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Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles With Operando X-ray Absorption Spectroscopy

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles With Operando X-ray Absorption Spectroscopy

Lea Nowack, Daniel Grolimund, Vallerie Samson, Federica Marone, Vanessa Wood

Sci Rep. 2016 Feb 24;6:21479.

PMID: 26908198

Abstract:

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP193214243	Lithium nickel cobalt aluminium oxide		193214-24-3	Price

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