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Title: Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. New York Univ., New York, NY (United States)
  3. General Motors Global R&D Center, Warren, MI (United States)
  4. Optimal CAE Inc., Plymouth, MI (United States)
+ Show Author Affiliations

The LiNi0.5Mn1.5O4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs Li/Li+). Although it is widely believed that the full range of electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi0.5Mn1.5O4 electrode is half charged. This provides a direct verification of single-electron-transfer reactions in LiNi0.5Mn1.5O4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft X-ray absorption spectroscopy also reveals the electrochemically inactive Ni2+ and Mn2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi0.5Mn1.5O4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Ni-based battery electrodes.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1393001
Journal Information:
Journal of Physical Chemistry. C, Vol. 119, Issue 49; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 103 works
Citation information provided by
Web of Science

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Cited By (16)

Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides journal February 2019
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy journal September 2016
Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries journal May 2019
Reversible Anionic Redox Activities in Conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes journal March 2020
Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment journal December 2019
Nano‐Sized AlPO 4 Coating Layer on Graphite Powder to Improve the Electrochemical Properties of High‐Voltage Graphite/LiNi 0.5 Mn 1.5 O 4 Li‐Ion Cells journal June 2019
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering journal January 2019
Direct Visualization of the Reversible O 2− /O − Redox Process in Li-Rich Cathode Materials journal February 2018
Construction of uniform transition-metal phosphate nanoshells and their potential for improving Li-ion battery performance journal January 2018
Synchrotron-Based X-ray Absorption Fine Structures, X-ray Diffraction, and X-ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries journal April 2018
Elucidating anionic oxygen activity in lithium-rich layered oxides journal March 2018
Soft x-ray spectroscopy of high pressure liquid journal January 2018
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides journal December 2017
Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles journal May 2016
Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting journal June 2018
Reversible Anionic Redox Activities in Conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes journal March 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
high voltage spinel
LiNi0.5Mn1.5O4
Ni(III)
soft x-ray spectroscopy