Strain-driven surface reconstruction and cation segregation in layered Li(Ni1–x–yMnxCoy)O2 (NMC) cathode materials

Garcia, Juan C.; Bareño, Javier; Chen, Guoying; Croy, Jason R.; Iddir, Hakim

doi:10.1039/d0cp03942j

Title: Strain-driven surface reconstruction and cation segregation in layered Li(Ni_1–x–yMn_xCo_y)O₂ (NMC) cathode materials

Journal Article · Wed Oct 14 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp03942j· OSTI ID:1775102

Garcia, Juan C. ^[1]; Bareño, Javier ^[1];

^[2]; Croy, Jason R. ^[1];

^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The composition, structure and phase transformations occurring on cathode surfaces greatly affect the performance of Li-ion batteries. Li-Ion diffusion and surface–electrolyte interaction are two major phenomena that impact the capacity and cell impedance. The effects of surface reconstruction (SR) of cathode materials on the performance of Li-ion batteries are of current interest. However, the origin and evolution of the SR are still not well understood. In this work, density functional theory (DFT) calculations are used to investigate the processes taking place during surface segregation and reconstruction. Facet dependent segregation was found in Li(Ni_1–x–yMn_xCo_y)O₂ (NMC) cathodes. Specifically, Co tends to segregate to the (104) surface of the primary particles within the transition metal layer, while Ni ions tend to segregate to the (012) surface in the Li layer, forming a SR. Experimental evidence shows the SR to be epitaxial with the bulk of the as-synthesized material, and the new SR phase is pinned to the NMC unit cell leading to a strained SR. Here, we demonstrate that strain can stabilize a spinel structure of the SR layers. Understanding the effects of surface strain opens a new avenue for the design of cathode materials with enhanced surface properties.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

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

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1775102

Alternate ID(s):: OSTI ID: 1682363

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 22, Issue 42; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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