The application of protonic ceramic electrolysis cells (PCECs) for ammonia (NH3) synthesis has been evaluated over the past 14 years. While nitrogen (N2) is the conventional fuel on the cathode side, various fuels such as methane (CH4), hydrogen (H2), and steam (H2O) have been investigated for the oxygen evolution reaction (OER) on the anode side. Because H2 is predominantly produced through CO2-emitting methane reforming, H2O has been the conventional carbon-free option thus far. Although the potential of utilizing H2O and N2 as fuels is considerable, studies exploring this specific combination remain limited. PCEC fabrication technologies are being developed extensively, thus necessitating a comprehensive review. Several strategies for electrode fabrication, deposition, and electrolyte design are discussed herein. The progress in electrode development for PCECs has also been delineated. Finally, the existing challenges and prospective outlook of PCEC for NH3 synthesis are analyzed and discussed. The most significant finding is the lack of past research involving PCEC with H2O and N2 as fuel configurations and the diversity of nitrogen reduction reaction catalysts. This review indicates that the maximum NH3 synthesis rate is 14 × 10−9 mol cm−2 s−1, and the maximum current density for the OER catalyst is 1.241 A cm−2. Moreover, the pellet electrolyte thickness must be maintained at approximately 0.8–1.5 mm, and the stability of thin-film electrolytes must be improved.
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