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 »
- Authors:
-
- Univ. of Texas, Austin, TX (United States)
- 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}
}
Web of Science
Works referenced in this record:
Advanced Electrodes for High Power Li-ion Batteries
journal, March 2013
- Zaghib, Karim; Mauger, Alain; Groult, Henri
- Materials, Vol. 6, Issue 3
A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries
journal, January 2014
- Manthiram, Arumugam; Chemelewski, Katharine; Lee, Eun-Sung
- Energy & Environmental Science, Vol. 7, Issue 4
Challenges and Approaches for High-Voltage Spinel Lithium-Ion Batteries
journal, May 2014
- Kim, Jung-Hyun; Pieczonka, Nicholas P. W.; Yang, Li
- ChemPhysChem, Vol. 15, Issue 10
Review of 5-V electrodes for Li-ion batteries: status and trends
journal, May 2013
- Julien, C. M.; Mauger, A.
- Ionics, Vol. 19, Issue 7
High-voltage spinel cathodes for lithium-ion batteries: controlling the growth of preferred crystallographic planes through cation doping
journal, January 2013
- Chemelewski, Katharine R.; Li, Wei; Gutierrez, Arturo
- Journal of Materials Chemistry A, Vol. 1, Issue 48
The effect of particle surface facets on the kinetic properties of LiMn 1.5 Ni 0.5 O 4 cathode materials
journal, January 2013
- Hai, Bin; Shukla, Alpesh K.; Duncan, Hugues
- J. Mater. Chem. A, Vol. 1, Issue 3
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
- Lin, H. B.; Zhang, Y. M.; Rong, H. B.
- Journal of Materials Chemistry A, Vol. 2, Issue 30
A comparative study of Fd-3m and P4332 “LiNi0.5Mn1.5O4”
journal, June 2011
- Wang, Liping; Li, Hong; Huang, Xuejie
- Solid State Ionics, Vol. 193, Issue 1
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
- Yang, Jingang; Han, Xiaopeng; Zhang, Xiaolong
- Nano Research, Vol. 6, Issue 9
Enhanced Li+ ion transport in LiNi0.5Mn1.5O4 through control of site disorder
journal, January 2012
- Zheng, Jianming; Xiao, Jie; Yu, Xiqian
- Physical Chemistry Chemical Physics, Vol. 14, Issue 39
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
- Kim, Jung-Hyun; Huq, Ashfia; Chi, Miaofang
- Chemistry of Materials, Vol. 26, Issue 15
Interplay between two-phase and solid solution reactions in high voltage spinel cathode material for lithium ion batteries
journal, November 2013
- Xiao, Jie; Yu, Xiqian; Zheng, Jianming
- Journal of Power Sources, Vol. 242
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
- Lee, Eunseok; Persson, Kristin A.
- Chemistry of Materials, Vol. 25, Issue 14
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
- Kunduraci, M.; Amatucci, G. G.
- Journal of The Electrochemical Society, Vol. 153, Issue 7
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
- Kunduraci, Muharrem; Al-Sharab, Jafar F.; Amatucci, Glenn G.
- Chemistry of Materials, Vol. 18, Issue 15
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
- Duncan, Hugues; Hai, Bin; Leskes, Michal
- Chemistry of Materials, Vol. 26, Issue 18
A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
journal, January 2015
- Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert
- Scientific Reports, Vol. 5, Issue 1
Electrical-conductivity and Hall-effect measurements in semiconducting powders. Study of percolation effects
journal, August 1978
- Clarke, P. S.; Orton, J. W.; Guest, A. J.
- Physical Review B, Vol. 18, Issue 4
High Conductivity in Gallium-Doped Zinc Oxide Powders
journal, January 1996
- Wang, Ruiping; Sleight, Arthur W.; Cleary, David
- Chemistry of Materials, Vol. 8, Issue 2
Mass and charge transport involving interfaces
journal, June 1999
- Maier, Joachim
- Journal of the European Ceramic Society, Vol. 19, Issue 6-7
The grain boundary impedance of random microstructures: numerical simulations and implications for the analysis of experimental data
journal, September 2002
- Fleig, J.
- Solid State Ionics, Vol. 150, Issue 1-2
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
- Moorhead-Rosenberg, Zachary; Chemelewski, Katharine R.; Goodenough, John B.
- Journal of Materials Chemistry A, Vol. 1, Issue 36
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
- Mukai, Kazuhiko; Sugiyama, Jun
- Journal of The Electrochemical Society, Vol. 157, Issue 6
Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model
journal, July 2008
- Delmas, C.; Maccario, M.; Croguennec, L.
- Nature Materials, Vol. 7, Issue 8
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014
- Liu, H.; Strobridge, F. C.; Borkiewicz, O. J.
- Science, Vol. 344, Issue 6191
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997
- Padhi, A. K.
- Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
Resisitivity, thermopower, and susceptibility of R ( R =La,Pr)
journal, July 1993
- Xu, X. Q.; Peng, J. L.; Li, Z. Y.
- Physical Review B, Vol. 48, Issue 2
Conduction mechanism in operating a LiMn2O4 cathode
journal, February 2002
- Marzec, J.
- Solid State Ionics, Vol. 146, Issue 3-4
The effect of 3d substitutions in the manganese sublattice on the charge transport mechanism and electrochemical properties of manganese spinel
journal, July 2004
- Molenda, J.
- Solid State Ionics, Vol. 171, Issue 3-4
The effect of mixed Mn valences on Li migration in LiMn2O4 spinel: A molecular dynamics study
journal, January 2004
- Tateishi, Kenji; du Boulay, Douglas; Ishizawa, Nobuo
- Applied Physics Letters, Vol. 84, Issue 4
Electrical transport properties in LiMn 2 O 4
journal, July 1998
- Iguchi, E.; Nakamura, N.; Aoki, A.
- Philosophical Magazine B, Vol. 78, Issue 1
Electrical transport properties in LiMn2O4, Li0.95Mn2O4, and LiMn1.95B0.05O4 (B=Al or Ga) around room temperature
journal, February 2002
- Iguchi, E.; Tokuda, Y.; Nakatsugawa, H.
- Journal of Applied Physics, Vol. 91, Issue 4
Polarons in crystalline and non-crystalline materials
journal, November 2001
- Austin, I. G.; Mott, N. F.
- Advances in Physics, Vol. 50, Issue 7
Small polaron migration in LixMn2O4: From first principles calculations
journal, July 2009
- Ouyang, Chuying; Du, Yanlan; Shi, Siqi
- Physics Letters A, Vol. 373, Issue 31
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
- Kunduraci, M.; Amatucci, G. G.
- Electrochimica Acta, Vol. 53, Issue 12
Improving rate capability of high potential LiNi0.5Mn1.5O4− cathode materials via increasing oxygen non-stoichiometries
journal, May 2012
- Jin, Yi-Chun; Lin, Chih-Yuan; Duh, Jenq-Gong
- Electrochimica Acta, Vol. 69
Understanding the Improved Electrochemical Performances of Fe-Substituted 5 V Spinel Cathode LiMn 1.5 Ni 0.5 O 4
journal, July 2009
- Liu, Jun; Manthiram, Arumugam
- The Journal of Physical Chemistry C, Vol. 113, Issue 33
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
- Song, Jie; Shin, Dong Wook; Lu, Yuhao
- Chemistry of Materials, Vol. 24, Issue 15
Structure and insertion properties of disordered and ordered LiNi0.5Mn1.5O4 spinels prepared by wet chemistry
journal, June 2006
- Amdouni, N.; Zaghib, K.; Gendron, F.
- Ionics, Vol. 12, Issue 2
Composition-Structure Relationships in the Li-Ion Battery Electrode Material LiNi 0.5 Mn 1.5 O 4
journal, August 2012
- Cabana, Jordi; Casas-Cabanas, Montserrat; Omenya, Fredrick O.
- Chemistry of Materials, Vol. 24, Issue 15
High-Performance LiNi 0.5 Mn 1.5 O 4 Spinel Controlled by Mn 3+ Concentration and Site Disorder
journal, March 2012
- Xiao, Jie; Chen, Xilin; Sushko, Peter V.
- Advanced Materials, Vol. 24, Issue 16
Microwave-Assisted Synthesis of High-Voltage Nanostructured LiMn1.5Ni0.5O4 Spinel: Tuning the Mn3+ Content and Electrochemical Performance
journal, July 2013
- Jafta, Charl J.; Mathe, Mkhulu K.; Manyala, Ncholu
- ACS Applied Materials & Interfaces, Vol. 5, Issue 15, p. 7592-7598
Solid Solution Domains at Phase Transition Front of Li x Ni 0.5 Mn 1.5 O 4
journal, July 2015
- Komatsu, Hideyuki; Arai, Hajime; Koyama, Yukinori
- Advanced Energy Materials, Vol. 5, Issue 17
Works referencing / citing this record:
Broken translational and rotational symmetries in LiMn 1.5 Ni 0.5 O 4 spinel
journal, July 2019
- Singh, Birender; Kumar, Sunil; Kumar, Pradeep
- Journal of Physics: Condensed Matter, Vol. 31, Issue 39
Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High-Performance Cathode
journal, October 2017
- Xiao, Biwei; Liu, Hanshuo; Liu, Jian
- Advanced Materials, Vol. 29, Issue 47
Comparative study of the electrochemical properties of P4332 and Fd3m space group of LiNi0.45Cu0.05Mn1.5O4 cathode materials
journal, November 2018
- Deng, Miao-Miao; Zhang, Da-Wei; Yasmin, Aqsa
- SN Applied Sciences, Vol. 1, Issue 1
Comparative study of the electrochemical properties of LiNi0.5Mn1.5O4 doped by bivalent ions (Cu2+, Mg2+, and Zn2+)
journal, March 2017
- Deng, Miao-Miao; Zou, Bang-Kun; Shao, Yu
- Journal of Solid State Electrochemistry, Vol. 21, Issue 6
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
- Gao, Yanshen; Wang, Xinlu; Yu, Wensheng
- RSC Advances, Vol. 9, Issue 36
Extending the Service Life of High-Ni Layered Oxides by Tuning the Electrode-Electrolyte Interphase
journal, September 2018
- Li, Jianyu; Li, Wangda; You, Ya
- Advanced Energy Materials, Vol. 8, Issue 29
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis
journal, May 2018
- Yang, Shuo; Schmidt, Dirk; Khetan, Abhishek
- Materials, Vol. 11, Issue 5
High-voltage positive electrode materials for lithium-ion batteries
journal, January 2017
- Li, Wangda; Song, Bohang; Manthiram, Arumugam
- Chemical Society Reviews, Vol. 46, Issue 10
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis
text, January 2018
- Yang, Shuo; Schmidt, Dirk Oliver; Khetan, Abhishek
- RWTH Aachen University
Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis
journal, May 2018
- Yang, Shuo; Schmidt, Dirk; Khetan, Abhishek
- Materials, Vol. 11, Issue 5
Anodic Decomposition of Surface Films on High Voltage Spinel Surfaces -- Density Function Theory and Experimental Study
text, January 2020
- Leung, Kevin; Noked, Malachi
- arXiv