메조페이스 핏치로부터 균질한 다공성 탄소 제조 및 이를 이용한 직접 메탄올 연료전지의 촉매 담지체 특성

김태진; 김상경; 이병록; 백동현; 정두환; 남기돈; 유승곤; Tae-Jin Kim; Sang-Kyung Kim; Byoung-Rok Lee; Dong-Hyun Peck; Doo-Hwan Jung; Ki-Don Nam; Seung-Kon Ryu

Journal of the Korean Industrial and Engineering Chemistry, Vol.17, No.2, 223-228, April, 2006

Preparation of Uniform Porous Carbon from Mesophase Pitch and Its Characteristics of Catalyst Support for the Direct Methanol Fuel Cell

김태진¹, 김상경 ¹, 이병록¹, 백동현 ¹, 정두환^{1, †}, 남기돈^{1, 2}, 유승곤 ²

¹한국에너지기술연구원 신에너지연구부
²충남대학교 화학공학과

Tae-Jin Kim¹, Sang-Kyung Kim¹, Byoung-Rok Lee¹, Dong-Hyun Peck¹, Doo-Hwan Jung^{1, †}, Ki-Don Nam^{1, 2}, and Seung-Kon Ryu²

¹Advanced Energy Research Department, Korea Institute of Energy Research, Jang-dong 71-2, Yuseong-gu, Daejeon 305-343, Korea
²Department of Chemical Engineering, Chungnam National University, 220, Gung-dong, Yuseong-gu, Daejeon 305-764, Korea

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초록

직접 메탄올 연료전지에서 촉매 담지체로서 세공 크기별 균질한 다공성 탄소는 메조페이스 핏치와 졸-겔법으로 직접 합성한 구형 실리카를 이용하여 제조하였다. Tetrahydrofuran (THF)에 용해된 핏치와 메탄올에 분산된 구상의 실리카를 혼합하고 탄화한 후에 5 M NaOH로 실리카를 식각하여 다공성 탄소를 만들었다. 이 다공성탄소의 비표 면적은 사용된 구형 실리카의 입자 크기가 작을수록 증가하였으며, 14.7~87.7 m2/g 범위를 나타내었다. 평균 기공 직경 또한 사용된 실리카 입자크기에 따라 50~550 nm로 다양하게 나타났다. 다공성 탄소 담지체에 백금과 루테늄을 담지시키기 위해 액상환원법을 사용하였고, 60 wt% 백금 루테늄이 담지된 촉매의 전기 산화 활성 및 전극 성능 특성은 순환 전압 전류법과 단위전지 시험으로 평가하였다. 본 실험 범위 중 50 nm 실리카를 이용하여 제조한 백금-루테늄/다공성탄소의 경우(60 wt% Pt-Ru/porous carbon), 순환 전압 전류법 시험에서 0.4 V에서의 전류 밀도 값이 123 mA/cm2가 측정되었고, 단위전지 성능 시험에서는 최대 전력 밀도 값이 60℃와 80℃, 산소분위기에서 각각 105, 162 mW/cm2를 나타내었다.

Pore-size controlled porous carbons for the catalyst supports of the direct methanol fuel cell were prepared from the mesophase pitch by using the silica spheres with different sizes. Pitch solution in THF and spheres were mixed, carbonized and etched by 5 M NaOH to make porous carbon. Specific surface area of the porous carbons was 14.7～87.7 m2/g and average pore diameter was 50~550 nm which were dependent on the size of silica spheres. Aqueous reduction method was used to load 60 wt% PtRu on the prepared porous carbon supports. The electro-oxidation activity of the supported 60 wt% Pt-Ru catalysts was measured by cyclic voltammetry and unit cell test. For the 60 wt% Pt-Ru/porous carbon synthesized by 50 nm silica, current density value in the cyclic voltammetry test was 123 mA/cm2 at 0.4 V and peak power density in the unit cell test were 105 and 162 mW/cm2 under oxygen at 60 and 80 ℃, respectively.

Keywords:DMFC;silica sphere;porous carbon;catalyst support;cyclic voltammetry

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Osseo-Asare K, Arriagada FJ, Colloids Surf., 50, 321 (1990)
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Messing GL, Mazdiyasni KS, McCauley JW, Haber RA, Ceram. Powder Sci., 21, 121 (1987)
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[2] Scott K, Taama WM, Argyropoulos P, J. Power Sources, 79(1), 43 (1999)

[3] Heinzel A, Barragan VM, J. Power Sources, 84(1), 70 (1999)

[4] Watanabe M, Motoo S, J. Electroanal. Chem., 60, 259 (1975)

[5] Rajesh B, Karthik V, Karthikeyan S, Thampi KR, Bonard JM, Viswanathan B, Fuel, 81, 2177 (2002)

[6] Ryoo R, Joo SH, Kruk M, Jaroniec M, Adv. Mater., 13, 677 (2001)

[7] Chai GS, Yoon SB, Kang S, Choi JH, Sung YE, Ahn YS, Kim HS, Yu JS, Electrochim. Acta, 50, 823 (1992)

[8] Beauharnois ME, Edie DD, Thies MC, Carbon, 39, 2101 (2001)

[9] Jones SP, Fain CC, Edie DD, Carbon, 35, 1533 (1997)

[10] Osseo-Asare K, Arriagada FJ, Colloids Surf., 50, 321 (1990)

[11] Kawaguchi T, Sugimoto W, Murakami Y, Takasu Y, J. Catal., 229(1), 176 (2005)

[12] Burke LD, Casey JK, Electrochim. Acta, 37, 1817 (1992)

[13] Rand DAJ, Woods R, J. Electroanal. Chem., 36, 57 (1972)

[14] Okunev AG, Shaurman SA, Danilyuk AF, Aristov YI, Bergeret G, Renuprez A, J. Non-Cryst. Solids, 260, 21 (1999)

[15] Allongue P, Brune H, Gerscher H, Surf. Sci., 275, 414 (1992)

[16] Messing GL, Mazdiyasni KS, McCauley JW, Haber RA, Ceram. Powder Sci., 21, 121 (1987)

[17] Lee Y, Lee CW, Kang HS, Jang YH, Hahm YM, Appl. Chem., 1(2), 398 (1997)

[18] Poppe T, Icarus, 164, 139 (2003)

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