Enhancing the Ion Transport in LiMn1.5Ni0.5O4 by Altering the Particle Wulff Shape via Anisotropic Surface Segregation

Jiajia Huang; Haodong Liu; Naixie Zhou; Ke An; Ying Shirley Meng; Jian Luo

doi:10.1021/acsami.7b09903

Enhancing the Ion Transport in LiMn_1.5Ni_0.5O₄ by Altering the Particle Wulff Shape via Anisotropic Surface Segregation

Jiajia Huang, Haodong Liu, Naixie Zhou, Ke An, Ying Shirley Meng, Jian Luo

Materials Engineering

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

43 Scopus citations

Abstract

Spontaneous and anisotropic surface segregation of W cations in LiMn_1.5Ni_0.5O₄ particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by -5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn³⁺ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. This is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn_1.5Ni_0.5O₄ spinel materials.

Original language	English
Pages (from-to)	36745-36754
Number of pages	10
Journal	ACS Applied Materials and Interfaces
Volume	9
Issue number	42
DOIs	https://doi.org/10.1021/acsami.7b09903
State	Published - Oct 25 2017

Funding

This work was partially supported by a Vannevar Bush Faculty Fellowship sponsored by the Basic Research Office of the Assistant Secretary of Defense for Research and Engineering and funded by the Office of Naval Research through grant N00014-16-1-2569. H.L. and Y.S.M. acknowledge the partial support by the U.S. Department of Energy, Office of Basic Energy Sciences, under Award Number DE-SC0002357. We thank Dr. Lee Ilkeun and Prof. Zaera from University of California Riverside for collecting the XPS data using the instrument funded by the U.S. National Science Foundation under the Major Research Instrumentation Program through grant DMR-0958796. The neutron experiments benefited from the SNS user facility, sponsored by the office of Basic Energy Sciences (BES), the Office of Science of the DOE.

Keywords

Wulff shape
anisotropic surface segregation
high-voltage spinel
lithium-ion batteries
neutron diffraction

Access to Document

10.1021/acsami.7b09903

Cite this

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title = "Enhancing the Ion Transport in LiMn1.5Ni0.5O4 by Altering the Particle Wulff Shape via Anisotropic Surface Segregation",

abstract = "Spontaneous and anisotropic surface segregation of W cations in LiMn1.5Ni0.5O4 particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by -5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn3+ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. This is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn1.5Ni0.5O4 spinel materials.",

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AU - Liu, Haodong

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AU - An, Ke

AU - Meng, Ying Shirley

AU - Luo, Jian

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AB - Spontaneous and anisotropic surface segregation of W cations in LiMn1.5Ni0.5O4 particles can alter the Wulff shape and improve surface stability, thereby significantly improving the electrochemical performance. An Auger electron nanoprobe was employed to identify the anisotropic surface segregation, whereby W cations prefer to segregate to {110} surface facets to decrease its relative surface energy according to Gibbs adsorption theory and subsequently increase its surface area according to Wulff theory. Consequently, the rate performance is improved (e.g., by -5-fold at a high rate of 25C) because the {110} facets have more open channels for fast lithium ion diffusion. Furthermore, X-ray photoelectron spectroscopy (XPS) depth profiling suggested that the surface segregation and partial reduction of W cation inhibit the formation of Mn3+ on surfaces to improve cycling stability via enhancing the cathode electrolyte interphase (CEI) stability at high charging voltages. This is the first report of using anisotropic surface segregation to thermodynamically control the particle morphology as well as enhancing CEI stability as a facile, and potentially general, method to significantly improve the electrochemical performance of battery electrodes. Combining neutron diffraction, an Auger electron nanoprobe, XPS, and other characterizations, we depict the underlying mechanisms of improved ionic transport and CEI stability in high-voltage LiMn1.5Ni0.5O4 spinel materials.

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