고체전해질형 연료전지용 Pr1-xMxMnO3(M-Ca, Sr) 산소극 재료의 특성

임형렬; 정순기; 이주성

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.6, 1125-1131, December, 1996

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고체전해질형 연료전지용 Pr1-xMxMnO3(M-Ca, Sr) 산소극 재료의 특성

Characteristics of Pr_1-xM_xMnO₃(M=Ca, Sr) as a Cathode Material of Solid Oxide Fuel Cell

임형렬, 정순기, 이주성

초록

고체전해질형 연료전지의 산소극 재료로서 페롭스카이트 구조를 갖는 PrMnO₃ 에 Ca과 Sr을 도핑시켜 도핑량에 따른 전기전도도, 산소환원과전압 등의 전기화학적 특성과, 전해질인 yttria stabilized zirconia와의 반응성 그리고 열 팽창률 등을 살펴 보았다. 합성된 페롭스카이트 분말은 대략 2∼5㎛의 평균입자 크기를 나타내었는데 이때 입자크기 및 비표면적은 도핑량과 무관하였다. Ca이 30mo1% 도핑되었을 때 전기전도도는 1000℃에서 2665 S·cm^-1로 가장 높은 값을 나타내었고, 분극을 통해 살펴 본 산소환원특성도 Ca이 30mo1% 도핑되었을 때 가장 우수한 특성을 나타내었다. 전극물질과 전해질인 YSZ를 1200℃에서 100시간 동안 반응시킨 결과 PrMnO₃에 Sr을 도핑시켰을 때보다 Ca을 도핑시킨 것이 반응성이 훨씬 약한 결과를 나타내었다. Pr_0.7Ca_0.3MnO₃의 열팽창계수는 300∼1000℃의 영역에서 1.19×10^-5K^-1로 측정되었고 이 값은 YSZ의 열팽창계수 1.15×10^-5K^-1과 유사한 값이었다.

Ca or Sr-doped PrMnO₃ were prepared for cathode material of solid oxide fuel cell. The characteristics such as the electrical conductivity and the cathodic overpotential were investigated as to doping contents. Also the reactivity with yttria stabilized zirconia of electrolyte, and the thermal expansion coefficient were studied. The prepared perovskite powder had the mean particle size of 2∼5㎛, and the particle size and the surface area was out of relation to the doping content. When Ca doping amount of electrode material was 30mo1%, the electrical conductivity was the highest value of 266 S·cm^-1 at 1000℃, and also the polarization characteristics showed the best property. The reactivity between YSZ and Ca-doped PrMnO₃ at 1200 ℃ for 100hours was lower than that between YSZ and Sr-doped PrMnO₃. The thermal expansion coefficient of Pr_0.7 Ca_0.3MnO₃ was 1.19 × 10^-5K^-1 in the temperature range of 300∼1000℃, and this value was similar to that of YSZ, 1.15 × 10^-5K^-1 .

[References]

Minh NQ, J. Am. Ceram. Soc., 73, 563 (1993)
Takashima M, Kano G, Solid State Ion., 23, 99 (1987)
Cook RL, MacDuff RC, Sammells AF, J. Electrochem. Soc., 137, 3309 (1990)
Kilner JA, Barrow P, Brook RJ, Norgett MJ, J. Power Sources, 3, 67 (1978)
Ishihara T, Kudo T, Matsuda H, Takida Y, J. Am. Ceram. Soc., 77, 1682 (1994)
Ishihara T, Kudo T, Matsuda H, Takita Y, J. Electrochem. Soc., 142(5), 1519 (1995)
Watanabe M, Uchida H, Shibata M, Mochizuki N, Amikura K, J. Electrochem. Soc., 141(2), 342 (1994)
Rim HR, Lee JS, J. Korean Ind. Eng. Chem., 7(1), 9 (1996)
Gallagher PK, MacChesney JB, Buchanan DNE, J. Chem. Phys., 45, 2466 (1966)
Shannon RD, Acta Crystallogr. Sect. A, 32, 751 (1976)
Goodenough JB, Phys. Rev., 100, 564 (1955)
Takeda Y, Kanno R, Noda M, Tomida Y, Yamamoto D, J. Electrochem. Soc., 134, 2656 (1987)
Taimatsu H, Wada K, Kaneko H, J. Am. Ceram. Soc., 75, 401 (1992)
Labrincha JA, Frade JR, Margues FMB, J. Mater. Sci., 75, 401 (1992)
Ohno Y, Nagata S, Sato H, Solid State Ion., 9-10, 1001 (1989)

[Referenced By]

[1] Minh NQ, J. Am. Ceram. Soc., 73, 563 (1993)

[2] Takashima M, Kano G, Solid State Ion., 23, 99 (1987)

[3] Cook RL, MacDuff RC, Sammells AF, J. Electrochem. Soc., 137, 3309 (1990)

[4] Kilner JA, Barrow P, Brook RJ, Norgett MJ, J. Power Sources, 3, 67 (1978)

[5] Ishihara T, Kudo T, Matsuda H, Takida Y, J. Am. Ceram. Soc., 77, 1682 (1994)

[6] Ishihara T, Kudo T, Matsuda H, Takita Y, J. Electrochem. Soc., 142(5), 1519 (1995)

[7] Watanabe M, Uchida H, Shibata M, Mochizuki N, Amikura K, J. Electrochem. Soc., 141(2), 342 (1994)

[8] Rim HR, Lee JS, J. Korean Ind. Eng. Chem., 7(1), 9 (1996)

[9] Gallagher PK, MacChesney JB, Buchanan DNE, J. Chem. Phys., 45, 2466 (1966)

[10] Shannon RD, Acta Crystallogr. Sect. A, 32, 751 (1976)

[11] Goodenough JB, Phys. Rev., 100, 564 (1955)

[12] Takeda Y, Kanno R, Noda M, Tomida Y, Yamamoto D, J. Electrochem. Soc., 134, 2656 (1987)

[13] Taimatsu H, Wada K, Kaneko H, J. Am. Ceram. Soc., 75, 401 (1992)

[14] Labrincha JA, Frade JR, Margues FMB, J. Mater. Sci., 75, 401 (1992)

[15] Ohno Y, Nagata S, Sato H, Solid State Ion., 9-10, 1001 (1989)