Nanocrystalline surface layer of WO3 for enhanced proton transport during fuel cell operation

Funding Information: Funding: School of Electronic Engineering, Nanjing Xiaozhuang University, 211171 Nanjing, China for providing experimental facilities. Further, this work was supported by National Natural Science Foundation of China (NSFC) under the grant #51772080 and 11604088 and Southeast University (SEU PROJET # 3203002003A1). Dr. Asghar thanks the Hubei Talent 100 program and Academy of Finland (grant no. 13329016 and 13322738) for their support. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.High ionic conductivity in low-cost semiconductor oxides is essential to develop electrochemical energy devices for practical applications. These materials exhibit fast protonic or oxygen-ion transport in oxide materials by structural doping, but their application to solid oxide fuel cells (SOFCs) has remained a significant challenge. In this work, we have successfully synthesized nanostructured monoclinic WO3 through three steps: co-precipitation, hydrothermal, and dry freezing methods. The resulting WO3 exhibited good ionic conductivity of 6.12 × 10−2 S cm−1 and reached an excellent power density of 418 mW cm−2 at 550◦C using as an electrolyte in SOFC. To achieve such a high ionic conductivity and fuel cell performance without any doping contents was surprising, as there should not be any possibility of oxygen vacancies through the bulk structure for the ionic transport. Therefore, laterally we found that the surface layer of WO3 is reduced to oxygen-deficient when exposed to a reducing atmosphere and form WO3−δ/WO3 heterostructure, which reveals a unique ionic transport mechanism. Different microscopic and spectroscopic methods such as HR-TEM, SEM, EIS, Raman, UV-visible, XPS, and ESR spectroscopy were applied to investigate the structural, morphological, and electrochemical properties of WO3 electrolyte. The structural stability of the WO3 is explained by less dispersion between the valence and conduction bands of WO3−δ/WO3, which in turn could prevent current leakage in the fuel cell that is essential to reach high performance. This work provides some new insights for designing high-ion conducting electrolyte materials for energy storage and conversion devices.Peer reviewe