Accelerating the Electrochemical Formation of the δ Phase in Manganese-Rich Rocksalt Cathodes

Holstun, Tucker; Mishra, Tara P.; Huang, Liliang; Hau, Han‐Ming; Anand, Shashwat; Yang, Xiaochen; Ophus, Colin; Bustillo, Karen; ma, Lu; Ehrlich, Steven; Ceder, Gerbrand

doi:10.1002/adma.202412871

Title: Accelerating the Electrochemical Formation of the δ Phase in Manganese-Rich Rocksalt Cathodes

Journal Article · 23 December 2024 · Advanced Materials

DOI: https://doi.org/10.1002/adma.202412871 · OSTI ID:2483630

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University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Mn-rich disordered rocksalt materials with Li-excess (DRX) materials have emerged as a promising class of earth-abundant and energy-dense next-generation cathode materials for lithium-ion batteries. Recently, an electrochemical transformation to a spinel-like “δ” phase has been reported in Mn-rich DRX materials, with improved capacity, rate capability, and cycling stability compared with previous DRX compositions. However, this transformation unfolds slowly over the course of cycling, complicating the development and understanding of these materials. In this work, it is reported that the transformation of Mn-rich DRX materials to the promising δ phase can be promoted to occur much more rapidly by electrochemical pulsing at elevated temperature, rate, and voltage. To extend this concept, micron-sized single-crystal DRX particles are also transformed to the δ phase by the same method, possessing greatly improved cycling stability in the first demonstration of cycling for large, single-crystal DRX particles. To shed light on the formation and specific structure of the δ phase, X-ray diffraction, scanning electron nanodiffraction (SEND) and atomic resolution STEM-HAADF are used to reveal a nanodomain spinel structure with minimal remnant disorder.

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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); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 2483630

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 6 Vol. 37; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Accelerating the Electrochemical Formation of the δ Phase in Manganese-Rich Rocksalt Cathodes

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