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Title: Integrated Nano-Domains of Disordered and Ordered Spinel Phases in LiNi0.5Mn1.5O4 for Li-Ion Batteries

Journal Article · · Chemistry of Materials
DOI:https://doi.org/10.1021/cm501203r· OSTI ID:1511405
 [1];  [2];  [2];  [3];  [4];  [2];  [5];  [6];  [4];  [1]
  1. General Motors Global R & D Center, Warren, MI (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Optimal CAE Inc., Plymouth, MI (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. GM Global Powertrain, Warren, MI (United States)
  6. Univ. of Texas, Austin, TX (United States)
+ Show Author Affiliations

Recent calculations and experimental data suggest that understanding the local ordering behavior of Ni/Mn will be critical to optimize the electrochemical properties of LiNi0.5Mn1.5O4 (LNMO) high voltage spinel. In this study, we systematically controlled the evolution of Ni and Mn ordering in LNMO samples by annealing them at 700 °C in air for different dwelling times, followed by quenching to room temperature. The long- and short-range ordering behavior of Ni and Mn were analyzed by combining neutron powder diffraction, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) data. The results show that the fraction of ordered phase increases rapidly during initial annealing at 700 °C for 6 h, and accompanied by decreasing amounts of secondary phases. Annealing longer than 6 h led to the growth in size of ordered domains (i.e., increased segregation of ordered and disordered domains) along with a slow increase in the fraction of ordered phase. The dependence of open circuit voltages (OCVs) of the LNMO on the degree of ordering agrees well with recent calculations using the density functional theory. The increase in the degree of ordering increases the open circuit voltage (OCV) and the initial capacity but reduces cycle life and rate capability. The LNMO delivered optimal battery performances (capacity, cycle life, and rate capability) after annealing at 700 °C for 2 h. This partially ordered sample showed the respective advantages from both disordered and ordered spinels: better spinel-phase purity (thus, higher initial capacity) from the ordered LNMO and better cycle life and rate capability from the disordered LNMO.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1511405
Journal Information:
Chemistry of Materials, Vol. 26, Issue 15; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 120 works
Citation information provided by
Web of Science

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Cited By (14)

Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry journal January 2019
Li 4 Ti 5 O 12 Anode: Structural Design from Material to Electrode and the Construction of Energy Storage Devices journal October 2017
Aqueous rechargeable zinc/sodium vanadate batteries with enhanced performance from simultaneous insertion of dual carriers journal April 2018
Anodic decomposition of surface films on high voltage spinel surfaces—Density function theory and experimental study journal December 2019
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis journal May 2018
Hybrid electrolyte enables safe and practical 5 V LiNi 0.5 Mn 1.5 O 4 batteries journal January 2019
Truncated Octahedral High-Voltage Spinel LiNi 0.5 Mn 1.5 O 4 Cathode Materials for Lithium Ion Batteries: Positive Influences of Ni/Mn Disordering and Oxygen Vacancies journal January 2018
Understanding structural, optical, magnetic and electrical performances of Fe- or Co-substituted spinel LiMn1.5Ni0.5O4 cathode materials journal January 2019
Urea-assisted hydrothermal synthesis of a hollow hierarchical LiNi 0.5 Mn 1.5 O 4 cathode material with tunable morphology characteristics journal January 2018
In Situ Formation of a Cathode-Electrolyte Interface with Enhanced Stability by Titanium Substitution for High Voltage Spinel Lithium-Ion Batteries journal May 2015
Controlled Atomic Solubility in Mn‐Rich Composite Material to Achieve Superior Electrochemical Performance for Li‐Ion Batteries journal December 2019
Comparative study of the electrochemical properties of P4332 and Fd3m space group of LiNi0.45Cu0.05Mn1.5O4 cathode materials journal November 2018
Effect of Chemical Bonding Characteristics on Ordering Structure in Li Spinel Oxides journal November 2018
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis text January 2018

Figures / Tables (14)

Table 1(p. 3)table Table 1
Figure 1(p. 4)figure Figure 1
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Table 2(p. 6)table Table 2
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Table 3(p. 8)table Table 3
Figure 10(p. 9)figure Figure 10
Figure 9(p. 9)figure Figure 9
Figure 11(p. 10)figure Figure 11

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