Proton exchange membrane fuel cells (PEMFC) technology is already in commercialization phase for automotive applications. However, the biggest challenges for its successful mass commercialization are cost and durability. Current PEMFC technology can meet the lifetime targets but the cost to achieve it can be very high due to material’s cost and system level mitigation complexities. Understanding of the membrane electrode assemblies (MEA) degradations using relevant durability accelerated tests at early stages of development is essential. PEMFCs for automotive applications goes through thousands of cycles during normal operation of the vehicle over the expected life span of 10 years. These cycles include a combination of load or voltage cycles, start and stop cycles, humidity cycles and temperature cycles. Study have shown that start-stop cycling accounts for 44% of operation mode while load cycling and idling for 28% each (1). Under these cycles, fuel cells suffer from severe degradations of its main components; cathode, anode, membrane and bipolar plates.
The PEMFC cathode can degrade during start-stop operation via carbon corrosion (2). Cathode degradation can be mitigated by using stable materials or by applying system mitigations. System mitigation by a voltage limiting control (VLC) can be one of the effective measures (3). The VLC can, however, lead to voltage spikes (high positive potentials) at the anode during fuel cell start-up and shut-down. Moreover, during fuel (H2) starvation conditions, the potential at the anode can give rise to high positive potentials leading to anode catalyst layer degradation. During idling operation mode, PEMFC is at or near open circuit conditions which is known to accelerate proton exchange membrane (PEM) decomposition especially under low humidification (4). Peroxy-radicals originating from hydrogen peroxide produced at the anode catalyst surface cause the PEM degradation (5). Pt band formation in the membrane is also known to promote peroxide formation leading to membrane decomposition (6-7).
Several accelerated protocols are currently being used to evaluate the durability of PEMFC. At Nissan, our durability protocols are focused on understanding the material degradation under relevant automotive cycles and correlating single cell durability to the stack level. Start-stop accelerated protocol to evaluate the cathode support durability consist of potential cycling from 1.0 V to 1.5 V using triangular waveform for 1000 cycles with diagnostics conducted intermittently after certain number of cycles. Cathode catalyst durability is evaluated using load cycling accelerated protocol wherein the potential is cycled between 0.6 V to 0.95 V to simulate peak load and OCV/idle using a square wave profile with 3 second hold at each potential. The upper potential is known to have significant impact on catalyst degradation (8). Load cycling is performed for 10,000 cycles with diagnostics conducted intermittently. Anode degradation under cell reversal condition is evaluated using a protocol designed to simulate high voltage spikes at the anode. Cell reversal cycling is performed by applying a load of 0.2 A/cm2 for 1 sec while flowing N2 at the anode and air at the cathode while measuring the cell voltage under the applied load for a total of 200 cycles. Membrane durability is evaluated using humidity cycling (mechanical durability) and potential hold at open circuit (chemical durability). Membrane’s chemical durability is evaluated at 90 °C and 30% RH under hydrogen and oxygen by operating MEA at open circuit. The target of OCV hold test is 500 hrs while maintaining potential above 0.8 V. Mechanical durability of membrane is evaluated by cycling RH to simulate dry condition (0%) and wet condition (100%) for target of 20,000 cycles. All these accelerated tests are performed at ambient pressure and summarized in the Table 1 below.
The author would like to gratefully acknowledge Nissan Technical Center North America Fuel Cell Research team members (Dr. Amod Kumar, Dr. Ramesh Yadav and Dr. Cenk Gumeci) and Nissan Motor Co. Ltd Japan Fuel Cell research team members (Dr. Atsushi Ohma, Dr. Yoshihisa Furuya) for technical discussions and data.
R. Shimoi et al., JSAE Spring meeting , April 2009
R. Borup et. al., Chemical Reviews, 107 (10), 3904 (2007)
M. L. Perry, T. W. Patterson and C. Reiser, ECS Trans., 3 (1), 783 (2006)
S. Sugawara et al., J. of Power Sources, 187 (2009)
A.B LaConti et al., Handbook of Fuel Cells, vol 3
A. Ohma et al., ECS Trans., 11 (1), 1181 (2007)
A. Ohma et al., ECS Trans., 3 (1), 519 (2006)
A. Ohma et al., ECS Trans, 41 (1), 775 (2011)