Noble Way to Low-Cost Fuel Cells, Halogenated Graphene May Replace Expensive Platinum
June 5, 2013 — Ulsan, South Korea (Source: UNIST) — The research team of Ulsan National Institute of Science and Technology (UNIST) paved a new way to affordable fuel cells with efficient metal-free electrocatalysts using edge-halogenated graphene nanoplatelets.
The research team of Profs. Jong-Beam Baek and Noejung Park of UNIST, and Prof. Liming Dai of Case Western Reserve University, for the first time, reportedly synthesized a series of edge-selectively halogenated (Cl, Br and I) graphene nanoplatelets (XGnPs) by ball-milling graphite flake in the presence of chlorine (Cl2), bromine (Br2), or iodine (I2), respectively. The newly prepared XGnPs as metal-free electrocatalysts for oxygen reduction reaction (ORR) stand as a possible replacement for platinum (Pt), which is currently the most reliable material for cathodic ORR electrocatalysts in fuel cells.
Edge-halogenated graphene nanoplatelets (XGnPs) are solution processable, and show remarkable electrocatalytic activity toward ORR with a high selectivity, good tolerance and excellent long-term cycle stability.
One of the major drawbacks for commercialization of the fuel cell technology is the dragging ORR at cathode. So far, costly and precious Pt and its alloys have been considered to be the most reliable cathodic ORR electrocatalysts in fuel cells. However, Pt and its alloys have a drawback in that they suffer from methanol crossover/carbon monoxide (CO) poisoning effects and poor operation stability.
Although extensive efforts have been devoted to the development of non-precious metal-based electrocatalysts, their practical application is still far from being a reality due to their limited electrocatalytic activity, poor cycle stability, and sometimes environmental hazard.
Alternatively, carbon-based materials, doped with heteroatoms such as boron (B), halogen (Cl, Br, I) nitrogen (N), phosphorus (P), sulfur (S) and their mixtures, have attracted tremendous attentions as metal-free ORR electrocatalysts. However, full potential of these carbon-based, metal-free catalysts is hard to achieve without the synthetic capability for large-scale, low-cost production of the heteroatome-doped, carbon-based materials.
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These novel metal-free electrocatalysts were synthesized by ball-milling at high speed rotation (500 rpm) using stainless steel balls, generating sufficient kinetic energy to cause bond cleavages of the graphitic C-C framework. As a result, active carbon species formed at the broken edges of graphite, which were sufficiently reactive to pick up halogens in the sealed ball-mill capsule.
The resultant XGnPs were tested as cathode electrodes of fuel cells and revealed remarkable electrocatalytic activities for ORR with higher tolerance to methanol crossover/CO poisoning effects and longer-term stability than those of the original graphite and commercial Pt/C electrocatalysts.
Jong-Beom Baek, professor and director of the Interdisciplinary School of Green Energy/Low-Dimensional Carbon Materials Center, UNIST, Ulsan, South Korea, led the effort.
“Our result presents new insights and practical methods for designing edge-functionalized GnPs as high-performance metal-free ORR electrocatalysts through low-cost and scalable ball-milling techniques,” said Prof. Baek.
A description and details of the new research was published on June 5, 2013 (British Time) in the (Nature Publishing Group) Scientific Reports. (Title: Facile, scalable synthesis of edge-halogenated graphene nanoplatelets as efficient metal-free electrocatalysts for oxygen reduction reaction, DOI: 10.1038/srep01810)
World Class University (WCU), Mid-Career Researcher (MCR) and Basic Research Laboratory programs through the National Research Foundation of Korea, US-Korea NBIT and the U.S Air Force Office of Scientific Research funded the research.
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