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Title: Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

Journal Article · · Chemistry of Materials
 [1];  [2];  [1];  [1]
  1. Univ. of Texas, Austin, TX (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
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The electronic and electrochemical properties of the high-voltage spinel LiMn1.5Ni0.5O4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni2+/3+. and Ni3+/4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 in Li Li1-xMn1.5Ni0.5O4. Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn1.5Ni0.5O4 to Li0.5Mn1.5Ni0.5O4. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; DMR-1122603
OSTI ID:
1261474
Journal Information:
Chemistry of Materials, Vol. 27, Issue 20; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 53 works
Citation information provided by
Web of Science

References (44)

Advanced Electrodes for High Power Li-ion Batteries journal March 2013
A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries journal January 2014
Challenges and Approaches for High-Voltage Spinel Lithium-Ion Batteries journal May 2014
Review of 5-V electrodes for Li-ion batteries: status and trends journal May 2013
High-voltage spinel cathodes for lithium-ion batteries: controlling the growth of preferred crystallographic planes through cation doping journal January 2013
The effect of particle surface facets on the kinetic properties of LiMn 1.5 Ni 0.5 O 4 cathode materials journal January 2013
Crystallographic facet- and size-controllable synthesis of spinel LiNi 0.5 Mn 1.5 O 4 with excellent cyclic stability as cathode of high voltage lithium ion battery journal January 2014
A comparative study of Fd-3m and P4332 “LiNi0.5Mn1.5O4” journal June 2011
Spinel LiNi0.5Mn1.5O4 cathode for rechargeable lithiumion batteries: Nano vs micro, ordered phase (P4332) vs disordered phase (Fd $\bar 3$ m) journal July 2013
Enhanced Li+ ion transport in LiNi0.5Mn1.5O4 through control of site disorder journal January 2012
Integrated Nano-Domains of Disordered and Ordered Spinel Phases in LiNi 0.5 Mn 1.5 O 4 for Li-Ion Batteries journal July 2014
Interplay between two-phase and solid solution reactions in high voltage spinel cathode material for lithium ion batteries journal November 2013
Solid-Solution Li Intercalation as a Function of Cation Order/Disorder in the High-Voltage Li x Ni 0.5 Mn 1.5 O 4 Spinel journal July 2013
Synthesis and Characterization of Nanostructured 4.7 V Li[sub x]Mn[sub 1.5]Ni[sub 0.5]O[sub 4] Spinels for High-Power Lithium-Ion Batteries journal January 2006
High-Power Nanostructured LiMn 2 - x Ni x O 4 High-Voltage Lithium-Ion Battery Electrode Materials:  Electrochemical Impact of Electronic Conductivity and Morphology journal July 2006
Relationships between Mn 3+ Content, Structural Ordering, Phase Transformation, and Kinetic Properties in LiNi x Mn 2– x O 4 Cathode Materials journal September 2014
A study of room-temperature LixMn1.5Ni0.5O4 solid solutions journal January 2015
Electrical-conductivity and Hall-effect measurements in semiconducting powders. Study of percolation effects journal August 1978
High Conductivity in Gallium-Doped Zinc Oxide Powders journal January 1996
Mass and charge transport involving interfaces journal June 1999
The grain boundary impedance of random microstructures: numerical simulations and implications for the analysis of experimental data journal September 2002
Magnetic measurements as a viable tool to assess the relative degrees of cation ordering and Mn3+ content in doped LiMn1.5Ni0.5O4 spinel cathodes journal January 2013
An Indicator to Identify the Li[Ni[sub 1/2]Mn[sub 3/2]]O[sub 4] (P4[sub 3]32): DC-Susceptibility Measurements journal January 2010
Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model journal July 2008
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes journal June 2014
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries journal April 1997
Resisitivity, thermopower, and susceptibility of R NiO 3 ( R =La,Pr) journal July 1993
Conduction mechanism in operating a LiMn2O4 cathode journal February 2002
The effect of 3d substitutions in the manganese sublattice on the charge transport mechanism and electrochemical properties of manganese spinel journal July 2004
The effect of mixed Mn valences on Li migration in LiMn2O4 spinel: A molecular dynamics study journal January 2004
Electrical transport properties in LiMn 2 O 4 journal July 1998
Electrical transport properties in LiMn2O4, Li0.95Mn2O4, and LiMn1.95B0.05O4 (B=Al or Ga) around room temperature journal February 2002
Polarons in crystalline and non-crystalline materials journal November 2001
Small polarons journal June 1982
Small polaron migration in LixMn2O4: From first principles calculations journal July 2009
The effect of particle size and morphology on the rate capability of 4.7V LiMn1.5+δNi0.5−δO4 spinel lithium-ion battery cathodes journal May 2008
Improving rate capability of high potential LiNi0.5Mn1.5O4− cathode materials via increasing oxygen non-stoichiometries journal May 2012
Understanding the Improved Electrochemical Performances of Fe-Substituted 5 V Spinel Cathode LiMn 1.5 Ni 0.5 O 4 journal July 2009
Role of Oxygen Vacancies on the Performance of Li[Ni 0.5– x Mn 1.5+ x ]O 4 ( x = 0, 0.05, and 0.08) Spinel Cathodes for Lithium-Ion Batteries journal July 2012
Structure and insertion properties of disordered and ordered LiNi0.5Mn1.5O4 spinels prepared by wet chemistry journal June 2006
Composition-Structure Relationships in the Li-Ion Battery Electrode Material LiNi 0.5 Mn 1.5 O 4 journal August 2012
High-Performance LiNi 0.5 Mn 1.5 O 4 Spinel Controlled by Mn 3+ Concentration and Site Disorder journal March 2012
Microwave-Assisted Synthesis of High-Voltage Nanostructured LiMn1.5Ni0.5O4 Spinel: Tuning the Mn3+ Content and Electrochemical Performance journal July 2013
Solid Solution Domains at Phase Transition Front of Li x Ni 0.5 Mn 1.5 O 4 journal July 2015

Cited By (10)

Broken translational and rotational symmetries in LiMn 1.5 Ni 0.5 O 4 spinel journal July 2019
Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High-Performance Cathode journal October 2017
Comparative study of the electrochemical properties of P4332 and Fd3m space group of LiNi0.45Cu0.05Mn1.5O4 cathode materials journal November 2018
Comparative study of the electrochemical properties of LiNi0.5Mn1.5O4 doped by bivalent ions (Cu2+, Mg2+, and Zn2+) journal March 2017
Construction of LiMn 2 O 4 microcubes and spheres via the control of the (104) crystal planes of MnCO 3 for high rate Li-ions batteries journal January 2019
Extending the Service Life of High-Ni Layered Oxides by Tuning the Electrode-Electrolyte Interphase journal September 2018
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis journal May 2018
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis text January 2018
Anodic Decomposition of Surface Films on High Voltage Spinel Surfaces -- Density Function Theory and Experimental Study text January 2020

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