Lowering the operating temperature (ideally below 400 °C) for solid oxide fuel cell (SOFC) technology deployment has been an important transition that introduces the benefit of reduced operational costs and system durability. However, the key technical issue limiting the transition is the sluggish cathodic performance, namely the oxygen reduction reaction (ORR) rate of the conventional sponge‐like cathode dramatically drops as the temperature reduces. In this paper, 3D engineering of a cathode is conducted on a protonic ceramic fuel cell to obtain an enhanced ORR between 400 and 600 °C. Compared with a cell using a conventional sponge‐like cathode, 3D engineering improves the cathode ORR by 41% at 400 °C with a peak power density of 0.410 W cm−2. A phase field simulation is applied to assist the engineering by understanding the competition between the cathode mass and charge transfer with different cathode porosities. The results show that structural engineering of existing well‐developed cathodes is a simple and effective method to promote cathode ORR for low temperature SOFC by regulating the mass and charge transfer.

An A-site deficient layered perovskite PBCC95 is developed as a new oxygen electrode incorporated into a protonic ceramic electrochemical cell. The cell presents superior electrochemical performances and it can reversibly work between the electrolysis and fuel cell mode.

In article number 2102907, Wei Wu, Meng Zhou, Dong Ding, and co-workers develop a 3D engineered cathode to enhance oxygen reduction reaction kinetics on a proton-conducting fuel cell at <600 °C. The results demonstrate remarkable cell performance at 400-600 °C by effectively regulating the mass and charge transfer through the electrode and across the interface of electrolyte and electrode.

Porous electrodes that conduct electrons, protons, and oxygen ions with dramatically expanded catalytic active sites can replace conventional electrodes with sluggish kinetics in protonic ceramic electrochemical cells. In this work, a strategy is utilized to promote triple conduction by facilitating proton conduction in praseodymium cobaltite perovskite through engineering non‐equivalent B‐site Ni/Co occupancy. Surface infrared spectroscopy is used to study the dehydration behavior, which proves the existence of protons in the perovskite lattice. The proton mobility and proton stability are investigated by hydrogen/deuterium (H/D) isotope exchange and temperature‐programmed desorption. It is observed that the increased nickel replacement on the B‐site has a positive impact on proton defect stability, catalytic activity, and electrochemical performance. This doping strategy is demonstrated to be a promising pathway to increase catalytic activity toward the oxygen reduction and water splitting reactions. The chosen PrNi0.7Co0.3O3−δ oxygen electrode demonstrates excellent full‐cell performance with high electrolysis current density of −1.48 A cm−2 at 1.3 V and a peak fuel‐cell power density of 0.95 W cm−2 at 600 °C and also enables lower‐temperature operations down to 350 °C, and superior long‐term durability.