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Title: Insight into the Atomic Structure of High-Voltage Spinel LiNi0.5Mn1.5O4 Cathode Material in the First Cycle

Journal Article · · Chemistry of Materials
DOI:https://doi.org/10.1021/cm503972a· OSTI ID:1169558
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [1];  [1];  [3]
  1. Chinese Academy of Sciences, Beijing (China)
  2. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  3. CIC Energigune, Alava (Spain)
+ Show Author Affiliations

Application of high-voltage spinel LiNi0.5Mn1.5O4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi0.5Mn1.5O4 cathode material. Although it is well-known that the structure of LiNi0.5Mn1.5O4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood. Here, we report detailed investigations of local atomic-level and average structure of LiNi0.5Mn1.5O4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi0.5Mn1.5O4//Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi0.5Mn1.5O4 particles show migration of TM ions into tetrahedral Li sites to form a Mn3O4-like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely related to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi0.5Mn1.5O4 cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi0.5Mn1.5O4 structure to obtain better electrochemical performance.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
DE-SC00112704
OSTI ID:
1169558
Report Number(s):
BNL-107260-2014-JA; R&D Project: MA453MAEA; VT1201000
Journal Information:
Chemistry of Materials, Vol. 27, Issue 1; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 126 works
Citation information provided by
Web of Science

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Cited By (21)

Tuning Anionic Redox Activity and Reversibility for a High‐Capacity Li‐Rich Mn‐Based Oxide Cathode via an Integrated Strategy journal March 2019
Exploring the origin of electrochemical performance of Cr-doped LiNi 0.5 Mn 1.5 O 4 journal January 2020
Application of Li 2 S to compensate for loss of active lithium in a Si–C anode journal January 2018
Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High-Performance Cathode journal October 2017
Uniform Na + Doping‐Induced Defects in Li‐ and Mn‐Rich Cathodes for High‐Performance Lithium‐Ion Batteries journal May 2019
Atomic Insights into the Enhanced Surface Stability in High Voltage Cathode Materials by Ultrathin Coating journal January 2017
Multi-scale computation methods: Their applications in lithium-ion battery research and development journal January 2016
Atomic-Scale Direct Identification of Surface Variations in Cathode Oxides for Aqueous and Nonaqueous Lithium-Ion Batteries journal January 2019
Construction of uniform transition-metal phosphate nanoshells and their potential for improving Li-ion battery performance journal January 2018
High-Voltage Li 2 SiO 3 −LiNi 0.5 Mn 1.5 O 4 Hollow Spheres Prepared through In Situ Aerosol Spray Pyrolysis towards High-Energy Li-Ion Batteries journal February 2018
Comparative study of the electrochemical properties of P4332 and Fd3m space group of LiNi0.45Cu0.05Mn1.5O4 cathode materials journal November 2018
Three-dimensional atomic-scale observation of structural evolution of cathode material in a working all-solid-state battery journal August 2018
Impact of High Valence State Cation Ti/Ta Surface Doping on the Stabilization of Spinel LiNi 0.5 Mn 1.5 O 4 Cathode Materials: A Systematic Density Functional Theory Investigation journal April 2018
Exploration of Advanced Electrode Materials for Rechargeable Sodium‐Ion Batteries journal July 2018
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries journal January 2016
Advances in the Cathode Materials for Lithium Rechargeable Batteries journal February 2020
Comparative study of the electrochemical properties of LiNi0.5Mn1.5O4 doped by bivalent ions (Cu2+, Mg2+, and Zn2+) journal March 2017
Atomic-Scale Structure Evolution in a Quasi-Equilibrated Electrochemical Process of Electrode Materials for Rechargeable Batteries journal February 2015
Do imaging techniques add real value to the development of better post-Li-ion batteries? journal January 2018
Kathodenmaterialien für wiederaufladbare Lithiumbatterien journal November 2019
High-voltage positive electrode materials for lithium-ion batteries journal January 2017

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