Reactant Transport Engineering Approach at Cathode to High Power Direct Methanol Hydrogen Peroxide Fuel Cell
Authors: Sharma Kritika , Sankarasubramanian Shrihari , Wang Zhongyang , Ramani Vijay K 
Published: September 2023

The development of high-power fuel cells could advance the electrification of the transportation sector, including marine and air transport. Liquid-fueled fuel cells are particularly attractive for such applications as they obviate the issue of fuel transportation and storage. Herein, we report a direct methanol hydrogen peroxide fuel cell (DMHPFC) for high-power propulsion applications that delivers 0.8 W cm2 peak power density by using a pH gradient-enabled microscale bipolar interface (PMBI) to effectively meet the incongruent pH requirements for methanol oxidation/peroxide reduction reactions.
DMHPFCs are an important alternative to hydrogen-fed polymer electrode membrane fuel cell (PEMFCs) and anion exchange membrane fuel cells (AEMFCs) due to methanol’s high energy density compared to that of hydrogen and superior kinetics of hydrogen peroxide reduction reaction as compared to Oxygen. A unit volume of Hydrogen gas stored at a pressure of approximately 69 MPa corresponds to volume-specific energy density of roughly 2.1 kWh/l while 39% volume of aqueous methanol and 41% volume of aqueous hydrogen peroxide corresponds to volume-specific energy density of 9.2 kWh/l. So, DMHPFC’s energy density is approximately four times higher than hydrogen fuel cell’s energy density and is comparable to gasoline which contains roughly 9.2 kWh/l of available bond energy. The theoretical potential for Methanol oxidation reaction (MOR) in basic medium is lower than that in an acidic medium (-0.78 V vs. -0.02 V) and the theoretical potential for the Hydrogen peroxide reduction reaction (HPRR) is higher than that for oxygen reduction (1.77 V vs. 1.23 V in acidic medium). This results in the highest theoretically possible cell voltage for cells with alkaline anodes and acidic cathodes. We achieved sustained operation of the DMHPFC with an alkaline anode and an acidic cathode by incorporating our pH-gradient-enabled microscale bipolar interface (PMBI).
However, the system exhibits a relatively low Faradaic efficiency of 50% due to the parasitic evolution of O2 by the decomposition of H2O2. The O2 evolution results in a mixed potential at the cathode due to the occurrence of both the HPRR (E0 = 1.77 V versus standard hydrogen electrode [SHE]) and the oxygen reduction reaction (ORR); (E0 = 1.23 V versus SHE), lowering the overall cell potential. The O2 surface coverage reduces the available sites for the HPRR, effectively deactivating the catalyst. Electrocatalysts exhibiting a combination of high HPRR activity and selectivity (by inhibiting H2O2 decomposition, and hence inhibiting ORR) would result in higher faradic efficiency and have been the subject of sustained interest. Here, we examine an alternate reactant-transport engineering approach to improve the overall cell potential and cell performance of the DMHPFC. Our reactant-transport engineering approach has examined the impact of reactant flowrate, flow velocity, residence time, and flow regime (via the Reynolds number ([Re]) on DMHPFC performance. Balancing the competing demands of high residence time to improve Hydrogen peroxide reduction reaction (HPRR) rates with high flowrates to detach adsorbed O2, we identify a critical Re and Damkholer number (Da) to efficiently exclude O2 gas bubbles while maintaining large current densities during the operation of a DMHPFC. Reactant-transport engineering of the cathode flow field architecture and fuel flowrates mitigates parasitic hydrogen peroxide decomposition and oxygen reduction reactions and lessens cathode passivation by oxygen bubbles. DMHPCs fulfilling these criteria provide a power density of >500 mW cm-2 at 1.0 V compared to state-of-the-art polymer electrolyte membrane fuel cells (PEMFCs) that typically operate at 0.75 V. The high peak power density of 800 mW cm-2 at 1.1 V may offer a pathway to reduce fuel cell stack size for propulsion applications. Our work paves the way for such other liquid fuel cells with hydrogen peroxide as the oxidant and enabled with PMBI resulting in significantly improvement in the performance.

Figure 1