WO2014010553A1 - Matériau de scellement pour cellule solaire à colorant - Google Patents

Matériau de scellement pour cellule solaire à colorant Download PDF

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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
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Prior art keywords
glass
sealing material
dye
sensitized solar
content
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PCT/JP2013/068638
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English (en)
Japanese (ja)
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朋子 榎本
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日本電気硝子株式会社
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    • 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.

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  • Electrochemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Glass Compositions (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne un matériau de scellement pour cellule solaire à colorant qui contient au moins une poudre de verre à base de bismuth. Cette poudre de verre à base de bismuth est caractéristique en ce qu'elle comprend, pour la composition du verre, en % en moles, Bi2O3 : 25 à 35% (35.0% étant exclu) ; B2O3 : 20 à 40% ; SiO2 : 11 à 32% ; CuO : 5 à 20% ; ZnO : 0 à 20% ; Al2O3+ZrO2 : 0 à 20% ; et Fe2O3 : 0 à 5%.
PCT/JP2013/068638 2012-07-09 2013-07-08 Matériau de scellement pour cellule solaire à colorant WO2014010553A1 (fr)

Applications Claiming Priority (2)

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JP2012153321A JP2014015350A (ja) 2012-07-09 2012-07-09 色素増感型太陽電池用封着材料
JP2012-153321 2012-07-09

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WO2014010553A1 true WO2014010553A1 (fr) 2014-01-16

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JP6952950B2 (ja) * 2016-04-21 2021-10-27 日本電気硝子株式会社 複合粉末材料
JP6913276B2 (ja) * 2017-01-26 2021-08-04 日本電気硝子株式会社 気密パッケージ
US11177072B2 (en) * 2019-08-16 2021-11-16 Samsung Electro-Mechanics Co., Ltd. Multilayer capacitor and board having the same mounted thereon
CN113121120B (zh) * 2021-05-31 2022-11-22 四川华炫新材料科技有限公司 一种高耐碱玄武岩纤维及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006169018A (ja) * 2004-12-14 2006-06-29 Nippon Electric Glass Co Ltd ガラスタブレット、その製造方法およびガラスタブレット一体型排気管
JP2009234816A (ja) * 2008-03-26 2009-10-15 Nippon Electric Glass Co Ltd 有機ｅｌディスプレイ用封着材料
JP2010280554A (ja) * 2009-06-08 2010-12-16 Nippon Electric Glass Co Ltd 色素増感型太陽電池用ガラスおよび色素増感型太陽電池用材料
WO2010147160A1 (fr) * 2009-06-17 2010-12-23 旭硝子株式会社 Fritte de verre pour la formation d'une électrode et pâte électriquement conductrice pour la formation d'une électrode et photopile utilisant chacune celle-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006169018A (ja) * 2004-12-14 2006-06-29 Nippon Electric Glass Co Ltd ガラスタブレット、その製造方法およびガラスタブレット一体型排気管
JP2009234816A (ja) * 2008-03-26 2009-10-15 Nippon Electric Glass Co Ltd 有機ｅｌディスプレイ用封着材料
JP2010280554A (ja) * 2009-06-08 2010-12-16 Nippon Electric Glass Co Ltd 色素増感型太陽電池用ガラスおよび色素増感型太陽電池用材料
WO2010147160A1 (fr) * 2009-06-17 2010-12-23 旭硝子株式会社 Fritte de verre pour la formation d'une électrode et pâte électriquement conductrice pour la formation d'une électrode et photopile utilisant chacune celle-ci

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