to 10%, more preferably 0 to 7%.
  • the content of each of SrO, MgO and CaO is preferably 0 to 3%, more preferably 0 to 1%. When the content of each component is more than 3%, the glass is easily devitrified or phase-separated.
  • CeO 2 is a component that suppresses devitrification at the time of melting or laser irradiation, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. When the content of CeO 2 is more than 5%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  • P 2 O 5 is a component that hardly causes erosion of the glass by the iodine electrolyte, and its content is preferably 0 to 10%, particularly preferably 0 to 5%. When the content of P 2 O 5 is more than 10%, the glass is likely to be phase-separated at the time of melting.
  • Sb 2 O 3 is a component that enhances thermal stability, and its content is preferably 0 to 5%, more preferably 0 to 2%, and most preferably 0 to 1%.
  • the content of Sb 2 O 3 is more than 5%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  • WO 3 is a component that enhances thermal stability, and its content is preferably 0 to 5%, particularly preferably 0 to 2%. When the content of WO 3 is too large, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.
  • In 2 O 3 and Ga 2 O 3 are components that enhance the thermal stability, and the total content thereof is preferably 0 to 5%, more preferably 0 to 3%.
  • the total content of In 2 O 3 and Ga 2 O 3 is too large, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.
  • the oxides of Li, Na, K, and Cs are components that lower the softening point. However, since they have an effect of promoting devitrification at the time of melting, the total content is preferably 2% or less.
  • 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 of these is more than 3%, the softening point becomes too high, and the laser Even if light is irradiated, the glass becomes difficult to soften.
  • NiO, V 2 O 5 , CoO, MoO 3 , TiO 2 , and MnO 2 are components having light absorption characteristics. When light having a predetermined emission center wavelength is irradiated, the light is absorbed and the glass is softened. It is a component that facilitates. The total amount of these components is preferably 0 to 7%, particularly preferably 0 to 3%. If the total amount of these components is more than 7%, the glass tends to devitrify.
  • the bismuth-type glass powder concerning this invention does not contain PbO substantially from an environmental viewpoint and the viewpoint which prevents the glass erosion by an iodine electrolyte solution.
  • substantially no PbO refers to the case where the content of PbO in the glass composition is less than 1000 ppm.
  • the mass loss when immersed in an iodine electrolytic solution at 70 ° C. for 2 weeks is preferably 0.1 mg / cm 2 or less, more preferably 0.05 mg / cm. 2 or less, more preferably substantially no mass loss, that is, 0.01 mg / cm 2 or less is preferable.
  • the dye-sensitized solar cell sealing material of the present invention may contain a refractory filler powder in order to improve the thermal expansion coefficient matching with the glass substrate and the mechanical strength.
  • the mixing ratio of the glass powder and the refractory filler powder is preferably 30 to 100% by volume of the glass powder, 0 to 70% by volume of the refractory filler powder, more preferably 50 to 100% by volume of the refractory filler powder, and 0% of the refractory filler powder.
  • the content of the refractory filler powder is more than 70% by volume, the ratio of the glass powder becomes relatively low, and it becomes difficult to ensure desired fluidity.
  • the maximum particle diameter D max of the refractory filler powder is preferably 25 ⁇ m or less, and more preferably 15 ⁇ m or less.
  • the “maximum particle diameter D max ” represents a particle diameter in which the accumulated amount is 99% cumulative from the smaller particle in the volume-based cumulative particle size distribution curve measured by the laser diffraction method. .
  • refractory filler powder Various materials can be used as the refractory filler powder, but those that do not easily react with glass powder or iodine electrolyte are preferable.
  • refractory filler powder zircon, zirconia, tin oxide, aluminum titanate, quartz, ⁇ -spodumene, mullite, titania, quartz glass, ⁇ -eucryptite, ⁇ -quartz, zirconium phosphate, phosphorus Compounds 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. Or these solid solutions are preferable.
  • the dye-sensitized solar cell sealing material of the present invention is preferably used for laser sealing.
  • the sealing material can be locally heated. Therefore, it is possible to seal glass substrates together while preventing thermal deterioration of components such as iodine electrolyte.
  • the softening point is preferably 560 ° C or lower, more preferably 550 ° C or lower, and further preferably 530 ° C or lower. If the softening point is higher than 560 ° C, the viscosity of the glass becomes too high, and even when irradiated with laser light, the glass tends to be difficult to soften.
  • the output of the laser light must be increased. It is necessary to raise. When the output of the laser beam is increased, the ambient temperature of the glass substrate is increased. For example, when soda glass is used as the glass substrate, the glass substrate is easily deformed.
  • the thermal expansion coefficient is 90 ⁇ 10 ⁇ 7 / ° C. or less, particularly 85 ⁇ 10 ⁇ 7 / ° C. when soda glass or high strain point glass is used as the glass substrate. ° C or lower is preferable, and when alkali-free glass is used as the glass substrate, 55 ⁇ 10 ⁇ 7 / ° C. or lower, particularly 50 ⁇ 10 ⁇ 7 / ° C. or lower is preferable. In this way, the stress applied to the glass substrate and the sealing part is reduced, so that it becomes easy to prevent stress destruction of the sealing part.
  • the dye-sensitized solar cell sealing material of the present invention may further contain up to 10% by volume of an oxide pigment in order to promote light absorption of laser light.
  • the sealing material for dye-sensitized solar cells of the present invention further contains glass fiber, glass beads, silica beads, resin beads, etc. up to 10% by volume as spacers in order to make the thickness of the sealing part uniform. May be.
  • the sealing material for a dye-sensitized solar cell of the present invention may be used as a powder, but from the viewpoint of improving handleability, it is preferably kneaded uniformly with a vehicle and processed into a sealing material 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.
  • acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester, and the like can be used.
  • acrylic acid esters and nitrocellulose are preferable because they have good thermal decomposability.
  • Solvents include N, N′-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -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- Methyl-2-pyrrolidone or the like can be used.
  • ⁇ -terpineol is preferable because it is highly viscou
  • Table 1 shows examples of the present invention (sample Nos. 1 to 8).
  • Table 2 shows comparative examples (sample Nos. 9 and 10) of the present invention.
  • Each sample 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 glass batch was put in a platinum crucible and melted at 1000 to 1200 ° C. for 1 to 2 hours. Next, a part of the obtained molten glass was poured into a stainless steel mold as a sample for measuring the thermal expansion coefficient, and the other molten glass was formed into a flake shape with a water-cooled roller. Finally, the glass flakes were pulverized with a ball mill and passed through a sieve having an opening of 45 ⁇ m to obtain glass powders having an average particle diameter D 50 of about 5 ⁇ m. The sample for measuring the thermal expansion coefficient was subjected to a predetermined slow cooling (annealing) treatment after molding.
  • annealing slow cooling
  • the refractory filler powder was prepared using cordierite so that the average particle diameter D 50 was 2.5 ⁇ m and the maximum particle diameter D max was 10 ⁇ m.
  • the glass transition point and softening point were measured with a differential thermal analyzer. The measurement was performed in the atmosphere at a temperature rising rate of 10 ° C./min, and the measurement was started from room temperature.
  • the thermal expansion coefficient was obtained with a push rod type thermal expansion coefficient measuring device.
  • the measurement temperature range was 30 to 300 ° C.
  • Mass loss was calculated as follows. First, each sample and an ethylcellulose-based vehicle were kneaded and prepared so as to have a viscosity of about 150 Pa ⁇ s, and then kneaded uniformly into a paste with a three-roll mill to prepare a sealing material paste. Next, sample No.
  • the center of an alkali-free glass substrate (OA-10 manufactured by Nippon Electric Glass Co., Ltd., 30 mm ⁇ 30 mm ⁇ 0.7 mm thickness, thermal expansion coefficient [30 to 380 ° C.] 38 ⁇ 10 ⁇ 7 / ° C.)
  • the sealing material paste was printed and applied so as to have a thickness of 20 mm ⁇ 20 mm ⁇ 20 ⁇ m, it was dried in a drying oven at 120 ° C. for 30 minutes. Subsequently, the obtained dried film was baked for 15 minutes at a softening point of +20 to 40 ° C. shown in the table to obtain a sample for evaluation.
  • the temperature raising / lowering rate was 10 ° C./min.
  • the mass of the sample for evaluation and the surface area of the fired film in contact with the iodine electrolyte solution were measured, and then the sample for evaluation was immersed in an iodine electrolyte solution in a Teflon (registered trademark) sealed container, and a constant temperature of 70 ° C. A Teflon (registered trademark) sealed container was left in the tank for 2 weeks. Finally, the mass reduction was calculated by dividing the value obtained by subtracting the mass of the evaluation sample after immersion from the mass of the evaluation sample before immersion by the surface area of the fired film.
  • the iodine electrolyte used for the mass loss evaluation was 0.1M lithium iodide, 0.05M iodine, 0.5M 4-tert-butylpyridine, and 1,2-dimethyl-3-propylimidazolium with respect to acetonitrile. What added the iodide 0.6M was used.
  • sample no. For 1 to 6, 9, and 10 a high strain point glass substrate processed into a strip shape (PP-8C, 10 mm ⁇ 50 mm ⁇ 1.8 mm thickness, manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient [30 to 380 ° C.] 85 After printing and coating so that a line width of 0.8 mm ⁇ length of 4 mm ⁇ thickness of 20 ⁇ m was formed at the center of ( ⁇ 10 ⁇ 7 / ° C.), it was dried in a drying oven at 120 ° C. for 30 minutes.
  • the wavelength of 808 nm is formed along the fired film from the glass substrate side on which the fired film is not formed.
  • a semiconductor laser (output 20 W, scanning speed 2 mm / s) was irradiated.
  • the fired film was softened by laser light and both glass substrates were bonded together, “bondable”, and the fired film was not softened, and both glass substrates were bonded, "bonded not possible” evaluated.
  • sample No. Nos. 1 to 8 contained 11 mol% or more of SiO 2 in the glass composition, so the weight loss was 0.10 mg / cm 2 or less, and the resistance to iodine electrolyte was high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Glass Compositions (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)

Abstract

This sealing material for dye-sensitized solar cells contains at least a bismuth-based glass powder, and is characterized in that the bismuth-based glass powder has a glass composition which contains, in mol%, 25-35% of Bi2O3 (excluding 35.0%), 20-40% of B2O3, 11-32% of SiO2, 5-20% of CuO, 0-20% of ZnO, 0-20% of Al2O3 + ZrO2 and 0-5% of Fe2O3.

Description

色素増感型太陽電池用封着材料Dye-sensitized solar cell sealing material
　本発明は、色素増感型太陽電池用封着材料に関し、具体的にはレーザー光による封着処理（以下、レーザー封着）に好適な色素増感型太陽電池用封着材料に関する。 The present invention relates to a sealing material for a dye-sensitized solar cell, and specifically relates to a sealing material for a dye-sensitized solar cell suitable for sealing treatment with laser light (hereinafter referred to as laser sealing).
　グレッチェル等が開発した色素増感型太陽電池は、シリコン半導体を使用した太陽電池と比べて、低コストであり、且つ製造に必要な原料が豊富にあるため、次世代の太陽電池として期待されている。 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 because there are abundant raw materials necessary for production. Yes.
　色素増感型太陽電池は、透明導電膜が形成された透明電極基板と、透明電極基板に形成された多孔質酸化物半導体層（主にＴｉＯ2層）からなる多孔質酸化物半導体電極と、その多孔質酸化物半導体電極に吸着されたＲｕ色素等の有機色素と、ヨウ素を含むヨウ素電解液と、触媒膜と透明導電膜が形成された対極基板等とで構成される。 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, An organic dye such as a 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.
　透明電極基板と対極基板には、ガラス基板やプラスチック基板等が使用される。透明電極基板にプラスチック基板を使用すると、透明電極膜の抵抗値が大きくなり、色素増感型太陽電池の光電変換効率が低下する。一方、透明電極基板にガラス基板を使用すると、透明電極膜の抵抗値が上昇し難くなり、色素増感型太陽電池の光電変換効率を維持することができる。従って、近年では、透明電極基板と対極基板として、ガラス基板が使用されている。 A glass substrate or a plastic substrate is used for 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 for 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, glass substrates have been used as transparent electrode substrates and counter electrode substrates.
　また、色素増感型太陽電池では、透明電極基板と対極基板の間にヨウ素電解液が充填される。色素増感型太陽電池からヨウ素電解液の漏れを防止するためには、透明電極基板と対極基板の外周縁を封着する必要がある。 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 leakage of the iodine electrolyte from the dye-sensitized solar cell, it is necessary to seal the outer peripheral edges of the transparent electrode substrate and the counter electrode substrate.
特開平１－２２０３８０号公報Japanese Patent Laid-Open No. 1-220380 特開２００２－７５４７２号公報JP 2002-75472 A 特開２００４－２９２２４７号公報JP 2004-292247 A 米国特許第６４１６３７５号明細書US Pat. No. 6,416,375 特開２００６－３１５９０２号公報JP 2006-315902 A
  色素増感型太陽電池の実用化への課題は、長期耐久性の向上である。長期耐久性を損なう原因として、太陽電池部材（封着材料等）とヨウ素電解液の反応により太陽電池部材やヨウ素電解液が劣化したり、気密性が低いことにより水分が内部に侵入して、ヨウ素電解液が劣化することが挙げられる。特に、封着材料に樹脂を用い、ヨウ素電解液にアセトニトリル等の有機溶媒を用いたときに、その傾向が顕著である。この場合、水分が内部に侵入したり、樹脂がヨウ素電解液により侵食されて、ヨウ素電解液が劣化したり、太陽電池からヨウ素電解液が漏洩して、電池特性が著しく低下する。 The challenge to commercialization of soot dye-sensitized solar cells is to improve long-term durability. As a cause of impairing the long-term durability, the solar cell member or iodine electrolyte is deteriorated by the reaction between the solar cell member (sealing material, etc.) and the iodine electrolyte, or moisture enters the inside due to low airtightness. It is mentioned that an iodine electrolyte solution deteriorates. 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, moisture penetrates into the interior, the resin is eroded by the iodine electrolyte solution, the iodine electrolyte solution is deteriorated, or the iodine electrolyte solution leaks from the solar cell, and the battery characteristics are remarkably deteriorated.
  このような事情に鑑み、封着材料に樹脂を使用しない方法が提案されている。例えば、特許文献１には、透明電極基板と対極基板の外周縁をガラスで封着することが記載されている。また、特許文献２、３には、透明電極基板と対極基板の外周縁を鉛ガラスで封着することが記載されている。 鑑 み In view of such circumstances, a method that does not use a resin as a 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.
  しかし、鉛ガラスは、ヨウ素電解液に侵食され易いため、封着材料に鉛ガラスを使用した場合でも、長期間の使用により、鉛ガラスの成分がヨウ素電解液中に溶出し、その結果、ヨウ素電解液が劣化して、電池特性が低下してしまう。 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 electrolyte solution deteriorates and the battery characteristics are deteriorated.
  また、封着材料に使用されるガラス粉末は、一般的に、軟化点が３００℃以上である。このため、上記の封着材料でガラス基板同士を封着する場合、電気炉に色素増感型太陽電池全体を投入し、ガラス粉末の軟化点以上の温度で焼成する必要がある。しかし、色素増感型太陽電池に使用されるヨウ素電解液や有機色素は、１２０～１３０℃程度の耐熱性しか有しておらず、この方法でガラス基板同士を封着すると、ヨウ素電解液が揮発したり、有機色素が熱劣化してしまう。 ガ ラ ス Moreover, the glass powder used for the sealing material generally has a softening point of 300 ° C or higher. For this reason, when sealing glass substrates with said sealing material, it is necessary to throw the whole dye-sensitized solar cell into an electric furnace, and to bake at the temperature more than the softening point of glass powder. However, iodine electrolytes and organic dyes used in dye-sensitized solar cells have only heat resistance of about 120 to 130 ° C. When sealing glass substrates together by this method, iodine electrolytes are It volatilizes or the organic dye is thermally degraded.
  このような事情に鑑み、近年、封着材料にレーザー光を照射し、フィールドエミッションディスプレイを封着する方法が検討されている。レーザー光は、封着すべき部位のみを局所加熱できることから、ヨウ素電解液の揮発や有機色素の劣化を防止した上で、ガラス基板同士を封着し得る可能性がある。 In view of such circumstances, in recent years, a method for sealing a field emission display by irradiating a sealing material with laser light has been studied. Since the laser beam can locally heat only the part to be sealed, there is a possibility that the glass substrates can be sealed together while preventing volatilization of the iodine electrolyte and deterioration of the organic dye.
  特許文献４、５には、封着材料にレーザー光を照射して、フィールドエミッションディスプレイの前面ガラス基板と背面ガラス基板を封着する方法が記載されている。しかし、特許文献４、５には、この方法に好適なガラス系について具体的な記載がなく、従来の封着材料にレーザー光を照射しても、封着部位において、レーザー光の光エネルギーを熱エネルギーに効率良く変換させることが困難であった。よって、従来の封着材料を用いて、ガラス基板同士を封着するためには、レーザー光の出力を上げる必要があり、その結果、有機色素等に不当な熱履歴がかかり、電池特性が低下する虞があった。 Patent Documents 4 and 5 describe a method of sealing a front glass substrate and a rear glass substrate of a field emission display by irradiating a sealing material with laser light. However, Patent Documents 4 and 5 do not specifically describe a glass system suitable for this method, and even if a conventional sealing material is irradiated with laser light, the light energy of the laser light is reduced at the sealing site. It was difficult to efficiently convert to heat energy. Therefore, in order to seal glass substrates together using a conventional sealing material, it is necessary to increase the output of the laser beam. As a result, an unreasonable thermal history is applied to organic pigments and the battery characteristics are degraded. There was a fear.
  そこで、本発明は、耐ヨウ素電解液性が高く、且つレーザー封着に好適な色素増感型太陽電池用封着材料を創案することにより、色素増感型太陽電池の長期信頼性を高めることを技術的課題とする。 Therefore, the present invention improves the long-term reliability of dye-sensitized solar cells by creating a sealing material for dye-sensitized solar cells that is highly resistant to iodine electrolyte and suitable for laser sealing. Is a technical issue.
　本発明者は、鋭意努力の結果、ビスマス系ガラス（Ｂｉ2Ｏ3－Ｂ2Ｏ3系ガラス）粉末のガラス組成中にＳｉＯ2及びＣｕＯを必須成分として所定量導入し、これを色素増感型太陽電池用封着材料に適用することにより、上記技術的課題を解決できることを見出し、本発明として、提案するものである。すなわち、本発明の色素増感型太陽電池用封着材料は、少なくともビスマス系ガラス粉末を含む色素増感型太陽電池用封着材料であって、ビスマス系ガラス粉末が、ガラス組成として、モル％で、 Ｂｉ2Ｏ3　２５～３５％(但し３５．０％を含まない)、Ｂ2Ｏ3　２０～４０％、ＳｉＯ2  １１～３２％、ＣｕＯ　５～２０％、ＺｎＯ  ０～２０％、Ａｌ2Ｏ3＋ＺｒＯ2　０～２０％、Ｆｅ2Ｏ3　０～５％を含有することを特徴とする。ここで、「Ａｌ2Ｏ3＋ＺｒＯ2」は、Ａｌ2Ｏ3とＺｒＯ2の合量を指す。なお、本発明の色素増感型太陽電池用封着材料は、ビスマス系ガラス粉末のみで構成される態様のみならず、例えば、ビスマス系ガラス粉末と耐火性フィラー粉末の複合材料も含み得る。 As a result of diligent efforts, the inventor introduced a predetermined amount of SiO 2 and CuO as essential components into the glass composition of bismuth-based glass (Bi 2 O 3 —B 2 O 3 -based glass) powder, and this was dye-sensitized. The present invention finds that the above technical problem can be solved by applying to a sealing material for a solar cell, and proposes it as the present invention. That is, the sealing material for a dye-sensitized solar cell of the present invention is a sealing material for a dye-sensitized solar cell containing at least a bismuth-based glass powder, and the bismuth-based glass powder has a mol% as a glass composition. Bi 2 O 3 25-35% (excluding 35.0%), B 2 O 3 20-40%, SiO 2 11-32%, CuO 5-20%, ZnO 0-20%, Al 2 O 3 + ZrO 2 0-20%, Fe 2 O 3 0-5%. Here, “Al 2 O 3 + ZrO 2 ” refers to the total amount of Al 2 O 3 and ZrO 2 . In addition, the sealing material for dye-sensitized solar cells of the present invention can include not only an embodiment composed of only bismuth-based glass powder but also a composite material of bismuth-based glass powder and refractory filler powder, for example.
  ビスマス系ガラス粉末において、Ｂｉ2Ｏ3の含有量を２５～３５モル％(但し３５．０モル％を含まない)に規制すれば、熱的安定性の低下を抑制した上で、ガラスを低融点化することができる。また、Ｂ2Ｏ3の含有量を２０～４０モル％に規制すれば、低融点特性を維持しつつ、熱的安定性を高めることができる。更に、ＺｎＯの含有量を０～２０モル％に規制すれば、熱的安定性を高めることができる。 In the bismuth-based glass powder, if the Bi 2 O 3 content is regulated to 25 to 35 mol% (excluding 35.0 mol%), the thermal stability is prevented from lowering and the glass is reduced. The melting point can be reached. Further, if the content of B 2 O 3 is regulated to 20 to 40 mol%, the thermal stability can be enhanced while maintaining the low melting point characteristics. Furthermore, if the ZnO content is restricted to 0 to 20 mol%, the thermal stability can be improved.
  ＳｉＯ2の含有量を１１モル％以上に規制すれば、ガラスがヨウ素電解液に侵食され難くなる。また、ＳｉＯ2の含有量を３２モル％以下に規制すれば、軟化点が不当に上昇する事態を防止し易くなる。また、Ａｌ2Ｏ3＋ＺｒＯ2の含有量を０～２０モル％に規制すれば、レーザー光の照射時に、ガラスが失透する事態を防止し易くなる。 If the content of SiO 2 is regulated to 11 mol% or more, the glass is less likely to be eroded by the iodine electrolyte. Moreover, if the content of SiO 2 is regulated to 32 mol% or less, it is easy to prevent a situation where the softening point is unduly increased. Further, if the content of Al 2 O 3 + ZrO 2 is restricted to 0 to 20 mol%, it becomes easy to prevent the glass from devitrifying when irradiated with laser light.
  ＣｕＯの含有量を５モル％以上に規制すれば、レーザー光の光エネルギーが熱エネルギーに効率良く変換される。その結果、ヨウ素電解液の揮発や有機色素の劣化を防止した上で、ガラス基板同士を適正に封着することができる。なお、レーザー光で封着材料を局所加熱する場合、加熱箇所から１ｍｍ離れた部位の温度は１００℃以下になり、電解液の揮発や有機色素の劣化を防止することができる。また、ＣｕＯの含有量を２０％以下に規制すれば、レーザー光の照射時に、ガラスが失透する事態を防止することができる。 If the CuO content is regulated to 5 mol% or more, the light energy of the laser light is efficiently converted into thermal energy. As a result, the glass substrates can be properly sealed with each other while preventing volatilization of the iodine electrolyte and deterioration of the organic pigment. In addition, when the sealing material is locally heated with laser light, the temperature at a location 1 mm away from the heating location is 100 ° C. or less, and the volatilization of the electrolytic solution and the deterioration of the organic dye can be prevented. Moreover, if content of CuO is controlled to 20% or less, the situation where glass devitrifies at the time of laser light irradiation can be prevented.
  第二に、本発明の色素増感型太陽電池用封着材料は、実質的にＰｂＯを含有しないことが好ましい。ここで、「実質的にＰｂＯを含有しない」とは、封着材料中のＰｂＯの含有量が１０００ｐｐｍ未満の場合を指す。このようにすれば、近年の環境的要請を満たすことができる。 Secondly, it is preferable that the sealing material for dye-sensitized solar cell of the present invention does not substantially contain PbO. Here, “substantially does not contain PbO” refers to a case where the content of PbO in the sealing material is less than 1000 ppm. In this way, environmental demands in recent years can be satisfied.
  第三に、本発明の色素増感型太陽電池用封着材料は、７０℃のヨウ素電解液に２週間浸漬したときの質量減が０．１ｍｇ／ｃｍ2以下であることが好ましい。ここで、「ヨウ素電解液」には、アセトニトリル中に、ヨウ化リチウム０．１Ｍ、ヨウ素０．０５Ｍ、４－ｔｅｒｔ－ブチルピリジン０．５Ｍ、及び１，２－ジメチル－３－プロピルイミダゾリウムヨーダイド０．６Ｍを溶解させたものを使用する。また、「質量減」は、色素増感型太陽電池用封着材料を緻密に焼き付けたガラス基板（焼成膜付きガラス基板）を、密閉容器中にてヨウ素電解液に浸漬し、浸漬前の質量から２週間経過後の質量を減じた値を、ヨウ素電解液に接する焼成膜の面積で除することで算出する。なお、ガラス基板は、ヨウ素電解液によって侵食されないものを用いる。 Thirdly, it is preferable that the sealing material for dye-sensitized solar cells of the present invention has a mass loss of 0.1 mg / cm 2 or less when immersed in an iodine electrolytic solution at 70 ° C. for 2 weeks. Here, “iodine electrolyte” includes 0.1M lithium iodide, 0.05M iodine, 0.5M 4-tert-butylpyridine, and 1,2-dimethyl-3-propylimidazolium iodide in acetonitrile. Use a solution of 0.6M id. In addition, “mass loss” means that a glass substrate (glass substrate with a fired film) on which a dye-sensitized solar cell sealing material is baked densely is immersed in an iodine electrolyte solution in a sealed container, and the mass before immersion Is calculated by dividing the value obtained by subtracting the mass after two weeks from 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.
  第四に、本発明の色素増感型太陽電池用封着材料は、更に、耐火性フィラー粉末を含み、その含有量が０～７０体積％であることが好ましい。このようにすれば、ガラス基板の熱膨張係数に厳密に整合するように、封着材料の熱膨張係数を調整することができる。なお、耐火性フィラー粉末の含有量は、流動性確保の観点から５０体積％以下がより好ましく、さらに好ましくは３０体積％以下、最も好ましくは１０体積％以下である。また、耐火性フィラー粉末の含有量を低減すると、透明電極基板と対極基板のギャップを狭小化、均一化し易くなる。 Fourthly, it is preferable that the sealing material for dye-sensitized solar cell of the present invention further contains a refractory filler powder and the content thereof is 0 to 70% by volume. In this way, the thermal expansion coefficient of the sealing material can be adjusted so as to closely match the thermal expansion coefficient of the glass substrate. In addition, the content of the refractory filler powder is more preferably 50% by volume or less, more preferably 30% by volume or less, and most preferably 10% by volume or less from the viewpoint of ensuring fluidity. Further, when the content of the refractory filler powder is reduced, the gap between the transparent electrode substrate and the counter electrode substrate is easily narrowed and made uniform.
  第五に、本発明の色素増感型太陽電池用封着材料は、レーザー封着に用いることが好ましい。このようにすれば、封着材料が局所加熱されるため、ヨウ素電解液の揮発や有機色素の劣化を防止し易くなる。レーザー光の光源として、種々のレーザーを使用することができる。特に、半導体レーザー、ＹＡＧレーザー、ＣＯ2レーザー、エキシマレーザー、赤外レーザー等は、取り扱いが容易な点で好適である。また、ガラスにレーザー光を的確に吸収させるために、レーザー光の発光中心波長は、５００～１６００ｎｍ、特に７５０～１３００ｎｍが好ましい。 Fifth, the dye-sensitized solar cell sealing material of the present invention is preferably used for laser sealing. In this way, since the sealing material is locally heated, it is easy to prevent volatilization of the iodine electrolyte and deterioration of the organic dye. Various lasers can be used as a laser light source. 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. In order to allow the laser light to be absorbed accurately into the glass, the emission center wavelength of the laser light is preferably 500 to 1600 nm, particularly preferably 750 to 1300 nm.
マクロ型ＤＴＡ装置で測定した場合、軟化点（Ｔｓ）を示す概略図である。It is the schematic which shows a softening point (Ts) when it measures with a macro type | mold DTA apparatus.
　本発明の色素増感型太陽電池用封着材料において、上記のように、ビスマス系ガラス粉末の各成分の含有範囲を限定した理由を以下に説明する。なお、各成分の含有範囲の説明において、％表示は、特に断りがある場合を除き、モル％を指す。 In the dye-sensitized solar cell sealing material of the present invention, the reason for limiting the content range of each component of the bismuth-based glass powder as described above 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.
  Ｂｉ2Ｏ3は、軟化点を下げるための主要成分であり、その含有量は２５～３５％（但し、３５．０％を含まない）、好ましくは２９～３４％、より好ましくは３０～３３％である。Ｂｉ2Ｏ3の含有量が２５％より少ないと、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。一方、Ｂｉ2Ｏ3の含有量が３５．０％以上では、ガラスが熱的に不安定になり、溶融時又はレーザー照射時にガラスが失透し易くなる。 Bi 2 O 3 is a main component for lowering the softening point, and its content is 25 to 35% (excluding 35.0%), preferably 29 to 34%, more preferably 30 to 33. %. When the content of Bi 2 O 3 is less than 25%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light. On the other hand, if the Bi 2 O 3 content is 35.0% or more, the glass becomes thermally unstable, and the glass tends to devitrify during melting or laser irradiation.
  Ｂ2Ｏ3は、ビスマス系ガラスのガラスネットワークを形成する成分であり、その含有量は２０～４０％、好ましくは２５～３５％、より好ましくは２８～３３％である。Ｂ2Ｏ3の含有量が２０％より少ないと、ガラスが熱的に不安定になり、溶融時又はレーザー照射時にガラスが失透し易くなる。一方、Ｂ2Ｏ3の含有量が４０％より多いと、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。 B 2 O 3 is a component that forms a glass network of bismuth-based glass, and its content is 20 to 40%, preferably 25 to 35%, more preferably 28 to 33%. When the content of B 2 O 3 is less than 20%, the glass becomes thermally unstable, and the glass is easily devitrified during melting or laser irradiation. On the other hand, if the content of B 2 O 3 is more than 40%, the softening point becomes too high and the glass is difficult to soften even when irradiated with laser light.
  ＳｉＯ2は、ヨウ素電解液によるガラスの侵食を生じ難くする成分である。その含有量は１１～３２％、好ましくは１８～３０％、より好ましくは２１～３０％である。ＳｉＯ2の含有量が１１％より少ないと、ガラスがヨウ素電解液に侵食され易くなり、ヨウ素電解液や電池特性の劣化が進行する。一方、ＳｉＯ2の含有量が３２％より多いと、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。 SiO 2 is a component that makes it difficult for glass to be eroded by the iodine electrolyte. Its content is 11 to 32%, preferably 18 to 30%, more preferably 21 to 30%. If the content of SiO 2 is less than 11%, the glass is easily eroded by the iodine electrolyte solution, and the deterioration of the iodine electrolyte solution and battery characteristics proceeds. On the other hand, if the content of SiO 2 is more than 32%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.
  ＣｕＯは、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させ易くする成分であり、また溶融時又はレーザー照射時の失透を抑制する成分である。その含有量は５～２０％、好ましくは５～１５％、より好ましくは８～１５％である。ＣｕＯの含有量が２０％より多いと、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなり、封着材料の流動性が損なわれ易くなる。なお、ＣｕＯの含有量が５％より少ないと、光吸収特性が低くなり、レーザー光を照射しても、ガラスが軟化し難くなる。 CuO is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass easily, and devitrification during melting or laser irradiation. It is a component which suppresses. Its content is 5 to 20%, preferably 5 to 15%, more preferably 8 to 15%. When the content of CuO is more than 20%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified and the fluidity of the sealing material is easily impaired. If the CuO content is less than 5%, the light absorption characteristics are lowered, and the glass is difficult to soften even when irradiated with laser light.
  ＺｎＯは、溶融時又はレーザー照射時の失透を抑制しつつ、熱膨張係数を低下させる成分であり、その含有量は０～２０％、好ましくは５～１５％である。ＺｎＯの含有量が２０％より多いと、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 ZnO is a component that decreases the coefficient of thermal expansion while suppressing devitrification during melting or laser irradiation, and its content is 0 to 20%, preferably 5 to 15%. When the content of ZnO is more than 20%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  Ａｌ2Ｏ3＋ＺｒＯ2は、ヨウ素電解液によるガラスの侵食を生じ難くする成分である。その含有量は０～２０％、好ましくは１～１０％である。Ａｌ2Ｏ3＋ＺｒＯ2の含有量が２０％より多いと、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。 Al 2 O 3 + ZrO 2 is a component that makes it difficult for glass to be eroded by the iodine electrolyte. Its content is 0 to 20%, preferably 1 to 10%. If the content of Al 2 O 3 + ZrO 2 is more than 20%, the softening point becomes too high, and the glass is difficult to soften even when irradiated with laser light.
  Ｆｅ2Ｏ3は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させ易くする成分であり、また溶融時又はレーザー照射時の失透を抑制する成分であり、その含有量は０～５％、特に０．１～３％が好ましい。Ｆｅ2Ｏ3の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 Fe 2 O 3 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass, and also when melted or irradiated with laser Is a component that suppresses devitrification, and its content is preferably 0 to 5%, particularly preferably 0.1 to 3%. When the content of Fe 2 O 3 is more than 5%, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.
　上記成分以外にも、例えば、以下の成分を添加してもよい。 In addition to the above components, for example, the following components may be added.
  ＢａＯ、ＳｒＯ、ＭｇＯ、ＣａＯは、熱的安定性を高める成分であり、これらの成分の含有量は合量で１０％以下、特に５％以下が好ましい。これらの成分の合量が多過ぎると、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。 BaO, SrO, MgO, and CaO are components that enhance the thermal stability, and the total content of these components is preferably 10% or less, particularly preferably 5% or less. If the total amount of these components is too large, the softening point becomes too high, and the glass becomes difficult to soften even when irradiated with laser light.
  ＢａＯの含有量は０～１０％が好ましく、０～７％がより好ましい。ＢａＯの含有量が多過ぎると、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 The content of BaO is preferably 0 to 10%, more preferably 0 to 7%. When there is too much content of BaO, the component balance in a glass composition will be impaired and it will become easy to devitrify glass conversely.
  ＳｒＯ、ＭｇＯ、ＣａＯの各々の含有量は０～３％が好ましく、０～１％がより好ましい。各成分の含有量が３％より多いと、ガラスが失透、或いは分相し易くなる。 The content of each of SrO, MgO and CaO is preferably 0 to 3%, more preferably 0 to 1%. When the content of each component is more than 3%, the glass is easily devitrified or phase-separated.
  ＣｅＯ2は、溶融時又はレーザー照射時の失透を抑制する成分であり、その含有量は０～５％、好ましくは０～２％、より好ましくは０～１％である。ＣｅＯ2の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 CeO 2 is a component that suppresses devitrification at the time of melting or laser irradiation, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. When the content of CeO 2 is more than 5%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  Ｐ2Ｏ5は、ヨウ素電解液によるガラスの侵食を生じ難くする成分であり、その含有量は０～１０％、特に０～５％が好ましい。Ｐ2Ｏ5の含有量が１０％より多いと、溶融時にガラスが分相し易くなる。 P 2 O 5 is a component that hardly causes erosion of the glass by the iodine electrolyte, and its content is preferably 0 to 10%, particularly preferably 0 to 5%. When the content of P 2 O 5 is more than 10%, the glass is likely to be phase-separated at the time of melting.
  Ｓｂ2Ｏ3は、熱的安定性を高める成分であり、その含有量は０～５％が好ましく、より好ましくは０～２％、最も好ましくは０～１％である。Ｓｂ2Ｏ3の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 Sb 2 O 3 is a component that enhances thermal stability, and its content is preferably 0 to 5%, more preferably 0 to 2%, and most preferably 0 to 1%. When the content of Sb 2 O 3 is more than 5%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  ＷＯ3は、熱的安定性を高める成分であり、その含有量は０～５％、特に０～２％が好ましい。ＷＯ3の含有量が多過ぎると、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 WO 3 is a component that enhances thermal stability, and its content is preferably 0 to 5%, particularly preferably 0 to 2%. When the content of WO 3 is too large, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.
  Ｉｎ2Ｏ3、Ｇａ2Ｏ3は、熱的安定性を高める成分であり、その含有量は合量で０～５％が好ましく、０～３％がより好ましい。但し、Ｉｎ2Ｏ3とＧａ2Ｏ3の合量が多過ぎると、ガラス組成内の成分バランスが損なわれて、逆にガラスが失透し易くなる。 In 2 O 3 and Ga 2 O 3 are components that enhance the thermal stability, and the total content thereof is preferably 0 to 5%, more preferably 0 to 3%. However, when the total content of In 2 O 3 and Ga 2 O 3 is too large, is impaired balance of components in the glass composition, the glass is liable to devitrify reversed.
  Ｌｉ、Ｎａ、Ｋ、及びＣｓの酸化物は、軟化点を低下させる成分であるが、溶融時の失透を助長する作用を有するため、その含有量は合量で２％以下が好ましい。 酸化 物 The oxides of Li, Na, K, and Cs are components that lower the softening point. However, since they have an effect of promoting devitrification at the time of melting, the total content is preferably 2% or less.
  Ｌａ2Ｏ3、Ｙ2Ｏ3、及びＧｄ2Ｏ3は、溶融時の分相を抑制する成分であるが、これらの合量が３％より多いと、軟化点が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる。 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 of these is more than 3%, the softening point becomes too high, and the laser Even if light is irradiated, the glass becomes difficult to soften.
  ＮｉＯ、Ｖ2Ｏ5、ＣｏＯ、ＭｏＯ3、ＴｉＯ2、ＭｎＯ2は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させ易くする成分である。これらの成分は合量で０～７％、特に０～３％が好ましい。これらの成分の合量が７％より多いと、ガラスが失透し易くなる。 NiO, V 2 O 5 , CoO, MoO 3 , TiO 2 , and MnO 2 are components having light absorption characteristics. When light having a predetermined emission center wavelength is irradiated, the light is absorbed and the glass is softened. It is a component that facilitates. The total amount of these components is preferably 0 to 7%, particularly preferably 0 to 3%. If the total amount of these components is more than 7%, the glass tends to devitrify.
  また、上記以外の成分であっても、ガラス特性を損なわない範囲、例えば１０％（好ましくは５％）まで他の成分を添加してもよい。なお、本発明に係るビスマス系ガラス粉末は、環境的観点、及びヨウ素電解液によるガラスの侵食を防止する観点から、実質的にＰｂＯを含有しないことが好ましい。ここで、「実質的にＰｂＯを含有しない」とは、ガラス組成中のＰｂＯの含有量が１０００ｐｐｍ未満の場合を指す。 In addition, even if it is a component other than the above, other components may be added up to a range that does not impair the glass properties, for example, 10% (preferably 5%). In addition, it is preferable that the bismuth-type glass powder concerning this invention does not contain PbO substantially from an environmental viewpoint and the viewpoint which prevents the glass erosion by an iodine electrolyte solution. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is less than 1000 ppm.
  本発明の色素増感型太陽電池用封着材料において、７０℃のヨウ素電解液に２週間浸漬したときの質量減は、好ましくは０．１ｍｇ／ｃｍ2以下、より好ましくは０．０５ｍｇ／ｃｍ2以下、更に好ましくは実質的に質量減がない、つまり０．０１ｍｇ／ｃｍ2以下が好ましい。質量減が少ない程、長期間に亘り、ヨウ素電解液や電池特性の劣化を防止し易くなる。 In the sealing material for dye-sensitized solar cell of the present invention, the mass loss when immersed in an iodine electrolytic solution at 70 ° C. for 2 weeks is preferably 0.1 mg / cm 2 or less, more preferably 0.05 mg / cm. 2 or less, more preferably substantially no mass loss, that is, 0.01 mg / cm 2 or less is preferable. The smaller the mass loss, the easier it is to prevent the iodine electrolyte and battery characteristics from deteriorating over a long period of time.
  本発明の色素増感型太陽電池用封着材料は、ガラス基板との熱膨張係数の整合、機械的強度を向上させるために、耐火性フィラー粉末を添加してもよい。一方、耐火性フィラー粉末の添加量を低減すれば、色素増感型太陽電池用封着材料の流動性、特に封着強度を高めることができる。従って、ガラス粉末と耐火性フィラー粉末の混合割合は、好ましくはガラス粉末３０～１００体積％、耐火性フィラー粉末０～７０体積％、より好ましくはガラス粉末５０～１００体積％、耐火性フィラー粉末０～５０体積％、更に好ましくはガラス粉末９０～１００体積％、耐火性フィラー粉末０～１０体積％である。耐火性フィラー粉末の含有量が７０体積％より多いと、相対的にガラス粉末の割合が低くなり過ぎて、所望の流動性を確保し難くなる。 色素 The dye-sensitized solar cell sealing material of the present invention may contain a refractory filler powder in order to improve the thermal expansion coefficient matching with the glass substrate and the mechanical strength. On the other hand, if the addition amount of the refractory filler powder is reduced, the fluidity, particularly the sealing strength, of the dye-sensitized solar cell sealing material can be increased. Therefore, the mixing ratio of the glass powder and the refractory filler powder is preferably 30 to 100% by volume of the glass powder, 0 to 70% by volume of the refractory filler powder, more preferably 50 to 100% by volume of the refractory filler powder, and 0% of the refractory filler powder. -50% by volume, more preferably 90-100% by volume of glass powder, and 0-10% by volume of refractory filler powder. When the content of the refractory filler powder is more than 70% by volume, the ratio of the glass powder becomes relatively low, and it becomes difficult to ensure desired fluidity.
　耐火性フィラー粉末の粒子経が大き過ぎると、封着部分に局所的に突起物が発生するため、セルギャップを均一化し難くなる。このような事態を防止するために、耐火性フィラー粉末の最大粒子径Ｄmaxは２５μｍ以下が好ましく、１５μｍ以下がより好ましい。ここで、「最大粒子径Ｄmax」とは、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して９９％である粒子径を表す。 If the particle size of the refractory filler powder is too large, protrusions are locally generated at the sealed portion, making it difficult to make the cell gap uniform. In order to prevent such a situation, the maximum particle diameter D max of the refractory filler powder is preferably 25 μm or less, and more preferably 15 μm or less. Here, the “maximum particle diameter D max ” represents a particle diameter in which the accumulated amount is 99% cumulative from the smaller particle in the volume-based cumulative particle size distribution curve measured by the laser diffraction method. .
  耐火性フィラー粉末は、種々の材料が使用可能であるが、ガラス粉末やヨウ素電解液と反応し難いものが好ましい。具体的には、耐火性フィラー粉末として、ジルコン、ジルコニア、酸化錫、チタン酸アルミニウム、石英、β－スポジュメン、ムライト、チタニア、石英ガラス、β－ユークリプタイト、β－石英、リン酸ジルコニウム、リン酸タングステン酸ジルコニウム、タングステン酸ジルコニウム、ウイレマイト、［ＡＢ2（ＭＯ4）3］等のＮＺＰ型の基本構造を有する化合物、
Ａ：Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｕ、Ｎｉ、Ｍｎ等
Ｂ：Ｚｒ、Ｔｉ、Ｓｎ、Ｎｂ、Ａｌ、Ｓｃ、Ｙ等
Ｍ：Ｐ、Ｓｉ、Ｗ、Ｍｏ等
若しくはこれらの固溶体が好ましい。 Various materials can be used as the refractory filler powder, but those that do not easily react with glass powder or iodine electrolyte are preferable. 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 Compounds 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. Or these solid solutions are preferable.
　本発明の色素増感型太陽電池用封着材料は、レーザー封着に用いることが好ましい。レーザー封着を行うと、封着材料を局所加熱し得るため、ヨウ素電解液等の構成部材の熱劣化を防止した上で、ガラス基板同士を封着することができる。 The dye-sensitized solar cell sealing material of the present invention is preferably used for laser sealing. When laser sealing is performed, the sealing material can be locally heated. Therefore, it is possible to seal glass substrates together while preventing thermal deterioration of components such as iodine electrolyte.
  本発明の色素増感型太陽電池用封着材料において、軟化点は５６０℃以下が好ましく、５５０℃以下がより好ましく、５３０℃以下が更に好ましい。軟化点が５６０℃より高いと、ガラスの粘性が高くなり過ぎて、レーザー光を照射しても、ガラスが軟化し難くなる傾向があり、封着強度を高めるためには、レーザー光の出力を上げる必要がある。レーザー光の出力を上げると、ガラス基板の周辺温度が高くなり、例えば、ガラス基板として、ソーダガラス等を用いた場合、ガラス基板が変形し易くなる。 に お い て In the dye-sensitized solar cell sealing material of the present invention, the softening point is preferably 560 ° C or lower, more preferably 550 ° C or lower, and further preferably 530 ° C or lower. If the softening point is higher than 560 ° C, the viscosity of the glass becomes too high, and even when irradiated with laser light, the glass tends to be difficult to soften. To increase the sealing strength, the output of the laser light must be increased. It is necessary to raise. When the output of the laser beam is increased, the ambient temperature of the glass substrate is increased. For example, when soda glass is used as the glass substrate, the glass substrate is easily deformed.
  本発明の色素増感型太陽電池用封着材料において、熱膨張係数は、ガラス基板としてソーダガラスや高歪点ガラスを用いる場合、９０×１０-7／℃以下、特に８５×１０-7／℃以下が好ましく、ガラス基板として無アルカリガラスを用いる場合、５５×１０-7／℃以下、特に５０×１０-7／℃以下が好ましい。このようにすれば、ガラス基板や封着部位にかかる応力が低減されるため、封着部位の応力破壊を防止し易くなる。 In the sealing material for dye-sensitized solar cell of the present invention, the thermal expansion coefficient is 90 × 10 −7 / ° C. or less, particularly 85 × 10 −7 / ° C. when soda glass or high strain point glass is used as the glass substrate. ° C or lower is preferable, and when alkali-free glass is used as the glass substrate, 55 × 10 −7 / ° C. or lower, particularly 50 × 10 −7 / ° C. or lower is preferable. In this way, the stress applied to the glass substrate and the sealing part is reduced, so that it becomes easy to prevent stress destruction of the sealing part.
  本発明の色素増感型太陽電池用封着材料は、更に、レーザー光の光吸収を促進させるために、酸化物顔料を１０体積％まで含有してもよい。 色素 The dye-sensitized solar cell sealing material of the present invention may further contain up to 10% by volume of an oxide pigment in order to promote light absorption of laser light.
  本発明の色素増感型太陽電池用封着材料は、更に、封着部位の厚みを均一化するために、スペーサーとしてガラスファイバー、ガラスビーズ、シリカビーズ、樹脂ビーズ等を１０体積％まで含有してもよい。 The sealing material for dye-sensitized solar cells of the present invention further contains glass fiber, glass beads, silica beads, resin beads, etc. up to 10% by volume as spacers in order to make the thickness of the sealing part uniform. May be.
  本発明の色素増感型太陽電池用封着材料は、粉末のまま使用に供してもよいが、取扱い性向上の観点から、ビークルと均一に混練し、封着材料ペーストに加工することが好ましい。ビークルは、主に溶媒と樹脂とからなり、樹脂はペーストの粘性を調整する目的で添加される。また、必要に応じて、界面活性剤、増粘剤等を添加することもできる。作製されたペーストは、ディスペンサーやスクリーン印刷機等の塗布機を用いて塗布される。 The sealing material for a dye-sensitized solar cell of the present invention may be used as a powder, but from the viewpoint of improving handleability, it is preferably kneaded uniformly with a vehicle and processed into a sealing material 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.
  樹脂としては、アクリル酸エステル（アクリル樹脂）、エチルセルロース、ポリエチレングリコール誘導体、ニトロセルロース、ポリメチルスチレン、ポリエチレンカーボネート、メタクリル酸エステル等が使用可能である。特に、アクリル酸エステル、ニトロセルロースは、熱分解性が良好であるため、好ましい。 As the candy 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.
  溶媒としては、Ｎ、Ｎ’－ジメチルホルムアミド（ＤＭＦ）、α－ターピネオール、高級アルコール、γ－ブチルラクトン（γ－ＢＬ）、テトラリン、ブチルカルビトールアセテート、酢酸エチル、酢酸イソアミル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ベンジルアルコール、トルエン、３－メトキシ－３－メチルブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、プロピレンカーボネート、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ－メチル－２－ピロリドン等が使用可能である。特に、α－ターピネオールは、高粘性であり、樹脂等の溶解性も良好であるため、好ましい。 Solvents include 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- Methyl-2-pyrrolidone or 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.
  以下、実施例に基づいて本発明を詳細に説明する。但し、以下の実施例は、単なる例示である。本発明は、以下の実施例に何ら限定されない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples are merely illustrative. The present invention is not limited to the following examples.
  表１は、本発明の実施例（試料Ｎｏ．１～８）を示している。 Table 1 shows examples of the present invention (sample Nos. 1 to 8).
　表２は、本発明の比較例（試料Ｎｏ．９、１０）を示している。 Table 2 shows comparative examples (sample Nos. 9 and 10) of the present invention.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
  次のようにして、表中の各試料を調製した。まず表中のガラス組成になるように、各種酸化物、炭酸塩等の原料を調合したガラスバッチを準備し、このガラスバッチを白金坩堝に入れて１０００～１２００℃で１～２時間溶融した。次に、得られた溶融ガラスの一部を熱膨張係数測定用サンプルとしてステンレス製の金型に流し出し、その他の溶融ガラスを水冷ローラーにより薄片状に成形した。最後に、薄片状のガラスをボールミルにて粉砕後、目開き４５μｍの篩いを通過させて、平均粒子径Ｄ50が約５μｍの各ガラス粉末を得た。なお、熱膨張係数測定用サンプルは、成形後に所定の徐冷（アニール）処理を行った。 Each sample 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 glass batch was put in a platinum crucible and melted at 1000 to 1200 ° C. for 1 to 2 hours. Next, a part of the obtained molten glass was poured into a stainless steel mold as a sample for measuring the thermal expansion coefficient, and the other molten glass was formed into a flake shape with a water-cooled roller. Finally, the glass flakes were pulverized with a ball mill and passed through a sieve having an opening of 45 μm to obtain glass powders having an average particle diameter D 50 of about 5 μm. The sample for measuring the thermal expansion coefficient was subjected to a predetermined slow cooling (annealing) treatment after molding.
  耐火物フィラー粉末は、コーディエライトを用い、その平均粒子径Ｄ50が２．５μｍ、最大粒子径Ｄmaxが１０μｍになるように調製した。 The refractory filler powder was prepared using cordierite so that the average particle diameter D 50 was 2.5 μm and the maximum particle diameter D max was 10 μm.
  表中に示す通りに、ビスマス系ガラス粉末と耐火性フィラー粉末を混合し、試料Ｎｏ．１～１０を作製した。試料Ｎｏ．１～１０につき、ガラス転移点、軟化点、熱膨張係数、ヨウ素電解液に対する質量減、接合の可否を評価した。 示 す As shown in the table, bismuth-based glass powder and refractory filler powder were mixed and sample No. 1 to 10 were produced. Sample No. For 1 to 10, the glass transition point, the softening point, the thermal expansion coefficient, the mass loss with respect to the iodine electrolyte, and the possibility of bonding were evaluated.
  ガラス転移点、軟化点は、示差熱分析装置で測定した。測定は、大気中において、昇温速度１０℃／分で行い、室温から測定を開始した。 The glass transition point and softening point were measured with a differential thermal analyzer. The measurement was performed in the atmosphere at a temperature rising rate of 10 ° C./min, and the measurement was started from room temperature.
  熱膨張係数は、押棒式熱膨張係数測定装置で求めた。測定温度範囲を３０～３００℃とした。 The thermal expansion coefficient was obtained with a push rod type thermal expansion coefficient measuring device. The measurement temperature range was 30 to 300 ° C.
  以下のようにして、質量減を算出した。まず各試料とエチルセルロース系ビークルを混練し、粘度が約１５０Ｐａ・ｓになるように調製した後、更に三本ロールミルで均一に混錬、ペースト化して、封着材料ペーストを作製した。次に、試料Ｎｏ．１～６、９、１０については、高歪点ガラス基板（日本電気硝子株式会社製ＰＰ－８Ｃ、３０ｍｍ×３０ｍｍ×１．８ｍｍ厚、熱膨張係数［３０～３８０℃］８５×１０-7／℃）の中心部に、２０ｍｍ×２０ｍｍ×２０μｍ厚になるように、封着材料ペーストを印刷塗布した後、乾燥オーブンにより１２０℃で３０分間乾燥した。また、試料Ｎｏ．７、８については、無アルカリガラス基板（日本電気硝子株式会社製ＯＡ－１０、３０ｍｍ×３０ｍｍ×０．７ｍｍ厚、熱膨張係数［３０～３８０℃］３８×１０-7／℃）の中心部に２０ｍｍ×２０ｍｍ×２０μｍ厚になるように、封着材料ペーストを印刷塗布した後、乾燥オーブンにより１２０℃で３０分間乾燥した。続いて、得られた乾燥膜を表中に示す軟化点＋２０～４０℃で１５分間焼成して、評価用試料を得た。焼成に際し、昇降温速度を１０℃／分とした。更に、評価用試料の質量と、ヨウ素電解液に接する焼成膜の表面積とを測定し、次に評価用試料をテフロン（登録商標）製密閉容器中のヨウ素電解液に浸漬し、７０℃の恒温槽にテフロン（登録商標）製密閉容器を２週間静置した。最後に、浸漬前の評価用試料の質量から浸漬後の評価用試料の質量を減じた値を、焼成膜の表面積で除することで、質量減を算出した。質量減の評価に使用したヨウ素電解液は、アセトニトリルに対し、ヨウ化リチウム０．１Ｍ、ヨウ素０．０５Ｍ、４－ｔｅｒｔ－ブチルピリジン０．５Ｍ、及び１，２－ジメチル－３－プロピルイミダゾリウムヨーダイド０．６Ｍを加えたものを使用した。 Mass loss was calculated as follows. First, each sample and an ethylcellulose-based vehicle were kneaded and prepared so as to have a viscosity of about 150 Pa · s, and then kneaded uniformly into a paste with a three-roll mill to prepare a sealing material paste. Next, sample No. For 1 to 6, 9, and 10, high strain point glass substrates (PP-8C manufactured by Nippon Electric Glass Co., Ltd., 30 mm × 30 mm × 1.8 mm thickness, coefficient of thermal expansion [30 to 380 ° C.] 85 × 10 −7 / The sealing material paste was printed and applied to the central portion of (° C.) so as to have a thickness of 20 mm × 20 mm × 20 μm, and then dried at 120 ° C. for 30 minutes in a drying oven. Sample No. 7 and 8, the center of an alkali-free glass substrate (OA-10 manufactured by Nippon Electric Glass Co., Ltd., 30 mm × 30 mm × 0.7 mm thickness, thermal expansion coefficient [30 to 380 ° C.] 38 × 10 −7 / ° C.) After the sealing material paste was printed and applied so as to have a thickness of 20 mm × 20 mm × 20 μm, it was dried in a drying oven at 120 ° C. for 30 minutes. Subsequently, the obtained dried film was baked for 15 minutes at a softening point of +20 to 40 ° C. shown in the table to obtain a sample for evaluation. During firing, the temperature raising / lowering rate was 10 ° C./min. Furthermore, the mass of the sample for evaluation and the surface area of the fired film in contact with the iodine electrolyte solution were measured, and then the sample for evaluation was immersed in an iodine electrolyte solution in a Teflon (registered trademark) sealed container, and a constant temperature of 70 ° C. A Teflon (registered trademark) sealed container was left in the tank for 2 weeks. Finally, the mass reduction was calculated by dividing the value obtained by subtracting the mass of the evaluation sample after immersion from the mass of the evaluation sample before immersion by the surface area of the fired film. The iodine electrolyte used for the mass loss evaluation was 0.1M lithium iodide, 0.05M iodine, 0.5M 4-tert-butylpyridine, and 1,2-dimethyl-3-propylimidazolium with respect to acetonitrile. What added the iodide 0.6M was used.
  次のようにして、接合の可否を評価した。まず試料Ｎｏ．１～６、９、１０については、短冊状に加工した高歪点ガラス基板（日本電気硝子株式会社製ＰＰ－８Ｃ、１０ｍｍ×５０ｍｍ×１．８ｍｍ厚、熱膨張係数［３０～３８０℃］８５×１０-7／℃）の中心部に線幅０．８ｍｍ×長さ４ｍｍ×厚み２０μｍになるように、印刷塗布した後、乾燥オーブンにより１２０℃で３０分間乾燥した。また、試料Ｎｏ．７、８については、無アルカリガラス基板（日本電気硝子株式会社製ＯＡ－１０、１０ｍｍ×５０ｍｍ×０．７ｍｍ厚、熱膨張係数［３０～３８０℃］３８×１０-7／℃）の中心部に線幅０．８ｍｍ×長さ４ｍｍ×厚み２０μｍになるように、印刷塗布した後、乾燥オーブンにより１２０℃で３０分間乾燥した。次に、表中に示す軟化点で１２０分間焼成し、ビークルに含まれる樹脂成分を脱バインダーした。焼成に際し、昇降温速度を１０℃／分とした。続いて、焼成膜が形成されたガラス基板の上に、同一形状、同一材質のガラス基板を正確に重ねた後、焼成膜が形成されていないガラス基板側から焼成膜に沿って、波長８０８ｎｍの半導体レーザー（出力２０Ｗ、走査速度２ｍｍ／ｓ）を照射した。最後に、レーザー光により焼成膜が軟化し、両ガラス基板が接合されていたものを「接合可」、焼成膜が軟化せず、両ガラス基板が接合されていなかったものを「接合不可」と評価した。 The possibility of joining was evaluated as follows. First, sample no. For 1 to 6, 9, and 10, a high strain point glass substrate processed into a strip shape (PP-8C, 10 mm × 50 mm × 1.8 mm thickness, manufactured by Nippon Electric Glass Co., Ltd., thermal expansion coefficient [30 to 380 ° C.] 85 After printing and coating so that a line width of 0.8 mm × length of 4 mm × thickness of 20 μm was formed at the center of (× 10 −7 / ° C.), it was dried in a drying oven at 120 ° C. for 30 minutes. Sample No. 7 and 8, the center of an alkali-free glass substrate (OA-10, manufactured by Nippon Electric Glass Co., Ltd., 10 mm × 50 mm × 0.7 mm thickness, coefficient of thermal expansion [30 to 380 ° C.] 38 × 10 −7 / ° C.) After printing and coating so that the line width was 0.8 mm × length 4 mm × thickness 20 μm, it was dried in a drying oven at 120 ° C. for 30 minutes. Next, the resin component contained in the vehicle was debindered by baking for 120 minutes at the softening point shown in the table. During firing, the temperature raising / lowering rate was 10 ° C./min. Subsequently, after the glass substrate having the same shape and the same material is accurately stacked on the glass substrate on which the fired film is formed, the wavelength of 808 nm is formed along the fired film from the glass substrate side on which the fired film is not formed. A semiconductor laser (output 20 W, scanning speed 2 mm / s) was irradiated. Lastly, the fired film was softened by laser light and both glass substrates were bonded together, "bondable", and the fired film was not softened, and both glass substrates were bonded, "bonded not possible" evaluated.
  表１から明らかなように、試料Ｎｏ．１～８は、ガラス組成中にＳｉＯ2を１１モル％以上含んでいるため、質量減が０．１０ｍｇ／ｃｍ2以下であり、耐ヨウ素電解液性が高かった。また、試料Ｎｏ．１～８は、ガラス組成中にＣｕＯを５モル％以上含んでいるため、レーザー光の照射により、両ガラス基板を接合することができた。 As is clear from Table 1, sample No. Nos. 1 to 8 contained 11 mol% or more of SiO 2 in the glass composition, so the weight loss was 0.10 mg / cm 2 or less, and the resistance to iodine electrolyte was high. Sample No. In Nos. 1 to 8, since the glass composition contained 5 mol% or more of CuO, both glass substrates could be bonded by laser light irradiation.
  表２から明らかなように、試料Ｎｏ．９は、ガラス組成中にＣｕＯを所定量含んでいないため、レーザー光の照射により、両ガラス基板を接合することができなかった。また、試料Ｎｏ．１０は、ガラス組成中にＳｉＯ2を所定量含んでいないため、質量減が０．４５ｍｇ／ｃｍ2であり、耐ヨウ素電解性が低かった。 As apparent from Table 2, the sample No. Since No. 9 did not contain a predetermined amount of CuO in the glass composition, both glass substrates could not be bonded by laser light irradiation. Sample No. No. 10 did not contain a predetermined amount of SiO 2 in the glass composition, so the mass loss was 0.45 mg / cm 2 and the iodine resistance was low.

Claims (5)

  1. 　少なくともビスマス系ガラス粉末を含む色素増感型太陽電池用封着材料であって、
      ビスマス系ガラス粉末が、ガラス組成として、モル％で、 Ｂｉ2Ｏ3　２５～３５％(但し３５．０％を含まない)、Ｂ2Ｏ3　２０～４０％、ＳｉＯ2  １１～３２％、ＣｕＯ　５～２０％、ＺｎＯ  ０～２０％、Ａｌ2Ｏ3＋ＺｒＯ2　０～２０％、Ｆｅ2Ｏ3　０～５％を含有することを特徴とする色素増感型太陽電池用封着材料。     A dye-sensitized solar cell sealing material containing at least a bismuth-based glass powder,
    Bismuth-based glass powder has a glass composition of mol%, Bi 2 O 3 25-35% (excluding 35.0%), B 2 O 3 20-40%, SiO 2 11-32%, CuO A sealing material for a dye-sensitized solar cell, comprising 5 to 20%, ZnO 0 to 20%, Al 2 O 3 + ZrO 2 0 to 20%, and Fe 2 O 3 0 to 5%.
  2.   実質的にＰｂＯを含有しないことを特徴とする請求項１に記載の色素増感型太陽電池用封着材料。 The sealing material for a dye-sensitized solar cell according to claim 1, which contains substantially no PbO.
  3.   ７０℃のヨウ素電解液に２週間浸漬したときの質量減が０．１ｍｇ／ｃｍ2以下であることを特徴とする請求項１又は２に記載の色素増感型太陽電池用封着材料。 3. The dye-sensitized solar cell sealing material according to claim 1, wherein the weight loss when immersed in an iodine electrolyte at 70 ° C. for 2 weeks is 0.1 mg / cm 2 or less.
  4.   更に、耐火性フィラー粉末を含み、その含有量が０～７０体積％であることを特徴とする請求項１～３の何れか一項に記載の色素増感型太陽電池用封着材料。 The sealing material for a dye-sensitized solar cell according to any one of claims 1 to 3, further comprising a refractory filler powder, the content of which is 0 to 70% by volume.
  5.   レーザー封着に用いることを特徴とする請求項１～４の何れか一項に記載の色素増感型太陽電池用封着材料。 The dye-sensitized solar cell sealing material according to any one of claims 1 to 4, wherein the sealing material is used for laser sealing.
PCT/JP2013/068638 2012-07-09 2013-07-08 Sealing material for dye-sensitized solar cells WO2014010553A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012153321A JP2014015350A (en) 2012-07-09 2012-07-09 Sealing material for dye-sensitized solar cell
JP2012-153321 2012-07-09

Publications (1)

Publication Number Publication Date
WO2014010553A1 true WO2014010553A1 (en) 2014-01-16

Family

ID=49916007

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/068638 WO2014010553A1 (en) 2012-07-09 2013-07-08 Sealing material for dye-sensitized solar cells

Country Status (3)

Country Link
JP (1) JP2014015350A (en)
TW (1) TW201404751A (en)
WO (1) WO2014010553A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6952950B2 (en) * 2016-04-21 2021-10-27 日本電気硝子株式会社 Composite powder material
JP6913276B2 (en) * 2017-01-26 2021-08-04 日本電気硝子株式会社 Airtight package
KR102671969B1 (en) * 2019-08-16 2024-06-05 삼성전기주식회사 Multilayered capacitor and board having the same mounted thereon
CN113121120B (en) * 2021-05-31 2022-11-22 四川华炫新材料科技有限公司 High-alkali-resistance basalt fiber and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006169018A (en) * 2004-12-14 2006-06-29 Nippon Electric Glass Co Ltd Glass tablet, its manufacturing method, and glass tablet-integrated exhaust tube
JP2009234816A (en) * 2008-03-26 2009-10-15 Nippon Electric Glass Co Ltd Sealing material for organic el display
JP2010280554A (en) * 2009-06-08 2010-12-16 Nippon Electric Glass Co Ltd Glass for dye-sensitized solar cell, and material for dye-sensitized solar cell
WO2010147160A1 (en) * 2009-06-17 2010-12-23 旭硝子株式会社 Glass frit for formation of electrode, and electrically conductive paste for formation of electrode and solar cell each utilizing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006169018A (en) * 2004-12-14 2006-06-29 Nippon Electric Glass Co Ltd Glass tablet, its manufacturing method, and glass tablet-integrated exhaust tube
JP2009234816A (en) * 2008-03-26 2009-10-15 Nippon Electric Glass Co Ltd Sealing material for organic el display
JP2010280554A (en) * 2009-06-08 2010-12-16 Nippon Electric Glass Co Ltd Glass for dye-sensitized solar cell, and material for dye-sensitized solar cell
WO2010147160A1 (en) * 2009-06-17 2010-12-23 旭硝子株式会社 Glass frit for formation of electrode, and electrically conductive paste for formation of electrode and solar cell each utilizing same

Also Published As

Publication number Publication date
JP2014015350A (en) 2014-01-30
TW201404751A (en) 2014-02-01

Similar Documents

Publication Publication Date Title
JP5534550B2 (en) Dye-sensitized solar cell glass composition and dye-sensitized solar cell material
JP5489054B2 (en) Dye-sensitized solar cell glass composition and dye-sensitized solar cell material
JP5862973B2 (en) Manufacturing method of organic EL display
JP5500079B2 (en) Glass member with sealing material layer and manufacturing method thereof, and electronic device and manufacturing method thereof
JP5224102B2 (en) Sealing material for organic EL display
JP5713422B2 (en) Dye-sensitized solar cell glass composition and dye-sensitized solar cell material
CN113105117A (en) Glass composition, glass powder, sealing material, glass paste, sealing method, sealed package, and organic electroluminescent element
WO2014010553A1 (en) Sealing material for dye-sensitized solar cells
JP2011057477A (en) Sealing material
JP2010280554A (en) Glass for dye-sensitized solar cell, and material for dye-sensitized solar cell
JP5458648B2 (en) Sealing material for organic EL lighting
JP5370011B2 (en) Method for producing glass member with sealing material layer and method for producing electronic device
JP5713189B2 (en) Dye-sensitized solar cell glass and dye-sensitized solar cell material
JP2013119501A (en) Methods for producing glass member added with sealing material layer, and hermetic member
JP5994438B2 (en) Method for producing glass substrate with sealing material layer
JP2013155059A (en) Glass composition for dye-sensitized solar cell and material for the dye-sensitized solar cell
JP5534553B2 (en) Dye-sensitized solar cell glass composition and dye-sensitized solar cell material
JP2015020914A (en) Manufacturing method of glass package
JP5892467B2 (en) Glass substrate with sealing material layer and glass package using the same
JP6768194B2 (en) Bismuth-based glass, manufacturing method of bismuth-based glass and sealing material
JP6840982B2 (en) Bismuth glass and sealing materials using it
KR102427006B1 (en) Bismuth-based glass, bismuth-based glass manufacturing method and sealing material
KR101236373B1 (en) Manufacturing method for organic el display
JP2024019999A (en) Glass composition, glass paste, sealed package, and organic electroluminescence element
JP2012106900A (en) Sealing material, and paste material using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13817328

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13817328

Country of ref document: EP

Kind code of ref document: A1