Persistent and partially mobile oxygen vacancies in Li-rich layered oxides

Peter M. Csernica, Samanbir S. Kalirai, William E. Gent, Kipil Lim, Young-Sang Yu, Yunzhi Liu, Sung-Jin Ahn, Emma Kaeli, Xin Xu, Kevin H. Stone, Ann F. Marshall, Robert Sinclair, David A. Shapiro (), Michael F. Toney () and William C. Chueh ()
Additional contact information
Peter M. Csernica: Stanford University
Samanbir S. Kalirai: Stanford University
William E. Gent: Stanford University
Kipil Lim: Stanford University
Young-Sang Yu: Advanced Light Source, Lawrence Berkeley National Laboratory
Yunzhi Liu: Stanford University
Sung-Jin Ahn: Energy Lab, Samsung Advanced Institute of Technology
Emma Kaeli: Stanford University
Xin Xu: Stanford University
Kevin H. Stone: Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory
Ann F. Marshall: Stanford University
Robert Sinclair: Stanford University
David A. Shapiro: Advanced Light Source, Lawrence Berkeley National Laboratory
Michael F. Toney: Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory
William C. Chueh: Stanford University

Nature Energy, 2021, vol. 6, issue 6, 642-652

Abstract: Abstract Increasing the energy density of layered oxide battery electrodes is challenging as accessing high states of delithiation often triggers voltage degradation and oxygen release. Here we utilize transmission-based X-ray absorption spectromicroscopy and ptychography on mechanically cross-sectioned Li1.18–xNi0.21Mn0.53Co0.08O2–δ electrodes to quantitatively profile the oxygen deficiency over cycling at the nanoscale. The oxygen deficiency penetrates into the bulk of individual primary particles (~200 nm) and is well-described by oxygen vacancy diffusion. Using an array of characterization techniques, we demonstrate that, surprisingly, bulk oxygen vacancies that persist within the native layered phase are indeed responsible for the observed spectroscopic changes. We additionally show that the arrangement of primary particles within secondary particles (~5 μm) causes considerable heterogeneity in the extent of oxygen release between primary particles. Our work merges an ensemble of length-spanning characterization methods and informs promising approaches to mitigate the deleterious effects of oxygen release in lithium-ion battery electrodes.

Date: 2021
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DOI: 10.1038/s41560-021-00832-7

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