Because of the generally lower activation energy associated with proton conduction in oxides compared to oxygen ion conduction, protonic ceramic fuel cells (PCFCs) should be able to operate at lower temperatures than solid oxide fuel cells (250° to 550°C versus ≥600°C) on hydrogen and hydrocarbon fuels if fabrication challenges and suitable cathodes can be developed. We fabricated the complete sandwich structure of PCFCs directly from raw precursor oxides with only one moderate-temperature processing step through the use of sintering agents such as copper oxide. We also developed a proton-, oxygen-ion-, and electron-hole-conducting PCFC-compatible cathode material, BaCo(0.4)Fe(0.4)Zr(0.1)Y(0.1)O(3-δ) (BCFZY0.1), that greatly improved oxygen reduction reaction kinetics at intermediate to low temperatures. We demonstrated high performance from five different types of PCFC button cells without degradation after 1400 hours. Power densities as high as 455 milliwatts per square centimeter at 500°C on H2 and 142 milliwatts per square centimeter on CH4 were achieved, and operation was possible even at 350°C.

Protonic ceramic fuel cells, like their higher-temperature solid-oxide fuel cell counterparts, can directly use both hydrogen and hydrocarbon fuels to produce electricity at potentially more than 50 per cent efficiency. Most previous direct-hydrocarbon fuel cell research has focused on solid-oxide fuel cells based on oxygen-ion-conducting electrolytes, but carbon deposition (coking) and sulfur poisoning typically occur when such fuel cells are directly operated on hydrocarbon- and/or sulfur-containing fuels, resulting in severe performance degradation over time. Despite studies suggesting good performance and anti-coking resistance in hydrocarbon-fuelled protonic ceramic fuel cells, there have been no systematic studies of long-term durability. Here we present results from long-term testing of protonic ceramic fuel cells using a total of 11 different fuels (hydrogen, methane, domestic natural gas (with and without hydrogen sulfide), propane, n-butane, i-butane, iso-octane, methanol, ethanol and ammonia) at temperatures between 500 and 600 degrees Celsius. Several cells have been tested for over 6,000 hours, and we demonstrate excellent performance and exceptional durability (less than 1.5 per cent degradation per 1,000 hours in most cases) across all fuels without any modifications in the cell composition or architecture. Large fluctuations in temperature are tolerated, and coking is not observed even after thousands of hours of continuous operation. Finally, sulfur, a notorious poison for both low-temperature and high-temperature fuel cells, does not seem to affect the performance of protonic ceramic fuel cells when supplied at levels consistent with commercial fuels. The fuel flexibility and long-term durability demonstrated by the protonic ceramic fuel cell devices highlight the promise of this technology and its potential for commercial application.

Proton-conducting oxides are a class of solid-state ion-conducting ceramic materials that demonstrate significant hydrogen ion (proton) conductivity at intermediate temperatures (e.g., 300–700 °C). They are garnering significant attention due to several unique characteristics that distinguish them from both higher temperature oxygen ion conducting oxides and lower temperature proton-conducting polymers. By enabling proton-mediated electrochemistry under both dry and wet environments at moderate temperatures, protonic ceramics provide unique opportunities to enhance or synergize a diverse range of complementary electrochemical and thermochemical processes. Because of this potential, significant efforts have been devoted to advancing numerous energy-related applications using these materials. This review aims to comprehensively summarize these applications and analyze the most up-to-date and future developments of proton-conducting oxides. We aim to bring together this diverse subject matter by integrating the fundamentals of proton-conducting oxides with application-oriented insights. We begin with a historical roadmap, followed by a basic overview of the materials, theories and fundamentals, and fabrication and processing technologies underlying the field. The central section of our review summarizes major applications and developments of proton-conducting ceramics, ranging from maturing applications approaching commercialization to embryonic technologies just now emerging from the lab. These include protonic ceramic fuel cells, protonic ceramic electrolysis cells, reversible protonic ceramic electrochemical cells, protonic ceramic membrane reactors, and protonic ceramic electrochemical reactors. For each application, we analyze both the prospects and challenges and offer recommendations for future research directions so that tomorrow's researchers can continue to advance the development and commercialization of these fascinating materials.

BaCo0.4Fe0.4Zr0.1Y0.1O3−δis applied for the first time as a cathode for low-temperature solid oxide fuel cells (LT-SOFCs) with high power densities below 500 °C and 2500 hours stable performance.