Hidden structural order controls Li-ion transport in cation-disordered oxides for rechargeable lithium batteries

Abstract

Crystal structures play a vital role in determining materials properties. In Li-ion cathodes, the crystal structure defines the dimensionality and connectivity of interstitial sites, thus determining Li-ion diffusion kinetics. While a perfect crystal has infinite structural coherence, a class of recently discovered high-capacity cathodes, Li-excess cation-disordered rocksalts, falls on the other end of the spectrum: Their cation sublattices are assumed to be randomly populated by Li and transition metal ions with zero configurational coherence based on conventional X-ray diffraction, such that the Li transport is purely determined by statistical effects. In contrast to this prevailing view, we reveal that cation short-range order, hidden in diffraction, is ubiquitous in these long-range disordered materials and controls the local and macroscopic environments for Li-ion transport. Our work not only discovers a crucial property that has previously been overlooked, but also provides new guidelines for designing and engineering disordered rocksalts cathode materials.

References in corpus (3)

• The Effect of Lattice Vibrations on Substitutional Alloy Thermodynamics
• Compressive sensing as a new paradigm for model building
• The electronic-structure origin of cation disorder in transition-metal oxides

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• Anion-polarisation-directed short-range-order in antiperovskite Li${}_2$FeSO
• Giant Modulation of Refractive Index from Picoscale Atomic Displacements
• Modeling intercalation chemistry with multi-redox reactions by sparse lattice models in disordered rocksalt cathodes
• Ab-initio study of short-range ordering in vanadium-based disordered rocksalt structures
• Exploration of oxyfluoride frameworks as Na-ion cathodes
• Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine learning interatomic potentials
• Tailored ordering enables high-capacity cathode materials
• Short-Range Order and Li${}_x$TM${}_{4-x}$ Probability Maps for Disordered Rocksalt Cathodes