• 전기화학회지
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• 제16권1호
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• pp.52-58
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• 2013

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.

• Journal of Electrochemical Science and Technology
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• 제15권2호
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• pp.207-219
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• 2024

Metal-N-C (MNC) catalysts have been anticipated as promising candidates for oxygen reduction reaction (ORR) to achieve low-cost polymer electrolyte membrane fuel cells. The structure of the M-N_x moiety enabled a high catalytic activity that was not observed in previously reported transition metal nanoparticle-based catalysts. Despite progress in non-precious metal catalysts, the low density of active sites of MNCs, which resulted in lower single-cell performance than Pt/C, needs to be resolved for practical application. This review focused on the recent studies and methodologies aimed to overcome these limitations and develop an inexpensive catalyst with excellent activity and durability in an alkaline environment. It included the possibility of non-precious metals as active materials for ORR catalysts, starting from Co phthalocyanine as ORR catalyst and the development of methodologies (e.g., metal-coordinated N-containing polymers, metal-organic frameworks) to form active sites, M-N_x moieties. Thereafter, the motivation, procedures, and progress of the latest research on the design of catalyst morphology for improved mass transport ability and active site engineering that allowed the promoted ORR kinetics were discussed.

• 전기화학회지
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• 제15권1호
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• pp.12-18
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• 2012

다양한 응용분야에서 활용될 수 있는 고체고분자연료전지의 경우 현재 상용화에 가장 큰 걸림돌이 되고 있는 것이 고가의 백금 촉매이다. 따라서 특히 최근 들어 산소환원반응에서 백금을 대체하는 물질을 개발하기 위한 연구가 전세계적으로 확산되고 있다. 그러나 촉매 개발 시 경제성 관점 외에 내구성도 고려해야 하는데, 이런 관점에서 백금과 유사한 물성과 활성이 기대되는 백금족 원소들이 한 대안이 될 것이다. 가장 백금과 유사한 물성, 활성을 나타내는 팔라듐과 칼코겐화물 형태의 루테늄이 지금까지 가장 많이 연구가 되었으며 상대적으로 이리듐, 로듐, 오스뮴은 산소환원 촉매로 많은 연구가 되지 않았다. RDE (rotating disk electrode)를 이용한 반쪽전지 실험이나 연료전지 MEA (membrane electrode assembly) 운전을 통하여 백금과 활성을 비교해보면 팔라듐 계열의 비백금 촉매가 가장 백금에 가까운 활성을 나타내고 있음을 알 수 있다. 이 논문에서는 각 백금족 원소들 기반의, 현재까지 문헌상으로 보고된 촉매조성들을 분석하여 비백금 산소환원 촉매 개발에 도움이 되고자 한다.

• Korean Chemical Engineering Research
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• 제57권3호
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• pp.425-431
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• 2019

As rechargeable metal-air batteries will be ideal energy storage devices in the future, an active cathode electrocatalyst is required with bi-functionality on both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during discharge and charge, respectively. Here, a class of perovskite cathode catalyst with a micro-tubular structure has been developed by controlling bi-functionality from different Ru and Ni dopant ratios. A micro-tubular structure is achieved by the activated carbon fiber (ACF) templating method, which provides uniform size and shape. At the perovskite formula of $LaCrO_3$, the dual dopant system is successfully synthesized with a perfect incorporation into the single perovskite structure. The chemical oxidation states for each Ni and Ru also confirm the partial substitution to B-site of Cr without any changes in the major perovskite structure. From the electrochemical measurements, the micro-tubular feature reveals much more efficient catalytic activity on ORR and OER, comparing to the grain catalyst with same perovskite composition. By changing the Ru and Ni ratio, the $LaCr_{0.8}Ru_{0.1}Ni_{0.1}O_3$ micro-tubular catalyst exhibits great bi-functionality, especially on ORR, with low metal loading, which is comparable to the commercial catalyst of Pt and Ir. This advanced catalytic property on the micro-tubular structure and Ru/Ni synergy effect at the perovskite material may provide a new direction for the next-generation cathode catalyst in metal-air battery system.

• 세라미스트
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• 제21권4호
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• pp.331-348
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• 2018

With the expectation to overcome the problem of increasing energy consumption, polymer electrolyte membrane fuel cells are getting more attention as a promising environmentally friendly and sustainable next-generation energy conversion system. In spite of the rapid improvement of polymer electrolyte membrane fuel cells(PEMFCs), there are several critical issues still need to be resolved for practical commercialization. Out of the many issues, the main hurdle comes from oxygen reduction reaction(ORR), thus development of efficient ORR electrocatalysts is the main key for enhancing PEMFC performance. Among various catalysts, 1D nanostructured catalyst is a promising candidate because it holds many advantages that come from nanostructuring while supplementing the disadvantages of other nanostructures such as nanoparticles(0D) or gyroids(3D). This review focused on diverse 1D nanostructures and talks about their advantages as catalyst for ORR. Different 1D nanostructures will be introduced while applying the structures to different materials system showing the prospects of 1D nanostructures for improving PEMFC.

• Corrosion Science and Technology
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• 제21권5호
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• pp.412-417
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• 2022

Proton exchange membrane fuel cells (PEMFCs) provide zero emission power sources for electric vehicles and portable electronic devices. Although significant progresses for the widespread application of electrochemical energy technology have been achieved, some drawbacks such as catalytic activity, durability, and high cost of catalysts still remain. Pt-based catalysts are regarded as the most efficient catalysts for sluggish kinetics of oxygen reduction reaction (ORR). However, their prohibitive cost limits the commercialization of PEMFCs. Therefore, we proposed a NiCo@Au core shell structure as Pt-free ORR electrocatalyst in PEMFCs. NiCo alloy was synthesized as core to introduce ionization tendency and autoxidation reaction. Au as a shell was synthesized to prevent oxidation of core NiCo and increase catalytic activity for ORR. Herein, we report the synthesis, characterization, electrochemical properties, and PEMFCs performance of the novel NiCo@Au core-shell as a catalyst for ORR in PEMFCs application. Based on results of this study, possible mechanism for catalytic of autoxidation core@anti-oxidation shell in PEMFCs is suggested.

• Journal of Ceramic Processing Research
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• 제19권6호
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• pp.499-503
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• 2018

In this paper, cobalt embedded in nitrogen and sulfur co-doped carbon nanotubes (CoNSTs) were synthesized for oxygen reduction reaction (ORR) catalysts. The CoNSTs were prepared through a facile heat treatment method without any templates. Different amounts of the metal salt were employed to examine the physicochemical and electrochemical properties of the CoNSTs. The CoNSTs showed the bamboo-like tube morphology with the encased Co nanoparticles in the tubes. Through the x-ray photoelectron spectroscopy analysis, the catalysts exhibited different chemical states of the nitrogen and sulfur species. As a result, the CoNST performed high activity toward the ORR in an acidic condition with the onset potential of 0.863 V (vs. reversible hydrogen electrode). It was clearly demonstrated from the electrochemical characterizations that the quality of the nitrogen and sulfur species significantly influences the ORR activity rather than the total amount of the dopants.

• 대한화학회지
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• 제68권2호
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• pp.87-92
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• 2024

The commercialization of rechargeable metal-air batteries is extremely desirable but designing stable oxygen reduction reaction (ORR) catalysts with non-noble metal still has faced challenges to replace platinum-based catalysts. The nonnoble metal catalysts for ORR were prepared to improve the catalytic performance and stability by the thermal decomposition of ZIF-8 with optimum cobalt loading. The porous carbon was obtained by the calcination of ZIF-8 and different loading amounts of Co nanoparticles were anchored onto porous carbon forming a Co/PC catalyst. Co/PC composite shows a significant increase in the ORR value of current and stability (500 h) due to the good electronic conductive PCN support and optimum cobalt metal loading. The significantly improved catalytic performance is ascribed to the chemical structure, synergistic effects, porous carbon networks, and rich active sites. This method develops a new pathway for a highly active and advantageous catalyst for electrochemical devices.

• 한국태양에너지학회:학술대회논문집
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• 한국태양에너지학회 2012년도 춘계학술발표대회 논문집
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• pp.406-409
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• 2012

Recently, enormous research efforts have been focused on the development of non-precious catalysts to replace Pt for electrocatalytic oxygen reduction reaction (ORR), and to reduce the cost of proton exchange membrane fuel cells (PEMFCs). In recent years, heteroatom (N, B, and P) doped carbon nanostructures have been received enormous importance as a non-precious electrode materials for oxygen reduction. Doping of foreign atom into carbon is able to modify electronic properties of carbon materials. In this study, nitrogen and boron doped carbon nanostructures were synthesized by using a facile and cost-effective thermal annealing route and prepared nanostructures were used as a non-precious electrocatalysts for the ORR in alkaline electrolyte. The nitrogen doped carbon nanocapsules (NCNCs) exhibited higher activity than that of a commercial Pt/C catalyst, excellent stability and resistance to methanol oxidation. The boron-doped carbon nanostructure (BC) prepared at $900^{\circ}C$ showed higher ORR activity than BCs prepared lower temperature (800, $700^{\circ}C$). The heteroatom doped carbon nanomaterials could be promising candidates as a metal-free catalysts for ORR in the PEMFCs.

• 대한금속재료학회지
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• 제47권7호
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• pp.454-459
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• 2009

In order to commercialize Polymer Electrolyte Fuel Cell (PEFC), the cathode catalyst such as Platinum supported Carbon (Pt/C) need to have a high activity of Oxygen Reduction Reaction (ORR). In this study, the 20% Pt/C was synthesized using the chemical reduction method while the crystallinity of Platinum (Pt) particles were controlled under heat treatment conditions. The activity of synthesized Pt catalysts was evaluated using electrochemical measurement. Compared with the $i_{ORR}$ at 0.8 V of 20% Pt/C heat-treated at $500^{\circ}C$ and the 20% Pt/C that were not heated and commercial 20% Pt/C, the $i_{ORR}$ at 0.8 V of 20% Pt/C heattreated at $500^{\circ}C$ was 9.5 and 1.7 times higher than those of the 20% Pt/C and commercial 20% Pt/C that were not heated. It was considered that the crystallinity and particle size affect the ORR activity of the Pt/C catalysts.