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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

Abstract

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 ormore » 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.« less

Authors:
 [1];  [2];  [1];  [1]
  1. Univ. of Texas, Austin, TX (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1261474
Grant/Contract Number:  
AC05-00OR22725; DMR-1122603
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 20; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Moorhead-Rosenberg, Zach, Huq, Ashfia, Goodenough, John B., and Manthiram, Arumugam. 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. United States: N. p., 2015. Web. doi:10.1021/acs.chemmater.5b01356.
Moorhead-Rosenberg, Zach, Huq, Ashfia, Goodenough, John B., & Manthiram, Arumugam. 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. United States. https://doi.org/10.1021/acs.chemmater.5b01356
Moorhead-Rosenberg, Zach, Huq, Ashfia, Goodenough, John B., and Manthiram, Arumugam. 2015. "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". United States. https://doi.org/10.1021/acs.chemmater.5b01356. https://www.osti.gov/servlets/purl/1261474.
@article{osti_1261474,
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},
author = {Moorhead-Rosenberg, Zach and Huq, Ashfia and Goodenough, John B. and Manthiram, Arumugam},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.5b01356},
url = {https://www.osti.gov/biblio/1261474}, journal = {Chemistry of Materials},
issn = {0897-4756},
number = 20,
volume = 27,
place = {United States},
year = {Mon Oct 05 00:00:00 EDT 2015},
month = {Mon Oct 05 00:00:00 EDT 2015}
}

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Works referencing / citing this record:

Broken translational and rotational symmetries in LiMn 1.5 Ni 0.5 O 4 spinel
journal, July 2019


Comparative study of the electrochemical properties of LiNi0.5Mn1.5O4 doped by bivalent ions (Cu2+, Mg2+, and Zn2+)
journal, March 2017


Extending the Service Life of High-Ni Layered Oxides by Tuning the Electrode-Electrolyte Interphase
journal, September 2018


High-voltage positive electrode materials for lithium-ion batteries
journal, January 2017