The protonic ceramic electrochemical cell (PCEC) is an emerging and attractive technology that converts energy between power and hydrogen using solid oxide proton conductors at intermediate temperatures. To achieve efficient electrochemical hydrogen and power production with stable operation, highly robust and durable electrodes are urgently desired to facilitate water oxidation and oxygen reduction reactions, which are the critical steps for both electrolysis and fuel cell operation, especially at reduced temperatures. In this study, a triple conducting oxide of PrNi 0.5 Co 0.5 O 3-δ perovskite is developed as an oxygen electrode, presenting superior electrochemical performance at 400~600°C. More importantly, the selfsustainable and reversible operation is successfully demonstrated by converting the generated hydrogen in electrolysis mode to electricity without any hydrogen addition. The excellent electrocatalytic activity is attributed to the considerable proton conduction, as confirmed by hydrogen permeation experiment, remarkable hydration behavior and computations.

Reversible protonic ceramic electrochemical cells (R-PCECs) are a promising option for efficient and low-cost generation of electricity and hydrogen. Commercialization of R-PCECs, however, hinges on the development of highly active and robust air electrodes. Here, we report an air electrode consisting of PrBa 0.8 Ca 0.2 Co 2 O 5+δ and in situ exsolved BaCoO 3−δ nanoparticles (PBCC−BCO) that shows minimal polarization resistance (∼0.24 Ω cm 2 at 600 °C) and high stability when exposed to humidified air with 3−50% H 2 O. An R-PCEC utilizing PBCC-BCO demonstrates remarkable performances at 600 °C: achieving a peak power density of 1.06 W cm −2 in the fuel cell mode and a current density of 1.51 A cm −2 at 1.3 V in an electrolysis mode. More importantly, the R-PCECs demonstrate an exceptionally high durability over 1833 h of continuous operation in the electrolysis mode. This work offers an efficient approach to design of high-performance and durable electrodes for R-PCECs.

Protonic ceramic electrochemical cells hold the promise to be operated below 600 o C 1,2 . Although the high proton conductivity of the bulk electrolyte has been demonstrated, it cannot be fully utilized in electrochemical full cells due to unknown causes 3 . Here we showed that it all comes from poor contacts between the low-temperature processed oxygen electrode-electrolyte interface.We demonstrated that a simple acid treatment can effectively rejuvenate the high-temperature annealed electrolyte surface, resulting in reactive bonding between the oxygen electrode and the electrolyte and improved electrochemical performance and stability. This enables exceptional protonic ceramic fuel-cell performance down to 350 o C, with peak power densities of 1.6 W cm −2 at 600 o C, 650 mW cm −2 at 450 o C, and 300 mW cm −2 at 350 o C, as well as stable electrolysis operations with current densities above 3.9 A cm −2 at 1.4 V and 600 o C. Our work highlights the critical role of interfacial engineering in ceramic electrochemical devices and offers new understanding and practices towards sustainable energy infrastructure.

Hydrogen production via water electrolysis using solid oxide electrolysis cells (SOECs) has attracted considerable attention because of its favorable thermodynamics and kinetics. It is considered as the most efficient and low‐cost option for hydrogen production from renewable energies. By using proton‐conducting electrolyte (H‐SOECs), the operating temperature can be reduced from beyond 800 to 600 °C or even lower due to its higher conductivity and lower activation energy. Technical barriers associated with the conventional oxygen‐ion conducting SOECs (O‐SOECs), that is, hydrogen separation and electrode instability that is primarily due to the Ni oxidation at high steam concentration and delamination associated with oxygen evolution, can be remarkably mitigated. Here, a self‐architectured ultraporous (SAUP) 3D steam electrode is developed for efficient H‐SOECs below 600 °C. At 600 °C, the electrolysis current density reaches 2.02 A cm−2 at 1.6 V. Instead of fast degradation in most O‐SOECs, performance enhancement is observed during electrolysis at an applied voltage of 1.6 V at 500 °C for over 75 h, attributed to the “bridging” effect originating from reorganization of the steam electrode. The H‐SOEC with SAUP steam electrode demonstrates excellent performance, promising a new prospective for next‐generation steam electrolysis at reduced temperatures.

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