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

William E. Gent, Kipil Lim, Yufeng Liang, Qinghao Li, Taylor Barnes, Sung-Jin Ahn, Kevin H. Stone, Mitchell McIntire, Jihyun Hong, Jay Hyok Song, Yiyang Li, Apurva Mehta, Stefano Ermon, Tolek Tyliszczak, David Kilcoyne, David Vine, Jin-Hwan Park, Seok-Kwang Doo, Michael F. Toney (), Wanli Yang (), David Prendergast () and William C. Chueh ()
Additional contact information
William E. Gent: Stanford University
Kipil Lim: Stanford University
Yufeng Liang: Lawrence Berkeley National Laboratory
Qinghao Li: Lawrence Berkeley National Laboratory
Taylor Barnes: Lawrence Berkeley National Laboratory
Sung-Jin Ahn: Samsung Advanced Institute of Technology, 130, Samsung-ro
Kevin H. Stone: SLAC National Accelerator Laboratory
Mitchell McIntire: Stanford University
Jihyun Hong: Stanford University
Jay Hyok Song: Samsung SDI, 130, Samsung-ro
Yiyang Li: Stanford University
Apurva Mehta: SLAC National Accelerator Laboratory
Stefano Ermon: Stanford University
Tolek Tyliszczak: Lawrence Berkeley National Laboratory
David Kilcoyne: Lawrence Berkeley National Laboratory
David Vine: Lawrence Berkeley National Laboratory
Jin-Hwan Park: Samsung Advanced Institute of Technology, 130, Samsung-ro
Seok-Kwang Doo: Samsung Advanced Institute of Technology, 130, Samsung-ro
Michael F. Toney: SLAC National Accelerator Laboratory
Wanli Yang: Lawrence Berkeley National Laboratory
David Prendergast: Lawrence Berkeley National Laboratory
William C. Chueh: Stanford University

Nature Communications, 2017, vol. 8, issue 1, 1-12

Abstract: Abstract 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 Li1.17–x Ni0.21Co0.08Mn0.54O2, 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.

Date: 2017
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DOI: 10.1038/s41467-017-02041-x

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