Transparent Conducting Oxides As Cathodes in Li-O2 batteries: A First Principles Computational Investigation

Abstract

Li-O2batteries have traditionally used carbon based electrodes (graphite, buckypaper) as the cathode of choice due to its good electrical conductivity, stability against non-aqueous electrolytes like dimethoxyethane (DME) and ease of handling. But, the carbon cathode also leads to formation of carbonate by-products that increase overpotentials during charging leading to degradation of the cathode and reduction of cyclability. Recent investigations have focused on using metal-oxides like SnO2, TiO2 as viable cathodes-alternatives in Li-O2 systems. In this paper, we investigate transparent conducting oxides (TCOs) as cathodes with focus on the interface between the TCO surfaces and the discharge product, Li2O2, in the Li-O2battery using first principles computations. TCOs have found use as electrodes in photovoltaic cells and other semi-conductor applications due to their tunable conductivity via defects/doping, ease of synthesis of preferred surfaces and stability to environmental factors. These properties, along with their stability against ethers, make them a promising class of cathodes in Li-O2 battery. Using DFT computations and thermodynamic arguments, we predict the chemical and electrochemical stability of some of the well-known TCOs in a Li-O2 battery. Further, surface adsorption computations show that not all oxides promote formation of Li2O2 and different surfaces of same cathode material can behave differently. We also explore the role dopants can play in achieving a stable electrically conducting cathode that promotes discharge of Li2O2. We extend the analysis to suggest possible oxide chemistries that should be investigated as cathodes in Li-O2batteries.