Lithium Niobate for Fast Cycling in Li-ion Batteries: Review and New Experimental Results

Abstract

Li-Nb-O-based insertion layers between electrodes and electrolytes of Li-ion batteries (LIBs) are known to protect the electrodes and electrolytes from unwanted reactions and to enhance Li transport across interfaces. An improved operation of LIBs, including all-solid-state LIBs, is reached with Li-Nb-O-based insertion layers. This work reviews the suitability of polymorphic Li-Nb-O-based compounds (e.g., crystalline, amorphous, and mesoporous bulk materials and films produced by various methodologies) for LIB operation. The literature survey on the benefits of niobium-oxide-based materials for LIBs, and additional experimental results obtained from neutron scattering and electrochemical experiments on amorphous LiNbO3 films are the focus of the present work. Neutron reflectometry reveals a higher porosity in ion-beam sputtered amorphous LiNbO3 films (22% free volume) than in other metal oxide films such as amorphous LiAlO2 (8% free volume). The higher porosity explains the higher Li diffusivity reported in the literature for amorphous LiNbO3 films compared to other similar Li-metal oxides. The higher porosity is interpreted to be the reason for the better suitability of LiNbO3 compared to other metal oxides for improved LIB operation. New results are presented on gravimetric and volumetric capacity, potential-resolved Li+ uptake and release, pseudo-capacitive fractions, and Li diffusivities determined electrochemically during long-term cycling of LiNbO3 film electrodes with thicknesses between 14 and 150 nm. The films allow long-term cycling even for fast cycling with rates of 240C possessing reversible capacities as high as 600 mAhg−1. Electrochemical impedance spectroscopy (EIS) shows that the film atomic network is stable during cycling. The Li diffusivity estimated from the rate capability experiments is considerably lower than that obtained by EIS but coincides with that from secondary ion mass spectrometry. The mostly pseudo-capacitive behavior of the LiNbO3 films explains their ability of fast cycling. The results anticipate that amorphous LiNbO3 layers also contribute to the capacity of positive (LiNixMnyCozO2, NMC) and negative LIB electrode materials such as carbon and silicon. As an outlook, in addition to surface-engineering, the bulk-engineering of LIB electrodes may be possible with amorphous and porous LiNbO3 for fast cycling with high reversible capacity.