How Mn/Ni Ordering Controls Electrochemical Performance in High-Voltage Spinel LiNi0.44Mn1.56O4with Fixed Oxygen Content

Burak Aktekin, Felix Massel, Majid Ahmadi, Mario Valvo, Maria Hahlin, Wolfgang Zipprich, Fernanda Marzano, Laurent Duda, Reza Younesi, Kristina Edström, Daniel Brandell*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

The crystal structure of LiNi0.5Mn1.5O4 (LNMO) can adopt either low-symmetry ordered (Fd3¯ m) or high-symmetry disordered (P4332) space group depending on the synthesis conditions. A majority of published studies agree on superior electrochemical performance of disordered LNMO, but the underlying reasons for improvement remain unclear due to the fact that different thermal history of the samples affects other material properties such as oxygen content and particle morphology. In this study, ordered and disordered samples were prepared with a new strategy that renders samples with identical properties apart from their cation ordering degree. This was achieved by heat treatment of powders under pure oxygen atmosphere at high temperature with a final annealing step at 710 °C for both samples, followed by slow or fast cooling. Electrochemical testing showed that cation disordering improves the stability of material in charged (delithiated) state and mitigates the impedance rise in LNMO-1LTO (Li4Ti5O12) and LNMO-1Li cells. Through X-ray photoelectron spectroscopy (XPS), thicker surface films were observed on the ordered material, indicating more electrolyte side reactions. The ordered samples also showed significant changes in the Ni 2p XPS spectra, while the generation of ligand (oxygen) holes was observed in the Ni-O environment for both samples using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). Moreover, high-resolution transmission electron microscopy (HRTEM) images indicated that the ordered samples show a decrease in ordering near the particle surface after cycling and a tendency toward rock-salt-like phase transformations. These results show that the structural arrangement of Mn/Ni (alone) has an effect on the surface and "near-surface"properties of LNMO, particularly in delithiated state, which is likely connected to the bulk electronic properties of this electrode material.

Original languageEnglish
Pages (from-to)6001-6013
Number of pages13
JournalACS Applied Energy Materials
Volume3
Issue number6
DOIs
Publication statusPublished - 22-Jun-2020
Externally publishedYes

Keywords

  • anionic redox
  • cation ordering
  • high-voltage spinel
  • LNMO
  • oxygen deficiency
  • rock-salt

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