Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials

Radin, Maxwell D.; Vinckeviciute, Julija; Seshadri, Ram; Van der Ven, Anton

doi:10.1038/s41560-019-0439-6

Title: Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials

Journal Article · 29 July 2019 · Nature Energy

DOI: https://doi.org/10.1038/s41560-019-0439-6 · OSTI ID:1597014

Radin, Maxwell D. ^[1];

^[1]; Seshadri, Ram ^[1]; Van der Ven, Anton ^[1]

Univ. of California, Santa Barbara, CA (United States)

The lithium-excess manganese oxides are a candidate cathode material for the next generation of Li-ion batteries because of their ability to reversibly intercalate more Li than traditional cathode materials. Although reversible oxidation of lattice oxygen has been proposed as the origin of this anomalous excess capacity, questions about the underlying electrochemical reaction mechanisms remain unresolved. In this work, we critically analyse the O^2-/O^- oxygen redox hypothesis and explore alternative explanations for the origin of the anomalous capacity, including the formation of peroxide ions or trapped oxygen molecules and the oxidation of Mn. First-principles calculations motivated by the Li–Mn–O phase diagram show that the electrochemical behaviour of the Li-excess manganese oxides is thermodynamically consistent with the oxidation of Mn from the +4 oxidation state to the +7 oxidation state and the concomitant migration of Mn from octahedral sites to tetrahedral sites. Finally, it is shown that the Mn oxidation hypothesis can explain the poorly understood electrochemical behaviour of Li-excess materials, including the activation step, the voltage hysteresis and voltage fade.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES). Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR); Binghamton Univ., NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012583; SC0019381; AC02-05CH11231; DMR-1720256; CNS-1725797

OSTI ID:: 1597014

Journal Information:: Nature Energy, Vol. 4, Issue 8; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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