¾Å ÒÅ º Sm 0.15 Gd 0.05 Ce 0.8 O 1.9

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1 22 6 «Vol. 22, No Journal of Inorganic Materials Nov., 2007 : X(2007) ¾Å ÒÅ º Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 Å Õ» ¹ ¼¾ ½ º (µ ± ³ ² )  (EDTA)- µâá» - À»«ÈÙ ¼ØÏ Sm 0.15Gd 0.05Ce 0.8O 1.9(SGDC) ÄÇ Ñ Õ SGDC ËÆ ³Đ Û ÛÏÐ Á ÒÌ SGDC ³Đ Đ ËÚ ÒÌ (Coagulation factor) ÔÏ ¾Õ Đ SGDC Ò Ì º ÒÌ Ã ÃÉ ÕÔ SGDC ³Đ ÒÌ «ÏÅÏà ³ Ã Đ Þ SGDC ÒÌ Û 1.04 ³Đ «1300 C. É ºÑ ÃÉ Ð C «ÒÌ ÎÀ SGDC À Đ Đ Ù Sm 0.15Gd 0.05Ce 0.8O 1.9; ÒÌ ³ TM911 ÔØÎ A Effect of Agglomeration on the Densification Properties of Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 Electrolytes for Intermediate Temperature Solid Oxide Fuel Cells LUO Dan, LUO Zhong-Yang, YU Chun-Jiang (Institute for Thermal Power Engineering, State key laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou , China) Abstract: By synthesizing reactive powders via a self-sustaining combustion synthesis, the EDTAnitrate process, Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 was prepared. The resultant powders were dispersed with the terpineol as the dispersant by different methods such as ball milling and high-shear dispersing. Coagulation factor (CF) was adopted to denote the agglomeration degree of nano-scale SGDC in this work. The effect of agglomeration on the densification behaviors at different sintering temperatures was investigated. The studies indicate that agglomeration retards densification in the stage of sintering. The powders with better dispersion exhibit a higher sintered density at the same temperature. After effective dispersion measures taken, SGDC can fully densified at the sintering temperature of 1300 C. The densification temperature is significantly lower than those reported previously. Key words: SOFC; Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 ; agglomeration; densification 1 Þ ÅÚ «Äº à ѻ Þ Õ «¹²Á ¹ [1,2]. ÚÚ ÄĐ Û Î - Á ß Ò Å «Ø ÆÁÆ , Ú ÆÁÆ ²¼Æ (1977 ), ¹ÅÈ Å ld930@163.com µ Ä Đ Ù «ÄÙ Ý Ö Á Ò¹ Å Ú ÐĐ [3,4]. Å Ó Å Ð Ð Ö Æ Õ Ù Ð Ü Ç «Á ÄĐ Å Ú Á ³ Û Ü Õ ± Ï«Ç

2 1042 «22 Ù Å Ö Ù Ý ß [5 8]. ʱ Å Ó Å Ð Ä Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 «ÛÄ Ù Ý Ö «Ø Ð Ñ Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 ÐÜ±Ì ³Õ ÆÉ«Ð Ü Å Ú Á¼ Ç Ù Ò Ç Ú Ö «º SOFC Áß «ÛÄ «Ò Ö Ä ß Ê Å CeO 2 Å Á Đ Ä Ó 1600 C Ò Ó ß 95%; Reiss Ä 1700 C ÜÛ 95% 98% [9] ; Huang Ð ¼ - Á ¼ ½ Ce 0.9 Gd 0.1 O 1.95, 1585 C Ó Û 99% [10] ; K. Yamashita Û Ù Ce 0.8 M 0.2 O 2 (M=Ca 2+,Sr 2+,Sm 3+,Gd 3+,Y 3+ ), 1450 C Ó 98% [11]. Ê Ò Đ Ä Đ»ØÜ ± ± ½ ÓÍÊÛ «¹» SOFC ± ¹²Öß Î «Ü ÓºÓÍ SGDC Ü ÆÉ«Ø Ð ± Ç Sm 0.15 Gd 0.05 Ce 0.8 O 1.9, Å Í ÓÍ Ò Í ÓÍ Â Æ É Ó Í SGDC Ö ±«2 ÍßÜ Ü 2.1 «Ö Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 Ä» Í Ñ Ce(NO 3 ) 3 6H 2 O Sm 2 O 3 Ö Gd 2 O 3, Sm 2 O 3 Ö Gd 2 O 3 Æ Ã Ð ¼ Ð Ce(NO 3 ) 3 ËÐ Ù Ã ph Ù ßÜ Ý Û ÙÐ Ú (Ì ß ² 1), Ç Ã [12,13], ß ß Ù Å SGDC Ð «2.2 SGDC É µê Ä ¼ Ð Ü ÖÄ «2.2.1 Ã É µåñ Ñ φ3mm φ10mm Ñ Ò 6:1» Ð Ä [14], ¾Ê ¾ ( Ò XQM, ±Ì ÆÉÊ) «Ü 250r/min, Ü 2h Ö 6h ³ÂÈ É µ Å Ñ Ä ( Ò FA25 model, FLUKO Æ ¼ «) Û Ü Ö 28000r/min, Ü 30min. Ç ½ ßÀ Á Ê ß Ð Ì ¼»Ü SGDC-a( 2h) SGDC-b( 6h) SGDC-c( 10000r/min) Ö SGDC-d ( 28000r/min). µ Ç Ì Ä Ò 700 C Đ 2h, ¹Đ Ü 5 C/min. 2.3»Æ Ì µ ß SGDC Á Å Ý À «µ Ã Ô ¼ ± «µê Å Î Å (Ni-GDC) ¼ (KW-4A Ä Ø Ä½) ¾ À ± ¾ß³ Ü Óß 10µm, Á 12h ß Ä 1 C/min Đ 600 C, Đ 2h, ¹ ¾Đ«Ð Á¾ Ò C Đ 4h, Đ Ü 2 C/min, ¹Đ Ü 5 C/min. 2.4 ß SGDC Û ß Ý Rigaku Ç D/max-rA Ú 1 Đ«Õ Đ (EDTA)- Ö Ü Çµ - µ ÝÄË ÛÆ Ï Table 1 Stoichiometric reactions of EDTA-nitrate and sol-gel low temperature self-propagating Oxidant combustion Stoichiometric reactions Ce(NO 3) 3 7C 10H 16N 2O 8+20Ce(NO 3) 3 20CeO 2+56H 2O+10N 2+70CO 2 Sm(NO 3) 3 3C 10H 16N 2O 8+8Sm(NO 3) 3 4Sm 2O 3+24H 2O+4N 2+30CO 2 Gd(NO 3) 3 3C 10H 16N 2O 8+8Gd(NO 3) 3 4Gd 2O 3+24H 2O+4N 2+30CO 2 O 2 C 10H 16N 2O 8+10O 2 8H 2O+10CO 2+N 2

3 6 Ö ÒÌ Ã Đ Ù À Sm 0.15Gd 0.05Ce 0.8O 1.9 ³Đ Đ 1043 X É È ÐÔ Ô Þ ÓÖ FEI Æ SIRION È Å Ä À Ð Þ Î Æ QUANTACHROME AUTOSORB-1 Ù Ó ¹ µæ SGDC ½Ð Ù ± ÑË (CF) Ó ½ SGDC ÑË CF = d BET /d XRD (1) d XRD º XRD Þ Ë Ð Ð d BET º µ (2) Ä ÐÍ ÐÆ d BET = / S BET (2) S BET Ú Ë ¹ µæ Ø ß m 2 /g; Ú ß Ú ² Øß g/cm 3. = 4(0.8MCe M Gd M Sm + 1.9M O) a 3 N A (3) a º ½ Ð SGDC ÅÊ XRD N A Ú Đ Ê M Ú SGDC Ê Ù ± ² (ρ R ) Ó ½ ½È ² Ì Ä µú XRD Ê (a= Å) ¹ CeO 2 (a= å) Ô Sm 3+ Ô Gd 3+ Ø Æ Ú 1.08ÅÔ 1.05Å, ¹ Ce 4+ Ø Æ (0.97Å, 8 Ä ß ) Ô» Sm 3+ Ô Gd 3+ Ä CeO 2 Å ٠ÅƳ ² Å Ô ¹ CeO 2 Ô ¹ Sm 3+ Ô Gd 3+ CeO 2 ÅÂ Î ß 2 SGDC 5 Å C ² 2h Ý Å SGDC Í ÐÆÔ 20nm Æ Å Ë XRD Ð ÐÔ BET Ä È Í ÐÔ º Ð Ü ĐÅÐÆ» º ¹ ¹» Æ º ÑË ² ĐÅ Ð Æ Ã º Æ ÑËÈ Î ( µ 1). Å SGDC Ë ÑË ± 2. Ð ³ È Þ SGDC Î ÊÖ ÑË (CF).  SGDC-d CF Å Ö 28000r/min Â Í ρ R = ρ S (4) ρ S Ú½È ² Ú Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 Ú ² SGDC ² лӻ Ú ρ S = m ρ S H 2 O w W w H2 O m S Ú SGDC ½È Ë (5) w W Â Ý Ë È w H2 O Ú Ë ÂÌ È ρ H2 O Ú ÊÐ Ô H 2O ² ÐÀÐ Ø Ù SGDC XRD «(± 1), 700 C ² Ý Î È Þ µï Ò ½ (É ½ Ú 28.2, 32.9, 47.2,56.1,58.8,69.1, 76.3,78.7 ), Â Þ Gd 2 O 3 Sm 2 O 3 È Þ É ¹ SGDC ß Î Ñ Ø Ý Î Ë 700 C ² ÝÊ XRD É Þ ¹ Î ß 1 SGDC 700 C ³ 2h Þ XRD Ï Fig. 1 XRD patterns of SGDC powders calcined at 700 C for 2h Ú 2 Sm 0.15Gd 0.05Ce 0.8O 1.9 Ç ÑÙÞ Table 2 Properties of the Sm 0.15Gd 0.05Ce 0.8O 1.9 solid solution oxides dispersion by different methods calcined at 700 C for 2h SGDC-a SGDC-b SGDC-c SGDC-d CF /g cm d XRD/nm d BET/nm S BET/m 2 g

4 1044 «22 ÑË Ñ È Ë SGDC-a SGDC-b, 2h Þ 6h Ý ÑË ß SGDC-a Þ SGDC-d CF Ë ¹ Ë ÑË Å Ó 3.2 SGDC ¹ 2 Í Ð Ú C Đ» µ (4) Ô (5) Ä È SGDC ½È ² 700 C Ð Ê Ë Ç² Ð Ú 1400 C SGDC-a SGDC-b SGDC-c SGDC-d ² ÒÞÚ ² 99%, ² ¹ ÅÐ ÇØ EDTA- ÁÀ» Î Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 º 2 Ð SGDC ß 800 Ô 1000 C ¾Å ² SGDC-d 1000 C ² Ú 64%, Û Ð Æ Þ 1300 C ² ÂÞ 98% ÐÆ ¹ Ð Â SGDC-a ² ÔÚ Å Æ Ô Ð ÑË Å Ë ² Ê Â Ð ÑË SGDC ² Å ²Æ ºÑËÓ SGDC ß ¹Þ 3 Í Ð 4h Ý SGDC ² ÆÑË ½ Ñ Ñ Ë Æ² Ó Â¾ Ó È Õ Ð ( C) Æ ÑË Ô SGDC ² 2 SGDC ³ Fig. 2 Relative densities of the SGDC ceramics, as a function of sintering temperatures, with coagulation factors indicated 3 SGDC ³ ÒÌ Fig. 3 Relative densities of the SGDC ceramics, as a function of coagulation factors 1300 C CF Ú 1.19 SGDC Î ¾Å ² Û ÎÚ ¹ Ñ Ý ² Ô Â SGDC Ë (CF=1.04), Æ Ð Â Ð ² Ð Ú 1300 C ÒÞ ² Å SGDC ½È 4 È È Ë 1400 C Ð ² Ý ÐÎ ËÔÒ Æ 4 Â Ð Þ SGDC-d Ð Ú 1300 C Ú Æ² Ȳ Ð ¹Ð Ð ( C) Å SGDC-d Ų Ð Ì ÕÆ ¹ µæôå ÑË ( 2). ̲ Þ¹ 4 1. EDTA- ÁÀ ߺ - ºÅÐ ÇØ» Sm 0.15 Gd 0.05 Ce 0.8 O 1.9 ² Ð Ú 700 C ÐÎ Ô Ë Ñ ÎÔÒ SGDC ß 2. Â Ñ Ë ÂÈÓ SGDC ² Ð ÑË ¾Å Π² 3.  ( 28000r/min) Ý SGDC Ñ Ë Ú 1.04 ² Ð Å 1300 C. Ð ¹Ð ÂÈ C Ð Å ÑË Í SGDC

5 6 Ö ÒÌ Ã Đ Ù À Sm 0.15Gd 0.05Ce 0.8O 1.9 ³Đ Đ C SGDC-a(a) SGDC-b(b) SGDC-c(c) SGDC-d(d) Õ 1300 C SGDCd(e) É«Å É Fig. 4 FESEM micrographs of the four typical SGDC ceramics densified at 1400 C and the SGDC-d densified at 1300 C (a) SGDC-a-1400; (b) SGDC-b-1400; (c) SGDCc-1400; (d) SGDC-d-1400; (e) SGDC-d-1300 Ý Ó [1] Ü Ý Õ Þ (LI Song-Li, et al). (Journal of Inorganic Materials), 2006, 21 (5): [2] Í Ï (YANG Nai-Tao, et al). (Journal of Inorganic Materials), 2006, 21 (2): [3] Nguyen Q. Solid State Ionics, 2004, 174: [4] Tietz F, Buchkremer H.-P, Stöver D, et al. Solid State Ionics, 2002, 152: [5] Ji-Guang Li, Takayasu Ikegami, Toshiyuki Mori, et al. Acta Materialia, 2004, 52: [6] Alexander Alexandrovich Gromov, Ulrich Forter-Barth, Ulrich Teipel, et al. Powder Technology, 2006, 164: [7] Van herle, Horita T, Kawada T, et al. Solid State Ionics, 1996, 86: [8] Xia C, Liu M, et al. Solid State Ionics, 2002, : [9] Reiss I, Brounshitein D, Tannhauser D S, et al. J. Am. Ceram. Soc., 2001, 64: [10] Huang K, Feng M, Goodenough J B, et al. J. Am. Ceram. Soc., 1998, 81 (2): [11] Yamashita K, Ramanujachary K V, Hreenblattm, et al. Solid State Ionics, 1995, 181 (2): [12] Mather G C, Figueiredo F M, Jurado J R, et al. Solid State Ionics, 2003, 162: [13] Ringuede A, Labrincha J A, Frade J R. Solid State Ionics, 2001, : [14] Ruiz F, Perez-Robles, Gonzalez J, et al. Material letters, 2000, 42: