Quantitative Decoupling of Oxygen-Redox and Manganese-Redox Voltage Hysteresis in a Cation-Disordered Rock Salt Cathode

Huang, Tzu‐Yang; Cai, Zijian; Crafton, Matthew J.; Kaufman, Lori A.; Konz, Zachary M.; Bergstrom, Helen K.; Kedzie, Elyse A.; Hao, Han‐Ming; Ceder, Gerbrand; McCloskey, Bryan D.

doi:10.1002/aenm.202300241

Quantitative Decoupling of Oxygen-Redox and Manganese-Redox Voltage Hysteresis in a Cation-Disordered Rock Salt Cathode

Journal Article · Mon Apr 17 00:00:00 EDT 2023 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202300241· OSTI ID:2326179

^[1]; Cai, Zijian ^[1]; Crafton, Matthew J. ^[1]; Kaufman, Lori A. ^[1]; Konz, Zachary M. ^[1]; Bergstrom, Helen K. ^[1]; Kedzie, Elyse A. ^[1]; Hao, Han‐Ming ^[1]; ^[1]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Pronounced voltage hysteresis in Li-excess cathode materials is commonly thought to be associated with oxygen redox. However, these materials often possess overlapping oxygen and transition-metal redox, whose contributions to hysteresis between charge and discharge are challenging to distinguish. In this work, a two-step aqueous redox titration is developed with the aid of mass spectrometry (MS) to quantify oxidized lattice oxygen and Mn^3+/4+ redox in a representative Li-excess cation-disordered rock salt—Li_1.2Mn_0.4Ti_0.4O₂ (LMTO). Two MS-countable gas molecules evolve from two separate titrant-analyte reactions, thereby allowing Mn and O redox capacities to be decoupled. The decoupled O and Mn redox coulombic efficiencies are close to 100% for the LMTO cathode, indicating high charge-compensation reversibility. As incremental Mn and O redox capacities are quantitatively decoupled, each redox voltage hysteresis is further evaluated. Overall, LMTO voltage hysteresis arises not only from an intrinsic charge-discharge voltage mismatch related to O redox, but also from asymmetric Mn-redox overvoltages. The results reveal that O and Mn redox both contribute substantially to voltage hysteresis. In conclusion, this work further shows the potential of designing new analytical workflows to experimentally quantify key properties, even in a disordered material having complex local coordination environments.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2326179

Alternate ID(s):: OSTI ID: 1983486

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 21 Vol. 13; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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