. (SOFC). SOFC,.,.. PEMFC, 2020 SOFC. SOFC,,.., (sealing glass).,,.,.,.. SOFC,,.. 2.1 2.1.1,. 64
( )..,.,.,,.. Goldschmidt, Zacharisen, Sun, Smekal, Stanworth. 1).,,,... 3, 4.,.. (Network former), (Nerwork modifier), (Intermediate). Table 1.,,. 2), 3. SiO2, B2O3, P2O5.,.,., Al2O3, PbO, BeO. 2.1.1 3) 90,.,.. (wt%) 3.. (borosilicate glass) SiO2 B2O3(8%). B2O3,.,,., SiO2 50~60%, Al2O3 15~20% 15%. (). SOFC (crystallization glass).,,,,. 65
2.2 SOFC 2.2.1 SOFC 4-6) (SOFC: Solid Oxide Fuel Cell) H2, CO, CH4, 600~850. SOFC, (cathode)/ (electrolyte)/(anode),.. (Planar Solid Oxide Fuel Cell)SOFC, (sealing glass).,. anode() cathode( ), /, (phase). Fig. 2. SOFC 5) Cathode.,,. Anode.,.,,.,. 150, cathode anode. Fig. 1. SOFC 2.2.2 SOFC 7) (Planar Solid Oxide Fuel Cell). (gas tight sealing). SOFC. CTE 9.9-12.010 6 / 66
Table 2., 650-900 50,000... 10 4, < 35kPa, 14-35kPa. < 1%.., (mica),., 3.1 3.1.1 8) SOFC,,,. BaO-Al2O3-SiO2-B2O3, SrO-La2O3-Al2O3- B2O3-SiO2, MgO-Al2O3-P2O5, BaO-Al2O3-SiO2-ZnO, CaO-TiO2-SiO2. 800~1000 103Pas. 3510-7 / SOFC.., BaO-La2O3-Al2O3-B2O3-SiO2, SrO-La2O3-Al2O3- B2O3-SiO2, MgO-CaO-Al2O3-SiO2..,. SOFC,,,. 3.1.2 9) - / 10). Tg,. 20-45mol%, (Na 2 O+K 2 O)/ (CaO+MgO)0.03-1.8... Na2O 1.3-1.8mol% Tg 545-780, Ts 680-740, 7mol% K2O 67
Table 3. - Tg 470, Ts 530. SiO 2 5mol% Na2O Tg 35, Ts 60, 9.210-6 11.210-6 /K.. Tg Ts (Na2O+K2O)/ (CaO+MgO). SOFC Na2CrO3 K2CrO4,. Chou et al. Crofer22APU K2O. K2O (chromate). Crofer22APU (YSZ),. Na + GC/YSZ GC/. 11,12) - / SOFC.,, Tg, Ts, CTE,,,. BaO/SrO-Al2O3-SiO2, BaO/SrO- CaO-Al2O3-SiO2, BaO/SrO-CaO/MgO-Al2O3-SiO2-B2O3. 13) CaO SrO Tg Ts,.. Mg 2 +(0.45-0.51)> Ca 2 +(0.33-0.35)>Sr 2 +(0.27)> Ba 2 +(0.24). Mg, Mg 2+. 14) BaO 20 40mol%, BaO-Al2O3-La2O3-SiO2-B2O3 BaO 40mol% 1110-6 /K. SrO, SrO- Al2O3-La2O3-SiO2-B2O3 25.7mol% SrO 9.710-6 /K. Tg, Ts -. SOFC BaO B2O3. B2O3,. B2(OH)2 B(OH)3.. (Glass- Ceramics: GCs). GCs. CTE. 68
CTE CTE. CTE. CTE, mi CTE, a i. 15) Tg, Ts, (Tm), (Tc), CTE,. MgO CTE Al2O3 5mol% BaO-Al2O3-B2O3-SiO2 SOFC. 16) 3.1.3 Clinopyroxene() Pyroxene(), M2M1T 2O 6. M2 Mg 2+, Fe 2+, Mn 2+, Li +, Ca 2+, Na +. M1 Al 3+, Fe 3+, Ti 4+, Cr 3+, V 3+, Ti 3+, Zr 4+, Sc 3+, Zn 2+, Mg 2+, Fe 2+, Mn 2+. T Si 4+, Al 3+, Fe 3+. (monoclinic) pyroxene clinopyroxene. Clinopyroxene., clinopyroxene. Diopside{:CaMgSi 2 O 6 ] Ca-Tschermak[CaTs: CaAl2SiO6] clinopyroxene, Ca(Mg1-xAlx)(Si1-xAlx/2). clinopyroxene SOFC (8). - BaO GCs(Glass Ceramics) BaO. clinopyroxene celsian CTE CTE BaCrO 4 BaO 5.26%. BaO Di-CaTs 8.010-6 /K 8.110-6 /K, Ts 654 681. BaO BaO Ec 437kJ/mol 378kJ/mol. 17) - ZnO ZnO GCs MgO CaO. ZnO B2O 3. 10mol% ZnO Tg 50,. - La2O3 18) La2O3 GCs CTE. Diopside CaMgSi2O6 La2O3 1.3 2.6mol% Tg Ts55 16, 8.7 8.510-6 /K. La2O3 501 kj/mol 450 kj/mol. Diopside La2O3 1.3 mol% GCs CTE. - B2O3 B2O3. Sohn B2O3/SiO2 GC, CTE 69
. La2O3 BaO diopside B2O3 5-20wt.%. B2O3 Tg 685 490, Ts 716 665, 8.7 7.510-6 /K. - Mg2SiO4 BaSi2O5 19) Ca0.9MgAl0.1La0.1Si1.9O6 SOFC. CTE GC. - Mg2SiO4BaSi2O5. Ca0.9MgAl0.1La0.1Si1.9O6 Mg2SiO4 BaSi2O5, Ts, Mg2SiO4 9.4 9.810-6 /K, BaSi2O5 7.1 9.5 10-6 /K.. Table 3. - SrO 20) Diopside - (0.52mol%). CTE 7.110-6 /K GCs(1010-6 /K)., / Ca Sr SrO 7.1 11.310-6 /K. Ca- O(2.38), Sr-O(2.60 ). SrO, 900. SrO,,. 3.1.4 SOFC (self-healing),,.,,,.,..,,.. SOFC. 70
. Jen-Hsien Hsu (self-healing). 21) Teng Zhang SOFC CaB2O4. 40/ 900. 22) Wenning N. Liu BCAS. 56.4% BaO, 22.1% SiO2, 5.4% Al2O3, 8.8% CaO, 7.3% B2O3. Ni- YSZ YSZ. 23) 3.2 3.2.1,. SOFC,,,. 3.2.2-24) (Tg: Transition temperature) (Ts: Softening temperature). Tg Ts ~10 11.3 ~10 9 Pas., 10 9 Pas. Tg Ts,,,.,,,. Al2O3. Tg Ts SiO2 Fig. 3. (5) 55%. Tg 675-725, Ts 725-750. Tg 625-700, Ts 650-750. B2O3, B2O3 Tg Ts 50-100. MgO-BaO- 0.2-0.5% B2O3 Ts 50-100. Tg Ts.,,. boron anomaly Tg Ts. SiO2 B2O3 Tg Ts. 1-2% Na2O K2O Tg 493 480. K + (0.17) <Na + (0.19)<Li + (0.23), Ba 2+ (0.24) <Sr 2+ (0.27)<Ca 2+ (0.33-0.35)<Mg 2+ (0.45-0.51). Tg Ts., 8.6% (MgO+ CaO) (Na2O+K2O) Tg 110. Na2O 5% 71
Tg Ts ~270(786 562) ~300 (910 607). Al2O3. Al 3+ 4 Al2O3, Al 3+ 6. Al 3+ AlO 4-, Al 3+ 1:1 Tg Ts. Tg Ts. 10mol%. ZrO2 Al2O3 Tg Ts,. 25). La2O3. La2O3 5mol% Tg ~50. La2O3 3mol% Tg ~30. Nd2O3 1mol% Tg ~10. Y2O3. Na2O Y2O3 Tg Ts ~20. MgO 2~7mol% TiO2 Tg 15, Ni(<2mol%) Cr2O3(<2mol%) Tg ~20. BaO- ZrO2 3mol% Tg 15~20, Ni 5mol% 5~10. SrO-CaO- 5mol% NiO Tg ~25, Ts ~10. - (CTE).. (CTE>CTE) (CTE<CTE). CTE 110-6 /.. (15). CTE,. SiO2 CTE 0.610-6 / B2O3 14.410-6 /. CTE. molar-free volume CTE. Tg TsCTE. CTEadditive rule". SiO2 CTE, B2O3. 5mol% SiO2 CTE ~1.510 6 /. CTE B2O3/SiO2. B2O3/SiO2 0.0 0.33 CTE ~1.010-6 /. B2O3 CTE. 26) CTE,. Na2O 5mol% CTE 9.310-6 / 11.210-6 /. MgO-BaO-SiO2 2.6mol% K2O CTE ~3.010-6 /. CTE,. BaO CTE BaO ~8.010-6 / 12.010-6 /. Al2O3. Al 3+ 4 CTE 72
. SrO- Al2O3 9.5 14.5mol% CTE ~17.010-6 / ~9.5 10-6 /. CTE. CTE. BaO- SrO- 2.0~3.0mol% La2O3 CTE 1.010-6 /. BaO- 2mol% ZrO2 CTE 0.510-6 / MgO-. CTE. CTE. CTE. BaO- BaAl2Si2O8 750-800. BaAl2Si2O8,, celsian 3, CTE. CTE celsian. BaO- CTE ~11.510-6 / ~7.510-6 /. BaO /YSZ 800 50 BaZrO2 CTE ~9.510-6 / ~7.610-6 /. - 27),. Si2O5, Si2O6, Si2O7, SiO4. (Si3O4, Si3O10) (Si4O12, Si6O18). CaO- B2O3/SiO2. MgO- BaO-. B2O3/SiO2 0 0.57 (Tc)100(918 805). (Tx) B2O3/SiO2..., BaO MgO 100. BaO. BaO. SrO 750~800 SrB2O4, Sr2Al2SiO7, SrSiO3, Sr2SiO4, AlBO3, Sr2B2Al2O8. Al2O3. Al2O3 Al 3+ 4. Al2O3 Al 3+ 6., 10mol% Al2O3 MgO-., BaO- 5mol% La2O3 800 Ba4La6O(SiO4)4,.. TiO2 MgO-. ZrO2 BaO- MgO- Tc. SOFC 40-60mol%, 20-45mol%, 5-10 mol% Al2O3, 3-10 mol%. - Tg, Ts, CTE 73
.,. B2O3.,. B2O3. Tg Ts., Mg 2+ > Ca 2+ >Ba 2+. BaO SrO CaO MgO. 3.2.3-2.,,,. B2O3 SOFC., Al2O3... Na2O 750, 1000 13wt.%. B2O3. B2O3 HBO3,. RBO2(R=Na,K) B(OH)3. Tg B2O3 50-100. - 28) SOFC.,, (, ). SOFC. Cr2O3 (7.6910-4 S/cm 25, 110-2 S/cm 800). chromia forming, Crofer22 APU, AISI 441, AISI 430 AL29-4C. 22.0wt.% Cr. <10. BaO-CaO- Cr 800 ~10 ~15. Crofer 22 APU Fe, Ti Mn Sr, Si, La Al2-3. 3.2.4-29),,,. Na2O- /MgO SrO-CaO- Crofer 22 APU 1.87 6.2MPa..,. Na2O- /MgO SrO-CaO- Crofer 22 APU 74
70 75 1.85 2.36MPa. Co3O4 Crofer 22 APU 100 800kPa 1.30 1.81MPa. - 30). /, 70-200kPa.. /,. CTE.,,. 850 ~200GPa. CTE (delamination).,. 250. -. SrO-CaO-Y2O3-B2O3-SiO2 10-2 10-4 sccm/cm. 950 1.210-2 sccm/cm, 950 10 3 ~10-4 sccm/cm. (, ) ZrO2 650 800 ( <0.094sccm/cm). Na2O-Al2O3-SiO2/MgO 750 0.5-1.2L/min, 2500 0.2-0.4L/min. - SOFC... Ca 2+ Mg 2+. ZrO2. ZrO2,. 3.2.5 31) -, >10 4.,,.. 15Na2O-15BaO-10RmOn- 60SiO2 RmOn SiO2 10 11.4 B2O310 12.5. Cs + >Rb + > K + >Na +, Ba 2+ >Sr 2+ >Ca 2+ > Mg 2+.., BaO-SiO2(1 10 9 ) CaO-SiO2 (510 6 ), Ba 2+. -,,., Na2O-B2O3-SiO2 650-660 75
50 Na2O B2O3. Na2O B2O3.,. Arrhenius. 3.2.6. SOFC....,,. / /.,,. SOFC,. SOFC,,,,.,,,. 3.3 3.3.1 SOFC...,. 1300-1600..,..,. Al2O3, ZrO2... 3.3.2... 0.1 1000.. BET.,,.,.,, 76
.. X ICP. FTIR, MAS-NMR, XRD HMS(Hot-Stage Microscopy), EDS, SEM. (paste),,, thermal leak test. 32-33) 3.3.3,,, (),,,. (vehicle).,. (gasket).,,... 5-20 4. 4.1 4.1.1.,. KISTI Web of Science, Science direct. glass sealing, glass ceramic sealing, glass ceramic sealant. Web of Science(Thomson Reuters). 2006-2015 458. (, ), 414. 2015 8. KISTI (COMPAS: COMPetitve Analysis Service) D/B (Journal Article Analysis).., /, /,,,,. 4.2 4.2.1-2008 40,. - 36. USA 96 77
414 23.19%. China 78(18.84%), Germany 55(13.29%) 2, 3, 27(6.52%) 6. 15. Web of Science, Electrochemistry 160, Energy Fuel 158, Material - :. 1.0, 1.0. Fig. 5. Table 4. - 282. Pacific NW Natl Lab 39 414 9.42%. Table 5. Fig. 4. - 414 Article 398, Proceeding 34, 78
Ceramic 95, Chemistry Physical 65, Physics Applied 28.. Korea Inst Sci & Technol(6), Chonbuk Natl Univ(5), Myongji Univ(5), Sungkyunkwan Univ(4), Korea Inst Energy Res(2), Hanyang Univ(2), Chonnam Natl Univ(2), Konkuk Univ(2), Yeungnam Univ(2) 19. 4.2.2,,., JOURNAL OF POWER SOURCES, INTER JOURNAL OF HYDROGEN ENER- GY, FUEL CELLS CERAM- ICS INTERNATIONAL, J OF THE EUROPEAN CERAMIC SOCIETY, J OF NON CRYSTALLINE SOLIDS, J OF THE AMERICAN CERAMIC SOCIETY. SOFC 40. 15. Table 6., SOFC.,,... (SOFC).. SOFC,,., (sealing glass). SOFC,,,.., BaO-La2O3-Al2O3-B2O3-SiO2, SrO-La2O3-Al2O3-B2O3-SiO2, MgO-CaO-Al2O3-SiO2. 1990 SOFC.. 79
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