Nanocrystalline Surface Layer of WO3 for Enhanced Proton Transport during Fuel Cell Operation

Xiang Song,M A K Yousaf Shah,Peter D Lund,Muhammad Imran Asghar,Muhammad Sultan Irshad,Yuhong Guo,Naveed Mushtaq,Weiqing Guo

doi:10.3390/cryst11121595

Abstract

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.

Highlights

Fuel cells (FCs) provide a clean and efficient way to generate electricity from H2 and hydrocarbon fuels
The results demonstrate that the approach proposed is helpful for developing new materials with unique functionalities for advanced Protonic conducting fuel cells (PCFCs)/solid oxide fuel cells (SOFCs)
These results describe that when WO3 is exposed to the H2 atmosphere, its surface could be reduced to W5+ to form WO3−δ/ WO3, and protons can be transported through this layer as reported for CeO2

Summary

Introduction

Fuel cells (FCs) provide a clean and efficient way to generate electricity from H2 and hydrocarbon fuels. Structural doping has been remained a general methodology for developing high ionic conductivities [1,2] In this methodology, the host cations could often be replaced by a lower valence state, which produces an oxygen-deficient structure to conduct O2− (For example, Zr4+ or Ce4+ are replaced with Y3+ and Sm3+ ) [3,4]. The host cations could often be replaced by a lower valence state, which produces an oxygen-deficient structure to conduct O2− (For example, Zr4+ or Ce4+ are replaced with Y3+ and Sm3+ ) [3,4] This approach does not significantly enhance fuel cell performance at low operating temperatures due to limited ionic conductivity [4]

Methods

Results

Conclusion