DOE Award No. DE-FC36-03GO13108 NOVEL NON-PRECIOUS METAL CATALYSTS FOR PEMFC: CATALYST SELECTION THROUGH MOLECULAR MODELING AND DURABILITY STUDIES Final Report (September 2003 – October 2008)
The objective of this project is to develop novel non-precious metal electrocatalysts for oxygen reduction reaction (ORR), and demonstrate the potential of the catalysts to perform at least as good as conventional Pt catalysts currently in use in polymer electrolyte membrane fuel cell (PEMFC) with a cost at least 50 % less than a target of 0.2 g (Pt loading)/peak kW and with durability > 2,000 h operation with less than 10 % power degradation. A novel nitrogen-modified carbon-based catalyst was obtained by modifying carbon black with nitrogen-containing organic precursor in the absence of transition metal precursor. The catalyst shows the onset potential of approximately 0.76 V (NHE) for ORR and the amount of H2O2 of approximately 3% at 0.5 V (NHE). Furthermore, a carbon composite catalyst was achieved through the high-temperature pyrolysis of the precursors of transition metal (Co and Fe) and nitrogen supported on the nitrogen-modified carbon-based catalyst, followed by chemical post-treatment. This catalyst showed an onset potential for ORR as high as 0.87 V (NHE), and generated less than 1 % of H2O2. The PEM fuel cell exhibited a current density of 2.3 A cm-2 at 0.2 V for a catalyst loading of 6.0 mg cm-2. No significant performance degradation was observed for 480 h continuous operation. The characterization studies indicated that the metal-nitrogen chelate complexes decompose at the temperatures above 800 oC. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface modified with nitrogen is active for ORR. In order to elucidate the role of transition metal precursor played in the formation of active sites in the non-precious metal catalysts, a novel ruthenium-based chelate (RuNx) catalyst was synthesized by using RuCl3 and propylene diammine as the Ru and N precursors, respectively, followed by high-temperature pyrolysis. This catalyst exhibited comparable catalytic activity and selectivity for ORR as the Pt catalyst. A theoretical analysis is made of the four-electron reduction reaction of oxygen to water over the mixed anion and cation (202) surface of pentlandite structure Co9Se8, one of several selenide phases. Reversible potentials for forming adsorbed reaction intermediates in acid are predicted using adsorption energies calculated with the Vienna ab initio simulation program (VASP) and the known bulk solution values together in a linear Gibbs energy relationship. The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.
- Research Organization:
- University of South Carolina, Columbia, SC
- Sponsoring Organization:
- USDOE Office of Hydrogen, Fuel Cells, and Infrastructure Technologies Program (EE-2H)
- DOE Contract Number:
- FC36-03GO13108
- OSTI ID:
- 948557
- Report Number(s):
- DOE/GO/13108; TRN: US200908%%42
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
25 ENERGY STORAGE
08 HYDROGEN
36 MATERIALS SCIENCE
42 ENGINEERING
ADSORPTION
ANIONS
CARBON
CARBON BLACK
CATALYSTS
CATHODES
CATIONS
CHELATES
CURRENT DENSITY
DIFFUSION
ELECTROCATALYSTS
ELECTROLYTES
FUEL CELLS
GEOMETRY
KINETICS
MEMBRANES
NITROGEN
OXYGEN
POLYMERS
PRECURSOR
PROPYLENE
PYROLYSIS
REACTION INTERMEDIATES
SELENIDES
TARGETS
TRANSITION ELEMENTS
Non-precious metal catalyst
Fuel cell performance
Durability
Cost