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Enhancing the Ion Transport in LiMn1.5Ni0.5O4 by Altering the Particle Wulff Shape via Anisotropic Surface
Jiajia Huang1, Haodong Liu1, Naixie Zhou1
1Department of NanoEngineering, Program of Materials Science and Engineering, University of California, San Diego , 9500 Gilman Drive, La Jolla, California 92093-0448, United States.
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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