고분자 전해질 연료전지 캐소드용 코발트-폴리아닐린-탄소로 구성된 비귀금속 촉매의 제조 및 특성 평가
Synthesis and Characterization of Non-precious Metal Co-PANI-C Catalysts for Polymer Electrolyte Membrane Fuel Cell Cathodes
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초록
고분자 전해질 연료전지(Polymer Electrolyte Membrane Fuel Cell, PEMFC) 상용화를 위해 해결해야 할 과제 중의 하나인 가격 저감을 이루기 위한 방법으로 백금 촉매를 대신할 비귀금속(non-precious metal) 촉매 제조에 관한 연구를 수행하였다. 비귀금속 촉매의 합성은 산소환원반응(oxygen reduction reaction, ORR)의 활성점으로 알려져 있는 코발트-질소(Co-N) 결합을 형성하기 위해 질소를 포함하는 폴리아닐린(PANI)과 코발트염(Co precursor), 그리고 카본 블랙(C)을 일정한 비율대로 혼합한 후 특별한 열처리 과정 없이 단순한 화학적 환원법에 제조되었다. 제조된 Co-PANI-C 복합 촉매의 구조 분석을 위해 X-선 회절분석(X-ray diffraction, XRD)과 열중량분석(thermogravimetric analysis, TGA)을 실시하였고, ORR에 대한 활성을 평가하기 위해 rotating disk electrode(RDE) 및 rotating ring disk electrode(RRDE) 측정을 수행하였다. 그 결과 Co-PANI-C 복합 촉매는 ORR반응에 대한 개시 전압은 백금 촉매보다 60 mV 밖에 낮지 않은 값을 보였지만, 반응에 의해 발생되는 환원 전류는 여전히 백금 촉매보다 낮은 값을 보였다. 이 밖에도 전극 회전 속도에 따른 ORR 특성 변화, 전압 사이클 회수에 따른 내구성 변화, 연료전지 적용 시 성능 변화에 대해 논의할 것이다.
Abstract
In order to overcome the cost issue for commercialization of polymer electrolyte mem-brane fuel cell (PEMFC), this research was conducted for replacing platinum cathode catalyst with non-precious metal catalyst. The non-precious metal catalyst (Co-PANI-C) was synthesized by the simple reduction method with polyaniline (PANI), carbon black, and cobalt precursor without any heat treatment. Characterization of new Co-PANI-C composite catalysts was done by the mea-surement of X-ray diffraction (XRD) and thermogravimetric analysis (TGA) for structure analysis and performed by rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) for elec-trochemical analysis. As a result, Co-PANI-C catalyst showed 60 mV lower on-set potential for oxygen reduction reaction (ORR) than Pt/C catalyst, but the overall reduction current of Co-PANI-C catalysts by ORR was still smaller than that of Pt/C. In addition, the ORR behavior of Co-PANI-C catalysts depending on the rotation speed of electrode and the stability of Co-PANI-C catalyst under potential cycling and the performance of fuel cell conditions are also discussed.
참고문헌 (34)
- A. S. Arico, "DMFCs: From Fundamental Aspects to Technology Development", Fuel Cells, 1, pp.133~ (2001)
- K. Kordesch, "Fuel Cells and their Applications" (1996), Wiley-VCH
- S. Wasmus, "Methanol oxidation and direct methanol fuel cells: a selective review", J. Electroanal. Chem, 461, pp.14~ (1999)
- M. P. Hogarth, "Direct Methanol Fuel Cells: Technological Advances and Further requirements", Plat. Met. Rev, 40, pp.150~ (1996)
- D. J. Berger, "‘Fuel cells and precious-metal catalysts", Science, 286, pp.49~ (1999)
- T. A. Semelsberger, "Fuel effects on start-up energy and efficiency for automotive PEM fuel cell systems’", Int. J. Hydrogen Energy, 30, pp.425~ (2005)
- J. Xie, "Microstructural changes of membrane electrode assemblies during PEFC durability testing at high humidity conditions", J. Electrochem. Soc, 152, pp.A1011~ (2005)
- A. J. Appleby, "Electrocatalysis of aqueous dioxygen reduction", J. Electroanal. Chem, 357, pp.117~ (1993)
- M. Hayashi, "Reverse micelle assisted dispersion of lanthanum manganite on carbon support for oxygen reduction cathode", J. Electrochem. Soc, 151, pp.A158~ (2004)
- 최종호, "캐소드 루테늄 촉매의 전기화학적 환원 처리가 고분자 전해질 연료전지 성능에 미치는 영향", 전기화학회지, 14(2), pp.110~116 (2011), 한국전기화학회
- N. Alonso-Vante, "On the origin of the selectivity of oxygen reduction of rutheniumcontaining electrocatalysts in methanol-containing electrolyte", J. Cat, 190, pp.240~ (2000)
- T. J. Schmidt, "Oxygen reduction on Ru1.92 Mo0.08SeO4, Ru", carbon, and Pt, J. Electrochem. Soc, pp.2000, 147[DOI]
- 권경중, "고체 고분자 연료전지용 비백금계 산소환원촉매 조성 조사 및 분석", 전기화학회지, 15(1), pp.12~18 (2012), 한국전기화학회
- M. Lefèvre, "O2 reduction in PEM fuel cells: activity and active site structural information for catalysts obtained by the pyrolysis at high temperature of Fe precursors", J. Phys. Chem. B, 104, pp.11238~ (2000)
- G. Faubert, "Heat-treated iron and cobalt tetraphenylporphyrins adsorbed on carbon black: Physical characterization and catalytic properties of these materials for the reduction of oxygen in polymer electrolyte fuel cells", Electrochim. Acta, 41, pp.1689~ (1996)
- M. Bron, "EXAFS, XPS and electrochemical studies on oxygen reduction catalysts obtained by heat treatment of iron phenanthroline complexes supported on high surface area carbon black", J. Electroanal. Chem, 535, pp.113~ (2002)
- G. Faubert, "‘Oxygen reduction catalysts for polymer electrolyte fuel cells from the pyrolysis of Fe(II) acetate adsorbed on 3,4,9,10-perylenetetracarboxylic dianhydride", Electrochim. Acta, 44, pp.2589~ (1999)
- S. L. Gojkovic, "Heattreated iron(III) tetramethoxyphenyl porphyrin chloride supported on high-area carbon as an electrocatalyst for oxygen reduction: Part II. Kinetics of oxygen reduction", J. Electroanal. Chem, 462, pp.63~ (1999)
- G. Lalande, "Catalytic activity and stability of heat-treated iron phthalocyanines for the electroreduction of oxygen in polymer electrolyte fuel cells", J. Power Sources, 61, pp.227~ (1996)
- S. Maldonado, "Direct preparation of carbon nanofiber electrodes via pyrolysis of iron(II) phthalocyanine: electrocatalytic aspects for oxygen reduction", J. Phys. Chem. B, 108, pp.11375~ (2004)
- G. Wu, "Polyaniline-derived non-precious catalyst for the polymer electrolyte fuel cell cathode", ECS Trans, 16, pp.159~ (2008)
- G. Wu, "Nitrogendoped magnetic onion-like carbon as support for Pt particles in a hybrid cathode catalyst for fuel cells", J. Mater. Chem, 20, pp.3059~ (2010)
- V. Nallathambi, "Development of high performance carbon composite catalyst for oxygen reduction reaction in proton exchange membrane fuel cells", J. Power Sources, 183, pp.34~ (2008)
- M. Lefevre, "Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells", Science, 324, pp.71~ (2009)
- P. H. Matter, "Preparation of nanostructured nitrogen-containing carbon catalysts for the oxygen reduction reaction from SiO2 − and MgO− supported metal particles", J. Catal, 243, pp.395~ (2006)
- F. Jaouen, "Cross-laboratory experimental study of non-noble-metal electrocatalysts for the oxygen reduction reaction", ACS Appl. Materials & Interfaces, 1, pp.1623~ (2009)
- D. Villers, "Febased catalysts for oxygen reduction in PEM fuel cells: Pretreatment of the carbon support", J. Electrochem. Soc., 151, pp.A1507~ (2004)
- G. Wu, "Performance durability of polyaniline-derived non-precious cathode catalysts", ECS Trans, 25, pp.1299~ (2009)
- R. Bashyam, "A class of non-precious metal composite catalysts for fuel cells", Nature, 443, pp.63~ (2006)
- S. Khasim, "Synthesis, characterization and magnetic properties of polyaniline", γ- Fe2O3 composites, 2011, pp.34, 1557~
- M. Carmo, "Physical and electrochemical evaluation of commercial carbon black as electrocatalysts supports for DMFC applications", J. Power Sources, 173, pp.860~ (2007)
- G. P. Glaspell, "Formation of cobalt nitrate hydrate, cobalt oxide, and cobalt nanoparticles using laser vaporization controlled condensation", J. Phys. Chem. B, 108, pp.9604~ (2004)
- U. A. Paulus, "Oxygen reduction on a high-surface area Pt", Vulcan carbon catalyst: a thin-film rotating ring-disk electrode study, 2001, pp.495, 134~
- V. Prabhakaran, "Investigation of polymer electrolyte membrane chemical degradation and degradation mitigation using in situ fluorescence spectroscopy", PNAS, 109, pp.1029~ (2012)