Origin of Phase Separation in Ni-Rich Layered Oxide Cathode Materials During Electrochemical Cycling

Liu, Sizhan; West, Patrick J.; Zhong, Hui; Bai, Jianming; Stavitski, Eli; Leshchev, Denis; Marschilok, Amy C.; Takeuchi, Esther S.; Bock, David C.; Takeuchi, Kenneth J.

doi:10.1021/acs.chemmater.3c00924

Origin of Phase Separation in Ni-Rich Layered Oxide Cathode Materials During Electrochemical Cycling

Journal Article · Thu Oct 19 00:00:00 EDT 2023 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.3c00924· OSTI ID:2246889

^[1]; ^[2]; Zhong, Hui ^[2]; ^[3]; Stavitski, Eli ^[3]; ^[3]; Marschilok, Amy C. ^[4]; ^[4]; ^[4]; ^[4]

Brookhaven National Laboratory (BNL), Upton, NY (United States)
Stony Brook University, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook University, NY (United States)

In intercalation materials, the kinetics and uniformity of mass transport across the nanocrystalline domains dictate the structural reversibility and transport capability at the macroscopic level. (De)intercalation-induced interlayer disintegrations exhibit anisotropic crystallite size change. Due to the anisotropic mass transport mechanism, separated phases are inherently crystallographically oriented. One such material is LiNi_$1–x–y$Mn_$$x$$Co_$$y$$O₂, which plays a pivotal role in advanced Li-ion batteries but suffers from severe phase inhomogeneities under fast charge or electrochemical aging. Here, using operando synchrotron techniques, we probe the mechanistic origins of the compositional and orientational-dependent phase separations during the electrochemical cycling of LiNi_0.8Mn_0.1Co_0.1O₂ by comprehensive analysis of both in-plane and out-of-plane reflections. In the H2/H3 phase regime, in-plane domain propagation occurs due to increased covalency despite the severe decay of interlayer crystallographic order, resulting in the change of crystalline domain shape from 3D spheres to two-dimensional nanosheets. The crystallographically selective XRD line splitting is linked to the geometry of the facets as mass transfers along the ab plane. In conclusion, this work provides mechanistic insights into crystallographic orientation-dependent phase inhomogeneity under fast charge and extended cycling.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: DEVCOM Army Research Laboratory (ARL); New York State Energy Research and Development Authority (NYSERDA); New York State Department of Economic Development (DED); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 2246889

Report Number(s):: BNL--225103-2023-JAAM

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 21 Vol. 35; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Origin of Phase Separation in Ni-Rich Layered Oxide Cathode Materials During Electrochemical Cycling

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