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

Abstract

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. Here, we critically analyse the O2−/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. 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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Fig. 1: Comparison of the first-charge voltage curves of pure Li2MnO3 and Li2MnO3/LiMO2 composites.
Fig. 2: Theoretical phase diagrams and voltage curves for the Li2O–MnO2–O2 system.
Fig. 3: Hypothesized Li1/2MnO3 structure representing the Li2MnO3 component of the cathode material at the end of the activation plateau.
Fig. 4: Alternative charge mechanisms in Li-excess manganese oxides.

Data availability

The analysis presented here can be reproduced with the data provided in the paper, supporting information and cited references. Additional calculation data generated during this study are available upon reasonable request.

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Acknowledgements

We thank L. Piper and Z. Lebens-Higgins for the insightful discussion. This work was supported as part of the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award no. DE- SC0012583. The contributions of R.S. were supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0019381. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility operated under contract no. DE-AC02-05CH11231. Use of the Center for Scientific Computing at UC Santa Barbara supported by the National Science Foundation (NSF) Materials Research Science and Engineering Centers program through NSF DMR 1720256 and NSF CNS 1725797 is also acknowledged.

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All of the authors participated in the analysis of data and preparation of the manuscript. First-principles calculations were performed by M.D.R. and J.V.

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Correspondence to Maxwell D. Radin or Anton Van der Ven.

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Supplementary Information

Supplementary Figs. 1–2, Supplementary Table 1, Supplementary Discussion and Supplementary refs.

Supplementary Data 1

Hypothesized crystal structure for Li1/2MnO3, in VASP POSCAR format.

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Radin, M.D., Vinckeviciute, J., Seshadri, R. et al. Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials. Nat Energy 4, 639–646 (2019). https://doi.org/10.1038/s41560-019-0439-6

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