Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes

Linze Li; Ethan C. Self; Devendrasinh Darbar; Lianfeng Zou; Indranil Bhattacharya; Donghai Wang; Jagjit Nanda; Chongmin Wang

doi:10.1021/acs.nanolett.0c00380

Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes

Linze Li, Ethan C. Self, Devendrasinh Darbar, Lianfeng Zou, Indranil Bhattacharya, Donghai Wang, Jagjit Nanda, Chongmin Wang

Energy Storage & Conversion

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

Structural transformations near surfaces of solid-state materials underpin functional mechanisms of a broad range of applications including catalysis, memory, and energy storage. It has been a long-standing notion that the outermost free surfaces, accompanied by broken translational symmetry and altered atomic configurations, are usually the birthplace for structural transformations. Here, in a layered oxide cathode for Li-ion batteries, we for the first time observe the incipient state of the well-documented layered-to-spinel-like structural transformation, which is surprisingly initiated from the subsurface layer, rather than the very surface. Coupling atomic level scanning transmission electron microscopy imaging with electron energy loss spectroscopy, we discover that the reconstructed subsurfaces, featuring a mix of discrete patches of layered and spinel-like structures, are associated with selective atomic species partition and consequent nanoscale nonuniform composition gradient distribution at the subsurface. Our findings provide fundamental insights on atomic-scale mechanisms of structural transformation in layered cathodes.

Original language	English
Pages (from-to)	2756-2762
Number of pages	7
Journal	Nano Letters
Volume	20
Issue number	4
DOIs	https://doi.org/10.1021/acs.nanolett.0c00380
State	Published - Apr 8 2020

Funding

This work is supported by the Department of Energy Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technology Office, under Award Number DE-EE0008447. The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the Department of Energy under Contract DE-AC05-76RLO1830. This work is supported by the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technology Office, under Award Number DE-EE0008447. The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the Department of Energy under Contract DE-AC05-76RLO1830.

Funders	Funder number
U.S. Department of Energy
Office of Energy Efficiency and Renewable Energy	DE-AC05-76RLO1830, DE-EE0008447
Biological and Environmental Research
Pacific Northwest National Laboratory

Keywords

Li-ion batteries
layered oxide cathodes
scanning transmission electron microscopy
structural transformations
surface

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acs.nanolett.0c00380

Cite this

@article{516ceccecd3f4705a7b791b27c006c7f,

title = "Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes",

abstract = "Structural transformations near surfaces of solid-state materials underpin functional mechanisms of a broad range of applications including catalysis, memory, and energy storage. It has been a long-standing notion that the outermost free surfaces, accompanied by broken translational symmetry and altered atomic configurations, are usually the birthplace for structural transformations. Here, in a layered oxide cathode for Li-ion batteries, we for the first time observe the incipient state of the well-documented layered-to-spinel-like structural transformation, which is surprisingly initiated from the subsurface layer, rather than the very surface. Coupling atomic level scanning transmission electron microscopy imaging with electron energy loss spectroscopy, we discover that the reconstructed subsurfaces, featuring a mix of discrete patches of layered and spinel-like structures, are associated with selective atomic species partition and consequent nanoscale nonuniform composition gradient distribution at the subsurface. Our findings provide fundamental insights on atomic-scale mechanisms of structural transformation in layered cathodes.",

keywords = "Li-ion batteries, layered oxide cathodes, scanning transmission electron microscopy, structural transformations, surface",

author = "Linze Li and Self, {Ethan C.} and Devendrasinh Darbar and Lianfeng Zou and Indranil Bhattacharya and Donghai Wang and Jagjit Nanda and Chongmin Wang",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = apr,

day = "8",

doi = "10.1021/acs.nanolett.0c00380",

language = "English",

volume = "20",

pages = "2756--2762",

journal = "Nano Letters",

issn = "1530-6984",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes

AU - Li, Linze

AU - Self, Ethan C.

AU - Darbar, Devendrasinh

AU - Zou, Lianfeng

AU - Bhattacharya, Indranil

AU - Wang, Donghai

AU - Nanda, Jagjit

AU - Wang, Chongmin

PY - 2020/4/8

Y1 - 2020/4/8

N2 - Structural transformations near surfaces of solid-state materials underpin functional mechanisms of a broad range of applications including catalysis, memory, and energy storage. It has been a long-standing notion that the outermost free surfaces, accompanied by broken translational symmetry and altered atomic configurations, are usually the birthplace for structural transformations. Here, in a layered oxide cathode for Li-ion batteries, we for the first time observe the incipient state of the well-documented layered-to-spinel-like structural transformation, which is surprisingly initiated from the subsurface layer, rather than the very surface. Coupling atomic level scanning transmission electron microscopy imaging with electron energy loss spectroscopy, we discover that the reconstructed subsurfaces, featuring a mix of discrete patches of layered and spinel-like structures, are associated with selective atomic species partition and consequent nanoscale nonuniform composition gradient distribution at the subsurface. Our findings provide fundamental insights on atomic-scale mechanisms of structural transformation in layered cathodes.

AB - Structural transformations near surfaces of solid-state materials underpin functional mechanisms of a broad range of applications including catalysis, memory, and energy storage. It has been a long-standing notion that the outermost free surfaces, accompanied by broken translational symmetry and altered atomic configurations, are usually the birthplace for structural transformations. Here, in a layered oxide cathode for Li-ion batteries, we for the first time observe the incipient state of the well-documented layered-to-spinel-like structural transformation, which is surprisingly initiated from the subsurface layer, rather than the very surface. Coupling atomic level scanning transmission electron microscopy imaging with electron energy loss spectroscopy, we discover that the reconstructed subsurfaces, featuring a mix of discrete patches of layered and spinel-like structures, are associated with selective atomic species partition and consequent nanoscale nonuniform composition gradient distribution at the subsurface. Our findings provide fundamental insights on atomic-scale mechanisms of structural transformation in layered cathodes.

KW - Li-ion batteries

KW - layered oxide cathodes

KW - scanning transmission electron microscopy

KW - structural transformations

KW - surface

UR - http://www.scopus.com/inward/record.url?scp=85083002851&partnerID=8YFLogxK

U2 - 10.1021/acs.nanolett.0c00380

DO - 10.1021/acs.nanolett.0c00380

M3 - Article

C2 - 32119550

AN - SCOPUS:85083002851

SN - 1530-6984

VL - 20

SP - 2756

EP - 2762

JO - Nano Letters

JF - Nano Letters

IS - 4

ER -

Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes

Abstract

Funding

Keywords

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this