WO2010123745A1 - Verre exempt d'oxyde de baryum, d'oxyde de calcium, d'oxyde de magnésium et d'oxydes de métaux alcalins - Google Patents

Verre exempt d'oxyde de baryum, d'oxyde de calcium, d'oxyde de magnésium et d'oxydes de métaux alcalins Download PDF

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Publication number
WO2010123745A1
WO2010123745A1 PCT/US2010/031185 US2010031185W WO2010123745A1 WO 2010123745 A1 WO2010123745 A1 WO 2010123745A1 US 2010031185 W US2010031185 W US 2010031185W WO 2010123745 A1 WO2010123745 A1 WO 2010123745A1
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WO
WIPO (PCT)
Prior art keywords
mole percent
glass
oxide
sro
sofc
Prior art date
Application number
PCT/US2010/031185
Other languages
English (en)
Inventor
Peizhen Kathy Lu
Manoj Kumar Mahapatra
Original Assignee
United States Department Of Energy
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 United States Department Of Energy filed Critical United States Department Of Energy
Publication of WO2010123745A1 publication Critical patent/WO2010123745A1/fr

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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

Definitions

  • the present invention relates to a sealing glass, preferably for use in a solid oxide fuel/electrolyzer cell (SOFC) stack.
  • SOFC solid oxide fuel/electrolyzer cell
  • SOFC solid oxide fuel/electrolyzer cell
  • the chemical energy is supplied by reacting fuel (such as hydrogen) and oxidants (such as air).
  • fuel such as hydrogen
  • oxidants such as air
  • SOFCs When consuming pure hydrogen, SOFCs produces no greenhouse gasses. SOFCs can be run in reverse, as an electrolyzer cell, using electricity and steam and producing hydrogen. The produced hydrogen can then be used as an energy source elsewhere.
  • a SOFC has an anode, a cathode, and a solid electrolyte.
  • the operating temperature of a SOFC is rather high, generally ranging from 600 °C to 900 °C. Therefore, ceramic materials are used in SOFC as the solid electrolyte, cathode, and anode.
  • SOFC stacks require interconnects to transfer fuel, air, and electricity through each cell in the stack. Particularly, the fuel channels and the air channels have to be well sealed from each other to maximize efficiency.
  • a seal in a SOFC stack ideally must prevent the mixing of fuel and oxidant, prevent the mixing of the fuel and oxidant with the ambient environment, provide mechanical bonding of the components, and provide electrical insulation between the components of the stack.
  • Fuel cells increase in efficiency as operating temperatures increase. However, at high operating temperatures, the integrity of the cells degrades. Degradation in the SOFC stack causes the fuel, oxidants and other reactant gases to leak and mix, which reduces efficiency and long term stability of the stack.
  • Glass and glass-ceramic seals are a common seal used in fuel cells. Although inexpensive, current glass and glass-ceramic seals are brittle, and over time degrade. For example, most seals do not have a suitable coefficient of thermal expansion (CTE), resulting in stress fractures in the glass as well as additional stress on other components in the SOFC stack. Current glass and glass-ceramic seals also are known to volatize during operation (e.g. silica, borate, and other alkali metals), which may foul or poison the electrolyte and interact in an undesirable manner with other SOFC components.
  • CTE coefficient of thermal expansion
  • U.S. Patent 5,453,31 1 discloses a SrO-alumina-borosilicate sealing glass containing a high amount of B 2 O 3 and La 2 O 3 with a coefficient of thermal expansion (CTE) of 8.5-12 * 10 "6 /°C in 50-600 °C and glass transition temperature of 500-750 °C.
  • CTE coefficient of thermal expansion
  • these glasses are not thermally stable at high operating temperatures, such as 800 °C. Since the glass contains a high amount of B 2 O 3 , evaporation of boron oxides may take place, degrading the cells performance as the B 2 O 3 evaporates, causing the seal to fail.
  • U.S. Patent 6,291 ,092 discloses a B 2 O free, alkali oxide and BaO sealing glass.
  • the presence of alkali oxide decreases the electrical resistance due to the mobility of monovalent cations in the glass.
  • the monovalent cations of the alkali oxides can easily diffuse to the other sealed components in the SOFC stack, which change the glass compositions and thus degrade the cell's long term stability.
  • the presence of BaO in the glass reduces both thermal and chemical stability.
  • BaO-containing glasses crystallize near 750 °C to different polymorphs of barium-alumina-silicate phase with different coefficients of thermal expansion (CTE), leading to thermal stress.
  • CTE coefficient of thermal expansion
  • BaO reacts severely with chromium containing metallic interconnects to form BaCrO 4 , which has about twice the coefficient of thermal expansion (CTE) of the sealing glass and induces cracks in the seal.
  • Metal brazes which use a molten metal filler to ensure sealing, are another form of seal used in a SOFC stack. Although easy to manufacture, the brazes are electrically conductive, making them unsuitable for most seals. Few braze metals are compatible with the SOFC operating conditions, and commonly are made of expensive noble metals. There have been efforts to use silver, but its use in both oxidizing and reducing environments can lead to chemical instability.
  • a glass composition consisting essentially of: about 10-45 mole percent SrO; about 0-20 mole percent La 2 O 3 ; about 0-25 mole percent AI 2 O 3 ; about 0-15 mole percent B 2 O 3 ; about 35-75 mole percent SiO 2 ; and about 0-5 mole percent Ni.
  • the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide.
  • the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack.
  • SOFC stack comprises a plurality of SOFCs connected by one or more interconnects and manifold materials and sealed by the glass.
  • each SOFC comprises an anode, a cathode, and a solid electrolyte.
  • a glass composition consisting essentially of: about 10-45 mole percent SrO; about 0-20 mole percent La 2 O 3 ; about 0-25 mole percent AI 2 O 3 ; about 0-15 mole percent B 2 O 3 ; about 35-75 mole percent SiO 2 ; and about 0-5 mole percent Ni.
  • the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide.
  • the glass consists essentially of: about 28-30 mole percent SrO; about 5 mole percent La 2 O 3 ; about 5 mole percent AI 2 O 3 ; about 0-10 mole percent B 2 O 3 ; about 50-60 mole percent SiO 2 ; and about 0-2 mole percent of Ni.
  • the glass consists essentially of: about 30 mole percent SrO; about 5 mole percent La 2 O 3 ; about 5 mole percent AI 2 O 3 ; about 0-10 mole percent B 2 O 3 ; about 50-60 mole percent SiO 2 ; and about 2 mole percent of Ni.
  • the glass consists essentially of: about 30 mole percent SrO; about 5 mole percent La 2 O 3 ; about 5 mole percent AI 2 O 3 ; about 0-10 mole percent B 2 O 3 ; and about 55-60 mole percent SiO 2 .
  • the glass consists essentially of: about 28-30 mole percent SrO; about 5 mole percent La 2 O 3 ; about 5 mole percent AI 2 O 3 ; about 58-60 mole percent SiO 2 ; and about 0-2 mole percent of Ni.
  • the glass consists essentially of: about 28-30 mole percent SrO; about 5 mole percent La 2 O 3 ; about 5 mole percent AI 2 O 3 ; about 58- 60 mole percent SiO 2 ; and about 2 mole percent of Ni.
  • the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack comprising a plurality of SOFCs connected by one or more interconnects and manifold materials and sealed by the glass.
  • SOFC solid oxide fuel/electrolyzer cell
  • each SOFC comprises an anode, a cathode, and a solid electrolyte.
  • the glass when used as a seal in a SOFC stack, has a coefficient of thermal expansion (CTE) between 10.5 * 10 "6 /°C to 13 * 10 "6 /°C; a glass transition temperature greater than 700°C; and a dilatometric softening temperature greater than 750 °C.
  • CTE coefficient of thermal expansion
  • the glass is substantially free of alkaline oxides.
  • the presence of an alkali oxide reduces the electrical resistivity due to the mobility of monvalent cations in the glass.
  • the monovalent cations of the alkali oxide can easily diffuse to the other sealed components, which change the glass composition and thus degrade the SOFCs long term stability.
  • the glass is substantially free of BaO.
  • the presence of BaO in the glass reduces both the thermal and chemical stability.
  • BaO oxide based glasses crystallize near 750 °C to different polymorphs of baium-alumina-silicate phases differing in coefficient of thermal expansion (CTE) values sufficiently to develop thermal stress.
  • CTE coefficient of thermal expansion
  • BaO severely reacts with chromium containing metallic interconnects to form BaCrO 4 , which has about two times the coefficient of thermal expansion (CTE) than that of the sealing glass.
  • CTE coefficient of thermal expansion
  • the glass is also substantially free of B 2 O 3 , which may evaporate during operation of the SOFC. As B 2 O 3 evaporates, the glass composition will change and thus degrade the SOFC stack's long term stability.
  • the glass is made using conventional glass manufacturing techniques.
  • appropriate amounts of the glass ingredients for example, SrCO 3 , La 2 O 3 , AI 2 O 3 , B 2 O 3 , SiO2, Ni
  • the mixed powders are heated in a crucible.
  • the mixed powders are heated in a platinum crucible to 1 10O 0 C.
  • the mixed powders are kept in the crucible long enough for the SrCO 3 to decompose, preferably about an hour.
  • the mixture is then further heated into a melt, preferably to 1400°C for four hours.
  • the heating rate is 10°C/min.
  • the melt is then quenched into a mold, preferably a graphite mold. Glass powder having a particle size less than 36 microns can then be prepared by grinding the quenched glass.
  • the glass is made first by grinding SrO and SiO 2 into a powder, preferably with the use of a mortar and pestle.
  • a powder preferably with the use of a mortar and pestle.
  • one or more of La 2 O 3 ; AI 2 O 3 ; B 2 O 3 ; and Ni are also grinded into a powder.
  • SrO; SiO 2 ;La 2 O 3 ; AI 2 O 3 ; and B 2 O 3 are ground into a powder using a mortar and pestle.
  • the powders are then preferably mixed in a ball mill overnight and melted between 1300°C and 1400°C for three to five hours.
  • the melt is then poured in a mold, preferably a graphite mold, to obtain glass.
  • CTE coefficients of thermal expansion
  • T 9 glass transition temperature
  • T d dilatometric softening temperature
  • Table 2 Thermal properties obtained from the glass embodiments shown in Table 1.
  • CTE coefficients of thermal expansion
  • the same heating rate and cooling rate of 3°C/min were employed up to 900 °C for a dwell time of two hours.
  • Coefficients of thermal expansion (CTE) were in the range of 50 °C to glass transition temperature of the corresponding glass sample.
  • the data obtained in the first heating cycle of the glass is not consistent with the remaining cycles. Therefore, the data given in Table 2 does not include data obtained from the first heating cycle.
  • the compositions 6A and 7A indicate the same glass composition as 6 and 7 respectively, but were given a thermal treatment at 900 °C for five minutes.
  • the coefficients of thermal expansion (CTE) for all prepared glasses are in the range of 10.50 * 10 "6 /°C to 13.00 * 10 "6 /°C. These values match with the coefficients of thermal expansion (CTE) of the solid electrolyte, cathode, anode, interconnect, and manifold materials of a SOFC extremely well. Therefore, once solidified, the glass is well suited as a seal in SOFC stacks as the glass will not degrade over time due to thermal expansion mismatch.
  • the glass transition temperature (T 9 ) the glass will be in viscous form, whereby no thermal stress will be present to degrade the performance of the SOFC stack.
  • All of the prepared glasses have a glass transition temperature (T 9 ) higher than 650 °C, which is sufficient for use as a seal in a SOFC stack.
  • the glass is designed for a glass transition at more than 700 °C, when used as a seal in a SOFC stack.
  • the dilatometric softening temperature (T d ) is above 700 °C for each of the prepared glasses, which is sufficient to avoid the flow of glass at the operating temperature of the SOFC stack.
  • the dilatometric softening temperature (T d ) is preferably above 750 °C, to avoid the flow of glass at operating temperatures of SOFC stack. Since the dilatometric softening temperature (T d ) is lower than the cell operating temperature, the glass can be sealed below or at 1000 °C and provide superior bonding to the cell components which will increase the mechanical integrity and overall efficiency. More importantly, the glass embodies a self- healing capability during its softening process to provide a gas tight seal during repeated healing and cooling.
  • the coefficients of thermal expansion (CTE) for all the prepared glasses are in the range of 10.50x10 "6 /°C -13.00 x10 "6 /°C. Coefficients of thermal expansion provided are measured up to 50 °C below the glass transition temperature (T 9 ) of the corresponding prepared glass samples. These values match with the coefficients of thermal expansion (CTE) of electrolyter, cathode, anode, interconnect, and manifold materials of the SOFC stack and similar devices. Therefore, no SOFC stack degradation due to thermal expansion mismatch will occur when the glasses are used as sealing material at temperatures below the glass transition temperature (T 9 ). Above the glass transition temperature (T 9 ), the glasses outlined here will be in viscous form. Therefore, no thermal stress will be present to degrade the SOFC stack.
  • CTE coefficients of thermal expansion
  • the thermal stability of the glass was determined by inspecting the devitrification behavior of the glass after heat treatment to each sample at 850 °C for 50- 100 hours. No devitrified phase was detected for glasses 2 and 3. In glasses other than glasses 2 and 3, the devitrified phase was detected which is useful to enhance the mechanical strength of the stacks. In glass 7A, the coefficient of thermal expansion (CTE) is 10.57 * l O "6 / ⁇ , which is preferred for use in a SOFC stack. Therefore, the devitrified phases are also thermally stable and will not degrade the integrity of the cells due to thermal stress.
  • CTE coefficient of thermal expansion

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention porte sur une composition de verre, consistant essentiellement en : environ 10 à 45 pour cent en moles de SrO ; environ 0 à 20 pour cent en moles de La2O3 ; environ 0 à 25 pour cent en moles d'Al2O3 ; environ 0 à 15 pour cent en moles de B2O3 ; environ 35 à 75 pour cent en moles de SiO2 ; et environ 0 à 5 pour cent en moles de Ni. De préférence, le verre est pour l'essentiel exempt d'oxyde de baryum, d'oxyde de calcium, d'oxyde de magnésium et d'oxydes de métaux alcalins. De préférence, le verre est utilisé comme joint dans un empilement de piles à combustible à oxyde solide (SOFC)/cellules d'électrolyse. L'empilement de SOFC comprend une pluralité de SOFC connectées par un ou plusieurs matériaux d'interconnexion et de collecte et rendues étanches par le verre. De préférence, chaque SOFC comprend une anode, une cathode et un électrolyte solide.
PCT/US2010/031185 2009-04-23 2010-04-15 Verre exempt d'oxyde de baryum, d'oxyde de calcium, d'oxyde de magnésium et d'oxydes de métaux alcalins WO2010123745A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17189709P 2009-04-23 2009-04-23
US61/171,897 2009-04-23

Publications (1)

Publication Number Publication Date
WO2010123745A1 true WO2010123745A1 (fr) 2010-10-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541327B1 (en) 2011-10-21 2013-09-24 U.S. Department Of Energy Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615769A (en) * 1970-03-09 1971-10-26 Leitz Ernst Gmbh Lanthanum borosilicate optical glass
US3881904A (en) * 1971-03-24 1975-05-06 Lucas Industries Ltd Method of joining a pair of silicon nitride parts
US6124224A (en) * 1998-09-02 2000-09-26 Ferro Corporation High temperature sealing glass
US20060290257A1 (en) * 2005-06-24 2006-12-28 Lg Electronics Inc. Plasma display apparatus and driving method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615769A (en) * 1970-03-09 1971-10-26 Leitz Ernst Gmbh Lanthanum borosilicate optical glass
US3881904A (en) * 1971-03-24 1975-05-06 Lucas Industries Ltd Method of joining a pair of silicon nitride parts
US6124224A (en) * 1998-09-02 2000-09-26 Ferro Corporation High temperature sealing glass
US20060290257A1 (en) * 2005-06-24 2006-12-28 Lg Electronics Inc. Plasma display apparatus and driving method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541327B1 (en) 2011-10-21 2013-09-24 U.S. Department Of Energy Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

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