Density functional theory insights into the structural stability and Li diffusion properties of monoclinic and orthorhombic Li2FeSiO4 cathodes

Abstract Lithium iron orthosilicate (Li 2 FeSiO 4 ) is an important alternative cathode for next generation Li-ion batteries due to its high theoretical capacity (330 mA h/g). However, its development has faced great challenges arising from significant structural complexity, including the disordered arrangement/orientation of Fe/Si tetrahedra, polytypes and its poorly understood Li storage and transport properties. In this context, ab-initio calculations are employed to investigate the phase stability and Li diffusion profiles of both monoclinic ( P 2 1 ) and orthorhombic ( Pmn 2 1 ) Li 2 FeSiO 4 orthosilicates. The calculations demonstrate that formation of Li Fe antisites can induce a metastability competition between both phases, with neither dominating across nearly the entire discharging profile from Li 2 FeSiO 4 through to LiFeSiO 4 . Furthermore, structural instability is shown to be a serious concern at discharge concentrations below LiFeSiO 4 (1 Li extraction) due to the shared occupation of Li donated electrons with oxygen 2p orbitals – rather than the hypothesized transition to a tetravalent Fe 4+ state. This finding is further supported by diffusion calculations that have determined a high activation energy barrier towards fast charging and rapid phase transitions. In summary, these theoretical results provide critical and timely insight into the structural dynamics of lithium iron orthosilicate, in pursuit of high energy density cathodes.