Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li2MnO3·0.3LiFeO2 Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies

Kwok, Chun Yuen; Mallick, Subhadip; Pollock, Christopher J.; Gutierrez, Arturo; Dixit, Marm; Croy, Jason R.; Balasubramanian, Mahalingam

doi:10.1021/acs.chemmater.3c02111

Title: Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li₂MnO₃·0.3LiFeO₂ Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies

Journal Article · 07 November 2023 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.3c02111 · OSTI ID:2281138

Kwok, Chun Yuen ^[1]; Mallick, Subhadip ^[2];

^[3]; Gutierrez, Arturo ^[2];

^[1];

^[2];

^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Cornell University, Ithaca, NY (United States)

We report the use of iron 1s3p resonant X-ray emission processes to conduct spin-selective, high-energy resolution fluorescence detected X-ray absorption near-edge spectroscopy (HERFD-XANES) on an iron-containing, lithium- and manganese-rich, fully earth-abundant cathode material, Li_1.3Mn_0.5Fe_0.2O₂ (0.7Li₂MnO₃·0.3LiFeO₂). Coupling this technique with conventional Mn K-edge XANES and detailed extended X-ray absorption fine structure (EXAFS) analysis from both the Mn and Fe vantage points, we gain fundamental insights into the redox processes and migration tendencies of transition metals in this cathode material at the bulk level. We show that during the first charge, Fe³⁺ undergoes oxidation to form Fe⁴⁺ prior to the activation plateau. Toward the end of activation, a significant fraction of the iron is present as tetrahedral Fe³⁺. This observation reveals that iron migration from octahedral to tetrahedral sites and iron reduction are initiated during activation. Upon first discharge from the activated state, a continuous and overlapping reduction of both Fe and Mn is observed, with Fe largely restored back as an octahedrally coordinated Fe³⁺. The manganese local environment gradually changes to a distorted cooperative Jahn–Teller Mn³⁺ structure during discharge, with the clear presence of two Mn–O as well as two Mn–Mn correlation distances at 2.0 V. The significant reduction of manganese in the very first discharge is distinctly different from that seen in typical nickel-based lithium-manganese-rich materials but is similar to that observed for pure Li₂MnO₃. In conclusion, these findings shed light on key structure–property correlations in the cathode material and point to a causative relationship between the redox mechanisms as well as structural changes endured by the material and relatively poor performance during extended electrochemical cycling.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; AC02-06CH11357

OSTI ID:: 2281138

Alternate ID(s):: OSTI ID: 2481259

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 1 Vol. 36; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
earth-abundant cathode material
Li- Mn-rich cathode
LiFeO2
Li2MnO3
HERFD
XAFS
XES
XANES
EXAFS

Title: Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li2MnO3·0.3LiFeO2 Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies

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Title: Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li₂MnO₃·0.3LiFeO₂ Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies