Advanced Energy Materials
Advanced Energy Materials
5 years ago

Intrinsic Nanodomains in Triplite LiFeSO4F and Its Implication in Lithium-Ion Diffusion

Intrinsic Nanodomains in Triplite LiFeSO4F and Its Implication in Lithium-Ion Diffusion
Kyu-Young Park, Haegyeom Kim, Dong-Hwa Seo, Kisuk Kang, Sung-Kyun Jung, Min-Sik Park
Triplite-type LiFeSO4F has attracted considerable attention as a promising cathode for next-generation lithium-ion batteries because of its high redox potential based on earth-abundant Fe2+/3+. However, successful extraction/reinsertion of all the lithium ions in triplite host is challenging even at a low current rate, resulting in a low specific capacity. These experimental findings contrast with previous theoretical works that predicted that the triplite structure would be a fast ionic conductor with low activation barriers for lithium-ion hopping. Origin of this discrepancy is elusive to date. Herein, combined first-principles calculations and high-angle annular dark-field scanning transmission electron microscopy analyses reveal that typical triplite structure is composed of nanodomains consisting of corner-shared FeO4F2 octahedra, whereas their domain boundaries are regions of mixed corner/edge-shared FeO4F2 octahedra. More importantly, these locally disordered domain boundaries significantly reduce the overall lithium diffusivity of the materials. Inspired by these findings, this study redesigns triplite structure with sufficiently small sizes to avoid local bottlenecks arising from the domain boundaries, successfully achieving nearly full lithium extraction/reinsertion with high power and energy density. This work represents the first direct observation of the presence of domain boundaries within a crystalline structure playing a critical role in governing the lithium diffusivity in a battery electrode. The origin of slow kinetics of triplite electrode material is demonstrated for the first time. This study unveils that triplite LiFeSO4F particle is generally comprised of “nanodomains” of characteristic transition-metal arrangements, and the domain boundaries significantly reduce the overall lithium diffusivity. This work represents presence of domain boundaries within a crystalline structure playing a critical role in governing the lithium diffusivity.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/aenm.201701408

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