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Protonic ceramic electrochemical cells (PCECs) have received extensive research attention as full solid‐state, electrochemical devices that can interconvert electrical and chemical energies via rapid proton conduction at reduced temperatures. Nonetheless, the practical application of PCECs still faces numerous challenges. In addition to the development of electrode materials, the protonic ceramic electrolytes (PCEs), which are crucial for the performance and stability of PCECs, encounter issues such as poor sinterability, low ionic conductivity, and inadequate thermochemical matching. To address these obstacles, the design and optimization of protonic ceramic electrolytes have recently become essential research focuses in the field of PCECs. To achieve effective customization of the elemental composition, crystal structure, defect structure, ionic conductivity, and chemical stability, many candidates for electrolyte materials with various compositions have been proposed. This review also covers state‐of‐the‐art developments in PCE fabrication technologies, including powder synthesis, thin‐film deposition, more controllable sintering processes and interface treatments for structural integrity and ionic conductivity. This review comprehensively summarizes the most recent design approaches and optimization strategies for perovskite‐based protonic ceramic electrolyte materials and is crucial for advancing the commercialization of PCECs.
Protonic ceramic electrochemical cells (PCECs) have received extensive research attention as full solid‐state, electrochemical devices that can interconvert electrical and chemical energies via rapid proton conduction at reduced temperatures. Nonetheless, the practical application of PCECs still faces numerous challenges. In addition to the development of electrode materials, the protonic ceramic electrolytes (PCEs), which are crucial for the performance and stability of PCECs, encounter issues such as poor sinterability, low ionic conductivity, and inadequate thermochemical matching. To address these obstacles, the design and optimization of protonic ceramic electrolytes have recently become essential research focuses in the field of PCECs. To achieve effective customization of the elemental composition, crystal structure, defect structure, ionic conductivity, and chemical stability, many candidates for electrolyte materials with various compositions have been proposed. This review also covers state‐of‐the‐art developments in PCE fabrication technologies, including powder synthesis, thin‐film deposition, more controllable sintering processes and interface treatments for structural integrity and ionic conductivity. This review comprehensively summarizes the most recent design approaches and optimization strategies for perovskite‐based protonic ceramic electrolyte materials and is crucial for advancing the commercialization of PCECs.
Ceramic proton conductors have the potential to lower the operating temperature of solid oxide cells (SOCs) to the intermediate temperature range of 400–600 °C. This is attributed to their superior ionic conductivity compared to oxide ion conductors under these conditions. However, prominent proton-conducting materials, such as yttrium-doped barium cerates and zirconates with specified compositions like BaCe1−xYxO3−δ (BCY), BaZr1−xYxO3−δ (BZY), and Ba(Ce,Zr)1−yYyO3−δ (BCZY), face significant challenges in achieving dense electrolyte membranes. It is suggested that the incorporation of transition and alkali metal oxides as sintering additives can induce liquid phase sintering (LPS), offering an efficient method to facilitate the densification of these proton-conducting ceramics. However, current research underscores that incorporating these sintering additives may lead to adverse secondary effects on the ionic transport properties of these materials since the concentration and mobility of protonic defects in a perovskite are highly sensitive to symmetry change. Such a drop in ionic conductivity, specifically proton transference, can adversely affect the overall performance of cells. The extent of variation in the proton conductivity of the perovskite BCZY depends on the type and concentration of the sintering aid, the nature of the sintering aid precursors used, the incorporation technique, and the sintering profile. This review provides a synopsis of various potential sintering techniques, explores the influence of diverse sintering additives, and evaluates their effects on the densification, ionic transport, and electrochemical properties of BCZY. We also report the performance of most of these combinations in an actual test environment (fuel cell or electrolysis mode) and comparison with BCZY.
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