Multicomponent Mixed Ionic and Electronic Conducting (MIEC) Air Electrodes and Their Heterointerface for Effective Application in Reversible Solid Oxide Cell (R-SOC): Efficacy of Stoichiometric and Off-Stoichiometric Compositions

Abstract

Reversible solid oxide cell (R-SOC) has triggered research interest from the past few years for its reversible applicability for power-to-fuel (P2F) in electrolyser cell (SOEC) to generate hydrogen by splitting of high temperature steam and fuel-to-power (F2P) in fuel cell (SOFC) mode of operation to produce power by oxidation of fuel with >80% conversion efficiency [1]. Primarily, R-SOC consists of a dense electrolyte conventionally yttria stabilized zirconia (YSZ), bridged between two porous electrodes, e.g., strontium doped lanthanum manganite (LSM) as air electrode and Nickel (Ni)-YSZ cermet as fuel electrode. Significant research has been devoted to carry out the long-term stability (≥ 2000 h) degradation in endurance test primarily due to major challenges like highly humid environment in the fuel electrode, microstructural flaws and polarization losses under high operational temperature. In this context, mixed ionic and electronically conducting (MIEC) oxide-based La-Sr-Co-Fe-O (LSCF) and Ba-Sr-Co-Fe-O (BSCF) air electrodes has drawn significant attention for the effective oxygen reduction (ORR) and oxygen evolution (OER) reaction in the context of SOFC and SOEC operational mode [2,3].An attempt has been made in this present research work to establish the effect of off-stoichiometry in A-site lattice over the stoichiometric pristine compositions of La/Ba-Sr-Co-Fe-O (LSCF/BSCF)-based multicomponent MIEC-oxides and their associated heterostructure with optimised off-stoichiometric compositions that governs the electrochemical redox phenomena in conjunction with the functionally engineered Gd-doped ceria-based interlayer and buffer layer. Vacancy driven oxygen reduction (ORR) and oxide ion oxidation (OER) kinetics as a function of aliovalent charge compensation mechanism associated with the defect chemistry has also been investigated for these A-site non-stoichiometric compositions in the range of 1-0.92 for La/Ba(1-x)SrxCo1-yFeyO3-δ [x=0.4 and y=0.2]. A comparative study between the performance of the off-stoichiometric heterostructure synthesised using the optimised pristine compositions with that of the stoichiometric heterointerface has also been evaluated for their efficiency as catalyst for OER/ORR in reversible SOC mode of operation. The increasing trend of oxygen non-stoichiometry (δ) upon the transition from A-site stoichiometry to non-stoichiometric compositions reflected the formation of higher aliovalent cation of ‘Co’ to maintain the charge neutrality and thereby accelerates the associated oxygen redox kinetics. An optimum δ-value of 0.33 and 0.37 are found for LSCF and BSCF-compositions respectively having A-site non-stoichiometry of 0.94. Current density of 0.45 A.cm-2 at an applied voltage of 1.5 V @800℃ is obtained for stoichiometric composition of LSCF wherein 0.5 A.cm-2 is found for the off-stoichiometric batch corresponding to the hydrogen flux of 0.21Nl.h-1.cm-2. Such augmentation in performance may be related to the formation of higher lattice defect which eases the path for oxide ion oxidation. Formation of the interpenetrating heterointerface network at the air electrodes and electrode/electrolyte interfaces in the morphologically engineered cells having gradation in porosity has further been confirmed from Transmission Electron Microscopy (TEM) studies involving the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and the STEM-EDS elemental spectrum mapping images of the cross-section of the sintered cells and clinically corelated with SOC performances. Orientation of the crystal lattice planes in the two types of grains across the heterojunction has also been determined from the High-Resolution Transmission Electron Microscopy (HRTEM) images. Further study to envisage the presumed hypothesis, based on the rate determining steps involving the defect lattice formation and probable mechanism for selective ORR/OER application, will also be described through hole and/or oxygen vacancy formalism using XPS and density functional theory (DFT) for such hetero-interpenetrating air electrodes.