Abstract
Naturally occurring lithium-rich α-spodumene (α-LiAlSi2O6) is a technologically important mineral that has attracted considerable attention in ceramics, polymer industries, and rechargeable lithium ion batteries (LIBs). The defect chemistry and dopant properties of this material are studied using a well-established atomistic simulation technique based on classical pair-potentials. The most favorable intrinsic defect process is the Al-Si anti-site defect cluster (1.08 eV/defect). The second most favorable defect process is the Li-Al anti-site defect cluster (1.17 eV/defect). The Li-Frenkel is higher in energy by 0.33 eV than the Al-Si anti-site defect cluster. This process would ensure the formation of Li vacancies required for the Li diffusion via the vacancy-assisted mechanism. The Li-ion diffusion in this material is slow, with an activation energy of 2.62 eV. The most promising isovalent dopants on the Li, Al, and Si sites are found to be Na, Ga, and Ge, respectively. The formation of both Li interstitials and oxygen vacancies can be facilitated by doping of Ga on the Si site. The incorporation of lithium is studied using density functional theory simulations and the electronic structures of resultant complexes are discussed.
Highlights
Occurring lithium-rich α-spodumene (α-LiAlSi2 O6 ) is a technologically important mineral that has attracted considerable attention in ceramics, polymer industries, and rechargeable lithium ion batteries (LIBs)
Mineralogists describe that the spodumene has some associations with quartz and albite [10] and as a three-phase system [11,12]. α, β, and γ are the three major phases of spodumene, where α-spodumene (LiAlSi2 O6 ) is the mined natural material [1]
Spodumene has been experimentally studied in previous cases for its phase transformation mechanisms [18] and to clarify the density of defects in natural α-spodumene [19]
Summary
Escalating demand for mineral candidates, especially in industries of lithium ion batteries (LIBs), has fueled the transformational shift in mobile-electronics. Lithium-rich minerals have drawn the attention of investigators to analyze their potential candidacy [1]. Lithium-rich minerals are significant in modern industries of LIBs, alloys, and pharmacy [2,3,4]. Previous computational investigations have shown the significance of atomistic scale computation to reveal the defect energetic features of the minerals for energy applications [14,15,16,17]. Spodumene has been experimentally studied in previous cases for its phase transformation mechanisms [18] and to clarify the density of defects in natural α-spodumene [19]. We have attempted to elucidate the energetics of the optimized theoretical model of α-spodumene and its intrinsic defect processes employing atomistic simulations based on classical pair-potentials.
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