1. The hydrogen permeation ability of Ni-BaCe0.9Y0.1O3-δ (Ni-BCY) cermets with different Ni volume ratios were investigated from 600-750°C. 2. The highest hydrogen permeation rate was achieved with a Ni volume ratio of 30%. 3. For Ni-BCY(40/60) cermets, hydrogen permeation was controlled by bulk diffusion for thicknesses above 0.6mm, but was controlled by surface exchange for thicknesses of 0.36mm or less.

1. 22 6 ¿ ¼ ´«Ì Vol. 22, No. 6
2007 ´ 11 § Journal of Inorganic Materials Nov., 2007
Æ È: 1000-324X(2007)06-1243-04
Ni-BaCe0.9 Y0.1O3−δ ÕÙ Þ¤ §℄
¹ ¥¸¾» ¥ ½ ¥¶·¼ ¥º ¿
(µ ² ² ²´ °± ´ ³ ¢ 230026)
­ ª ª © Ni-BaCe Y O (Ni-BCY) Ê ¯ ­ 600∼ 750 C ı § Û± ◦
Ni-BCY Ê ¯ º ¶ Ü £Ó Ni ¦ Ë 25%
Ò ÏË ¾ - ¾» É £Ñ ±
0.9 0.1 3−δ
30:70 º Û ¤ ¥ §± ² º ª Ni-BCY(40/60) £² ­ 0.6mm
Ý Ùͱ´ £ÑÆ ² Á 0.36mm ± Ô ±´ §
Æ Ï ª Ni-BaCe Y O Ê ¯ ­ ­ Ú Ý
Â È ª TB34 ¡ Ò
ª A
0.9 0.1 3−δ
Hydrogen Permeation of Ni-BaCe0.9 Y0.1 O3−δ Cermet
YANG Jing, FANG Shu-Min, WU Xiu-Sheng, CHEN Chu-Sheng, LIU Wei
(Lab of Advanced Functional Materials and Advices, Department of Materials Science and Engineering, Univer-
sity of Science and Technology of China, Hefei, 230026, China)
Abstract: Hydrogen permeation ability of Ni-BaCe0.9 Y0.1 O3−δ (Ni-BCY)cermet with different Ni
volume ratios were investigated at intermediate temperatures (600–750◦C). The experimental results
show that proton-electronic mixed conductors are formed when Ni volume ratio is up to 25%, and the
hydrogen permeation rate reaches the highest when Ni volume ratio is 30%. The hydrogen permeation
measurement results of Ni-BCY(40/60) cermet with different thicknesses indicate that the bulk diffusion
controls hydrogen permeation when thicknesses of samples are above 0.6mm, however, as reducing sample
thickness to 0.36mm or less hydrogen permeation is controlled by surface exchange process.
Key words: Ni-BaCe0.9 Y0.1 O3−δ cermet; volume ratio; hydrogen separation
1 «¨ Ç· ÆÏ ¦Ò ²¾ Ų Ì
² ²À ²§« ¦ Æ¡± Á § Æ ¦ Á Û Þ ¦Ë Ni ²
¿ - °¿¼ Ê
ÓÐ È¡ ×Õ ¦ °§²§ Ì ©Ò Y » ª BaCeO (BCY) ² 3
¥ ¦Â ¼ Á § ħ ¦° ¼ ¾×½»Ã Ê
Å¥ ¥·°¿ Ê , ÓË [4]
¡ ¦Ò ¦ÆÕÉ ×¦ Ô Å ²¤È Ni Æ Ì ÛÞ µ¬© «
² ¾ Í ¦ ¦Ü¦Þ Ì ³Û ©Æ ¯ ª Ni-BCY Ì
» ³ Ð Ni
± ½È À ¼ ±ÛÞ Ü¦ § Ni-BCY Ì
Ų Ö ¦ Æ
Ú Ì Á ÛÞ Ü ¡½È
ª ¥
Ų Ü ©
¡ª Ų ÙÖ ¦¦Ü¦Þ Ì Å 2 Ñ©
¶ . [1−6]
Ì Ni Ü ÉÈ ¦ ··Ü BCY(BaCe Y O ) Ú Ö Õ Õ
0.9 0.1 ¦À
3−δ
· Ø , È (1453 C) Ê Ð °¿ Ê
[6] ◦
BaCO3 (99.9%), CeO2 (99.9%) Y2 O3 (99.9%)
ÔÅ « 2006–12–14, Ô ¥ ÄÅ «2007–02–02
Ì £ « ÀÑÍ Ë (50332040, 20371045)
¯Î « (1981– ), ¶ ¤£Ô ¨ ݦ «Æ µ ¨ E-mail:wliu@ustc.edu.cn

2. 1244 ¼ ´«Ì 22
Ý Ø§ ± ±¢ ¦Æ 24h, ¹Ü Ĺ ² Ç£  ¬ÎË Ù ± ©
950, 1200 1400 C Û ¡ 10h,
◦
¡ ´ ¬ ÑØ ¾ (Shimadzu GC-14C) · §´ ± Ä
¦ BCY Ý XRD ·× ¡ §
Ì´ ± § ¦Ú ·
Ø ©Á´ ¦À BCY Ý Ni Ý (99.9%) Û Ä §Ó ² Þ Æ Ê µ ¦Ð
Ni § (40vol%, 35vol%, 30vol%, ±ÞÆ Æ 90% Ð ©
25vol%, 20vol%) ´Æ ±¼ 24h, Ì Ð ´
»Ø X Ý
¼ Ý ¬ ½ ´Ï¹ Á ¦ Ì φ20mm ÇÆ ¦· X ÑØ Cu Kα(0.15418nm)
£¹ ¦¬Æ 300MPa ℄ÏÏÐ ¦ 7%H 2 ©
§ N -H ¼ ±Æ 1440 C ¥· Ç 5h Ì ◦
ÇÉÛ
2 2
Ì
» ©Æ¡Ó±Ø ¯ ÎÕ· 3
93%.
3.1 XRD Ó
§ 25% Ð
»ÆÚ·
Î ·
Ç ¾Ê
Ni
BCY Ý
§ Ê (
10Ω), ± Ni  ªÌ XRD
2 «Ó © ¹ ¨ ¦ ß BaCe Y O (JCPDS
³ ºÇÆ ¦ÓÐØÜÎÃ
Ð © 0.9 0.1 2.95
Æ Ð Ú ¹ · §
¦· § 822372) » ¹¹ ¦² Ä¡ ØÇÆ ©
¹ Ê 1 «Ó ¦· §· ² 600∼ 750 C.
Ð ± ² Ni-BCY Ì
» XRD Û ¿ ¬«Ü
»
◦
· Ý ¦
» Ø 600 Ì À ¨ ¦¬
¿ ß © Þ Ø Rull ° ¡¸ Ø 502 ª Ni BCY ß ¦½ ¬ª ¦Ö ×
á Æ · ¦¬À ´
» ª Ni-BCY Ì ¤ © 3 ±¨ ª
Æ ° ¡¸ ¦Æ 800 C · 30min ÎÃ Þ Æ ¦ ± Ni-BCY ² 40/60
» XRD ¾ ©
ÐßØ ÊËÀ
◦
Á´Â· Ì 750 C ÎÃ
· § ¦· § ± 3.2 Ni-BCY(40/60)
4 ײ ³ Ni-BCY(40/60)
»Æ 600∼
◦
·¦ Õ Æ 2 C/min Þ ©²ª Ø ·
◦
± Ni · ¦ Ï ÑØ 35ppm H Ar 2
¦¯§² 20mL/min. Î ÑØ H (20mL/min) 2
N (80mL/min) ¼
2 ©¼ ¦
°·¡ ± ( Õ ¡ · ² 25 C) Ü Þ ◦
¿¡ ÌÖ¼ ¦Ð Â Ë § ¡ ©Á´
2 BCY Ü X ½
Fig. 2 XRD pattern of BCY powder
1 ℄¸ 3 Ni-BCY(40/60) º X ½
Fig. 1 Equipment for hydrogen permeation Fig. 3 XRD pattern of Ni-BCY (40/60)

3. 6 ¿ £ ª Ni-BaCe 0.9 Y0.1 O3−δ Ê ¯ ı 1245
750◦ C
¦ ª· · · · ©· §«Ø
» ³ ¦
©Ú Ó ¦ª ¼ ³ ² Â℄¦ ¡ · Õ Æ 25∼ 27 C, Ð · § ÓÐ ◦
§¦·
¦ Ü« ¥ ©© ØÜÎõ Å ©Ð Ç §
«· § ½·² E Û a × ¬Ç ³ ¦ ÜÅ Á Ö © ± ¦Ð Ni:BCY(vol%)=30:70
L=0.90mm ¦ Ea =48.3kJ/mol; L=0.59mm
¦ Á¦Ò ² 40:60 ¦
¦Ea =61.4kJ/mol;L=0.36mm ¦Ea =55.3kJ/mol; ² 5:65 25:75 ÆÏ © 7 ¨ ª 700 C ◦
L=0.27mm ¦ Ea =61.3kJ/mol, ¸ [7] ± ² Ni Û Ni-BCY Ì
¦
Í
½·²§ × © ¦ÓЪ Ð ² ©
×Þ ÚÎ ­ Ö º
¦ Ö ÓÐƲ ¦
¦Ç
F
»³ Ö ¦¢ H2 Ú Ì Ni
¿
Ê ¥ Á BCY Þ¿
µ Þ ÚÎÕ ¦Ö ¦ µ Þ Ê¦ Ni-BCY Ì
Õ Ò¤×
Õ ©Ò
F = , ± J ²
¦ H2
JH2
H2 ¦ Þ¿ ¥ÕÜ ß© ©Å ×
¦ µ ² · Ý
»¥ µ º Ô ·
µi
i ²
¿ - °¿¼ Ê ¦Ì ÆÌ ±ß
ÎÖ ¦ß µ = − ln =i
RT
ln
2F , ± ¦R
PH2 (l)
PH2 (h)
RT
2F
PH2 (h)
PH2 (l) É£ ¦
¿ Ê ℄ ²ª ¦
² ½ ¦ T ² · ¦ F ²ÕÛ ½ ¦ ʺ Ni-BCY ² 20:80
» ¦
P (h) ²¥ Û Ï
H2 Û Ï ¦ P (l) ² ℄ H2 Ú·
Á¦Ö × Ni §­ Ê Ì Æ
ÛÏ ÛÏ©
»± ² £ © Ni-BCY ² 25:75
¬Ò© Ð § Ì
F ³ H2 5 «Ó ©Æ³ ² 0.90 ¡
0.59mm ¦ ³ ¢ ¦
»
µ Þ ÚÎÕ ÆÒ ³ ² 0.36 ¡ 0.27mm ¦
·Ý ¸Þª³ ¦
µ Þ Õ © ¦Ð Ö ×· Å
℄ ¦ Õ Ö Á ©Ò ¦ Î ³
¥ Ų ¦Ã
»³ × ² ¯ ¦¹
È ÎÃØ Ç ÆÙР℄ ȸ
·ÎÖ ©
3.3 NiÜÍÃ×Á Ni-BCY ÖÚ ÐßØ
¬¢ 5 Ni-BCY(40/60) ²
6 ¨ ª ² Ni Û
»
¦ Fig. 5 Hydrogen permeability of Ni-BCY (40/60) as
a function of membrane thickness
4 ± ² Ni-BCY(40/60) ¥ ©¶ 6 Ni BCY ± Ni-BCY ¥
¶ ¶
Fig. 4 Hydrogen permeation rate of Ni-BCY (40/60) Fig. 6 Hydrogen permeation rate as a function of
as a function of temperature with different membrane temperature with different volume ratios of Ni to
thicknesses BCY, thicknesses of the samples are all about 1.0mm

4. 1246 ¼ ´«Ì 22
4
1.Æ Ni-BCY(40/60) ± ¦² ³
»
¬Æ³ 0.6mm
»
Ð Ú
βµ ¦Ò ³  0.36mm Ð ¦
²Ð Úβµ ©
2. Ç Ni-BCY ² 30:70 ¦ Ni-
BCY Ì
»
¦ Ì Á©
3. Ë Ni Ì ¼ Ê BCY
°¿ Ê
¦ ÜÅ Á ¥ ¦ ÎŲ
Ü Î ©Æ
¿ ¡°¿ Ü Ø · ¦
7 Ni ¦ Ni-BCY ¥ (700◦ C) Î ³
» ÇÆ¿ ÆÙ ¦Ü
Fig. 7 Hydrogen permeation rate of Ni-BCY as a
function of Ni volume ratio at 700◦ C
Î ³ ¥
¦ ©
» ¦Ì Ni ¨Á Ê ¦Å §Ç¸ ¦
¿
Ê ² Ê
Å ©Ç [1] Siriwardane R V, PostonJr J A, Fisher E P, et al. Applied
Ì 30:70 ¦
¿ Ê
°¿ Ê
· ¤ Surface Science, 2000, 167 (1–2): 34–50.
¦
¦ Ì Á©Î ³ Ì Ñ [2] Zhang G, Dorris S, Balachandran U, et al. Electrochemical
Ì 35:65, BCY ² Ê °¿
and Solid State Letters, 2002, 5 (3): J5–J7.
[3] Balachandran U, Lee T H, Wang S, et al. Current Sta-
Ê
² ¦
¦ ÖÒ Â © 40:60 tus of Dense Ceramic Membranes for Hydrogen Separa-
¦ BCY §ª Ñ
»
¦ tion, International Technical Conference on Coal Utiliza-
Î ³ Â ©Ç Á ¦ Ò¤
¢¹ tion and Fuel Systems, Clearwater, FL(US), March 4–7,
ºÞ Ì ¬Ò¤ Ö ¦Ê ÇÆ Ö ¦Ì Ni
2002: 1155–1165.
Â Ê º¿¹º Õ º £ Å
[4] Zhang G, Dorris S E, Balachandran U, et al. Solid State
Ionics, 2003, 159 (1–2): 121–134.
¦Ò º¿¹ºÑ £ ¦ Å [5] Zuo C D, Lee T H, Song S J, et al. Electrochemical and
Ni § Ü §℄ Ð º Ç
¿ Ê
Solid State Letters, 2005, 8 (12): J35–J37.
Å Æ­ ¦¥· Ni Ü , º [6] [6] Song S J, Wachsman E D, Dorris S E, et al. Journal of
¯ °Ì · ¦ Ò Ö
»
The Electrochemical Society, 2003, 150: A1484–A1490.
¦ ©
[7] Kreuer KD, et al. Solid State Ionics, 1999, 125 (1–4):
285–302.