skip to main content


Title: Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

© 2017 The Author(s). Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17-x Ni 0.21 Co 0.08 Mn 0.54 O 2 , these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.
ORCiD logo ; ; ; ; ; ; ORCiD logo ; ; ; ; ; ; ; ; ORCiD logo ; ; ; ; ORCiD logo ; ORCiD logo more »; ORCiD logo ; « less
Publication Date:
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
25 ENERGY STORAGE; Batteries; Solid-state chemistry
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1416944