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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–xNi0.21Co0.08Mn0.54O2, 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.
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1 Department of Chemistry, Stanford University, Stanford, CA, USA; The Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
2 Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA; Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA
3 The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
4 The Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA; School of Physics, National Key Laboratory of Crystal Materials, Shandong University, Jinan, China
5 Energy Lab, Samsung Advanced Institute of Technology, 130, Samsung-ro, Yeongtong-gu Suwon-si, Gyeonggi-do, South Korea
6 Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA
7 Department of Computer Science, Stanford University, Stanford, CA, USA
8 Energy1lab, Samsung SDI, 130, Samsung-ro, Yeongtong-gu Suwon-si, Gyeonggi-do, South Korea
9 Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA
10 The Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
11 Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA; Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA
12 Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA; Stanford Institute for Materials & Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA