The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5O4
Abstract
The migration of transition metal ions in the oxygen framework was recently proposed to be responsible for the continuous loss of average working potential of high energy density layered–layered composite cathodes for lithium-ion batteries. The potential migration pathway in a model material, LiNi 0.5 Mn 1.5O4 spinel, was investigated using in situ high-energy X-ray diffraction and in situ neutron diffraction during the solid state synthesis process. It was found that the migration of transition metal ions among octahedral sites is possible by using tetrahedral vacancies as intermediate sites. It was also suggested that the number of electrons in 3d orbitals has a significant impact on their mobility in the hosting oxygen framework.
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division, Spallation Neutron Source (SNS)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1327577
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 24; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Xu, Gui-Liang, Qin, Yan, Ren, Yang, Cai, Lu, An, Ke, Amine, Khalil, and Chen, Zonghai. The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5O4. United States: N. p., 2015.
Web. doi:10.1039/C5TA02522B.
Xu, Gui-Liang, Qin, Yan, Ren, Yang, Cai, Lu, An, Ke, Amine, Khalil, & Chen, Zonghai. The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5O4. United States. https://doi.org/10.1039/C5TA02522B
Xu, Gui-Liang, Qin, Yan, Ren, Yang, Cai, Lu, An, Ke, Amine, Khalil, and Chen, Zonghai. Tue .
"The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5O4". United States. https://doi.org/10.1039/C5TA02522B. https://www.osti.gov/servlets/purl/1327577.
@article{osti_1327577,
title = {The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5O4},
author = {Xu, Gui-Liang and Qin, Yan and Ren, Yang and Cai, Lu and An, Ke and Amine, Khalil and Chen, Zonghai},
abstractNote = {The migration of transition metal ions in the oxygen framework was recently proposed to be responsible for the continuous loss of average working potential of high energy density layered–layered composite cathodes for lithium-ion batteries. The potential migration pathway in a model material, LiNi 0.5 Mn 1.5O4 spinel, was investigated using in situ high-energy X-ray diffraction and in situ neutron diffraction during the solid state synthesis process. It was found that the migration of transition metal ions among octahedral sites is possible by using tetrahedral vacancies as intermediate sites. It was also suggested that the number of electrons in 3d orbitals has a significant impact on their mobility in the hosting oxygen framework.},
doi = {10.1039/C5TA02522B},
journal = {Journal of Materials Chemistry. A},
number = 24,
volume = 3,
place = {United States},
year = {Tue May 12 00:00:00 EDT 2015},
month = {Tue May 12 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 15 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Synthesis of single crystalline hexagonal nanobricks of LiNi1/3Co1/3Mn1/3O2 with high percentage of exposed {010} active facets as high rate performance cathode material for lithium-ion battery
journal, January 2013
- Fu, Fang; Xu, Gui-Liang; Wang, Qi
- Journal of Materials Chemistry A, Vol. 1, Issue 12
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
First In Situ Lattice Strains Measurements Under Load at VULCAN
journal, October 2010
- An, Ke; Skorpenske, Harley D.; Stoica, Alexandru D.
- Metallurgical and Materials Transactions A, Vol. 42, Issue 1
Layered xLiMO2·(1−x)Li2M′O3 electrodes for lithium batteries: a study of 0.95LiMn0.5Ni0.5O2·0.05Li2TiO3
journal, March 2002
- Kim, J.
- Electrochemistry Communications, Vol. 4, Issue 3
Effects of cycling temperatures on the voltage fade phenomenon in 0.5Li2MnO3·0.5LiNi0.375Mn0.375Co0.25O2 cathodes
journal, April 2015
- Vu, Anh; Walker, Lee K.; Bareño, Javier
- Journal of Power Sources, Vol. 280
Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution
journal, April 2014
- Zheng, Jianming; Gu, Meng; Genc, Arda
- Nano Letters, Vol. 14, Issue 5
Preparation of high quality layered-layered composite Li2MnO3–LiMO2 (M=Ni, Mn, Co) Li-ion cathodes by a ball milling–annealing process
journal, April 2012
- West, W. C.; Soler, J.; Ratnakumar, B. V.
- Journal of Power Sources, Vol. 204
Comments on the structural complexity of lithium-rich Li1+xM1−xO2 electrodes (M=Mn, Ni, Co) for lithium batteries
journal, September 2006
- Thackeray, M. M.; Kang, S.-H.; Johnson, C. S.
- Electrochemistry Communications, Vol. 8, Issue 9, p. 1531-1538
Electronic properties of transition-metal oxides—I
journal, January 1957
- Dunitz, J. D.; Orgel, L. E.
- Journal of Physics and Chemistry of Solids, Vol. 3, Issue 1-2
Recent Advances in First Principles Computational Research of Cathode Materials for Lithium-Ion Batteries
journal, April 2012
- Meng, Ying Shirley; Arroyo-de Dompablo, M. Elena
- Accounts of Chemical Research, Vol. 46, Issue 5
Unraveling structural evolution of LiNi0.5Mn1.5O4 by in situ neutron diffraction
journal, January 2013
- Cai, Lu; Liu, Zengcai; An, Ke
- Journal of Materials Chemistry A, Vol. 1, Issue 23
Single-Crystalline LiMn2O4 Nanotubes Synthesized Via Template-Engaged Reaction as Cathodes for High-Power Lithium Ion Batteries
journal, November 2010
- Ding, Yuan-Li; Xie, Jian; Cao, Gao-Shao
- Advanced Functional Materials, Vol. 21, Issue 2
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
Kinetics and Structural Changes of Li-Rich Layered Oxide 0.5Li 2 MnO 3 ·0.5LiNi 0.292 Co 0.375 Mn 0.333 O 2 Material Investigated by a Novel Technique Combining in Situ XRD and a Multipotential Step
journal, July 2014
- Shen, Chong-Heng; Huang, Ling; Lin, Zhou
- ACS Applied Materials & Interfaces, Vol. 6, Issue 15
Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014
- Sathiya, M.; Abakumov, A. M.; Foix, D.
- Nature Materials, Vol. 14, Issue 2
A comparison of destabilization mechanisms of the layered NaxMO2 and LixMO2 compounds upon alkali de-intercalation
journal, January 2012
- Kim, Sangtae; Ma, Xiaohua; Ong, Shyue Ping
- Physical Chemistry Chemical Physics, Vol. 14, Issue 44
Strain Effect on the Electrochemical Properties of Li2MnO3 Cathode Material: A First Principles Calculation
journal, July 2012
- Ren, Xiao Dong; Liu, Jian Jun; Zhang, Wen Qing
- Key Engineering Materials, Vol. 519
Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy Density
journal, January 2013
- Bettge, Martin; Li, Yan; Gallagher, Kevin
- Journal of The Electrochemical Society, Vol. 160, Issue 11
Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries
journal, June 1996
- Armstrong, A. Robert; Bruce, Peter G.
- Nature, Vol. 381, Issue 6582
LiNi x Cu0.5 − x Mn1.5 O 4 Spinel Electrodes, Superior High‐Potential Cathode Materials for Li Batteries: I. Electrochemical and Structural Studies
journal, March 1999
- Ein‐Eli, Yair; Vaughey, John T.; Thackeray, Michael M.
- Journal of The Electrochemical Society, Vol. 146, Issue 3
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
The distribution of transition metal cations in spinels
journal, January 1957
- McClure, Donald S.
- Journal of Physics and Chemistry of Solids, Vol. 3, Issue 3-4
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries
journal, July 2013
- Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François
- Nano Letters, Vol. 13, Issue 8
Nanostructured high-energy cathode materials for advanced lithium batteries
journal, October 2012
- Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo
- Nature Materials, Vol. 11, Issue 11
Direct observation of the partial formation of a framework structure for Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2 upon the first charge and discharge
journal, May 2011
- Ito, Atsushi; Shoda, Kaoru; Sato, Yuichi
- Journal of Power Sources, Vol. 196, Issue 10
Suppressed capacity/voltage fading of high-capacity lithium-rich layered materials via the design of heterogeneous distribution in the composition
journal, January 2014
- Yang, Xiukang; Wang, Di; Yu, Ruizhi
- Journal of Materials Chemistry A, Vol. 2, Issue 11
In situ Synchrotron X-ray Studies on Novel Mn Oxide Spinel Cathodes for Li-ion Batteries: Influence of Other Transition Elements
journal, January 1998
- Mukerjee, S.; Yang, X. Q.; Sun, X.
- MRS Proceedings, Vol. 548
Oxygen Nonstoichiometry and Phase Transitions in LiMn[sub 1.5]Ni[sub 0.5]O[sub 4−δ]
journal, January 2008
- Pasero, D.; Reeves, N.; Pralong, V.
- Journal of The Electrochemical Society, Vol. 155, Issue 4
Crystallinity Control of a Nanostructured LiNi0.5Mn1.5O4 Spinel via Polymer-Assisted Synthesis: A Method for Improving Its Rate Capability and Performance in 5 V Lithium Batteries
journal, September 2006
- Arrebola, J. C.; Caballero, A.; Cruz, M.
- Advanced Functional Materials, Vol. 16, Issue 14
Electrochemical kinetics of the 0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 ‘composite’ layered cathode material for lithium-ion batteries
journal, January 2012
- Yu, Haijun; Wang, Yarong; Asakura, Daisuke
- RSC Advances, Vol. 2, Issue 23
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries
journal, February 2006
- Kang, Kisuk; Shirley Meng, Ying; Breger, Julien
- Science, Vol. 311, Issue 5763, p. 977-980
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
LixNi0.25Mn0.75Oy (0.5 ≤x≤ 2, 2 ≤y≤ 2.75) compounds for high-energy lithium-ion batteries
journal, January 2009
- Deng, Haixia; Belharouak, Ilias; Sun, Yang-Kook
- Journal of Materials Chemistry, Vol. 19, Issue 26
Examining Hysteresis in Composite x Li 2 MnO 3 ·(1– x )LiMO 2 Cathode Structures
journal, March 2013
- Croy, Jason R.; Gallagher, Kevin G.; Balasubramanian, Mahalingam
- The Journal of Physical Chemistry C, Vol. 117, Issue 13
Understanding Li Diffusion in Li-Intercalation Compounds
journal, May 2012
- Van der Ven, Anton; Bhattacharya, Jishnu; Belak, Anna A.
- Accounts of Chemical Research, Vol. 46, Issue 5
Effect of (Al, Mg) substitution in LiNiO2 electrode for lithium batteries
journal, July 2006
- Kim, J.; Kim, B. H.; Baik, Y. H.
- Journal of Power Sources, Vol. 158, Issue 1
Crystal Habit-Tuned Nanoplate Material of Li[Li1/3-2x/3NixMn2/3-x/3]O2 for High-Rate Performance Lithium-Ion Batteries
journal, August 2010
- Wei, Guo-Zhen; Lu, Xia; Ke, Fu-Sheng
- Advanced Materials, Vol. 22, Issue 39
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
Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries
journal, January 2007
- Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S.
- Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125
Neutron Diffraction and Magnetic Susceptibility Studies on a High-Voltage Li 1.2 Mn 0.55 Ni 0.15 Co 0.10 O 2 Lithium Ion Battery Cathode: Insight into the Crystal Structure
journal, September 2013
- Mohanty, Debasish; Huq, Ashfia; Payzant, E. Andrew
- Chemistry of Materials, Vol. 25, Issue 20
Countering the Voltage Decay in High Capacity xLi 2 MnO 3 •(1–x)LiMO 2 Electrodes (M=Mn, Ni, Co) for Li + -Ion Batteries
journal, January 2012
- Croy, Jason R.; Kim, Donghan; Balasubramanian, Mahalingam
- Journal of The Electrochemical Society, Vol. 159, Issue 6
Comparative Study of LiNi 0.5 Mn 1.5 O 4 - δ and LiNi 0.5 Mn 1.5 O 4 Cathodes Having Two Crystallographic Structures: Fd 3̄ m and P 4 3 32
journal, March 2004
- Kim, J. -H.; Myung, S. -T.; Yoon, C. S.
- Chemistry of Materials, Vol. 16, Issue 5
High-energy cathode material for long-life and safe lithium batteries
journal, March 2009
- Sun, Yang-Kook; Myung, Seung-Taek; Park, Byung-Chun
- Nature Materials, Vol. 8, Issue 4
Migration of Mn cations in delithiated lithium manganese oxides
journal, January 2014
- Kan, Yongchun; Hu, Yuan; Lin, Chi-Kai
- Phys. Chem. Chem. Phys., Vol. 16, Issue 38
Atomic resolution of lithium ions in LiCoO2
journal, June 2003
- Shao-Horn, Yang; Croguennec, Laurence; Delmas, Claude
- Nature Materials, Vol. 2, Issue 7
Probing Thermally Induced Decomposition of Delithiated Li 1.2– x Ni 0.15 Mn 0.55 Co 0.1 O 2 by in Situ High-Energy X-ray Diffraction
journal, July 2014
- Lin, Chi-kai; Piao, Ying; Kan, Yongchun
- ACS Applied Materials & Interfaces, Vol. 6, Issue 15
Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study
journal, January 2013
- Mohanty, Debasish; Sefat, Athena S.; Li, Jianlin
- Physical Chemistry Chemical Physics, Vol. 15, Issue 44
Facile Synthesis of Hierarchical Micro/Nanostructured MnO Material and Its Excellent Lithium Storage Property and High Performance as Anode in a MnO/LiNi 0.5 Mn 1.5 O 4-δ Lithium Ion Battery
journal, June 2013
- Xu, Gui-Liang; Xu, Yue-Feng; Fang, Jun-Chuan
- ACS Applied Materials & Interfaces, Vol. 5, Issue 13
Stabilization of xLi2MnO3 ⋅ ( 1 − x ) LiMO2 Electrode Surfaces ( M = Mn , Ni , Co ) with Mildly Acidic, Fluorinated Solutions
journal, January 2008
- Kang, S.-H.; Thackeray, M. M.
- Journal of The Electrochemical Society, Vol. 155, Issue 4, p. A269-A275
The influence of compositional change of 0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (0.2≤x≤0.5, y=x−0.1) cathode materials prepared by co-precipitation
journal, April 2011
- Jeong, Ji-Hwa; Jin, Bong-Soo; Kim, Woo-Seong
- Journal of Power Sources, Vol. 196, Issue 7
Electronic properties of transition-metal oxides-II
journal, January 1957
- Dunitz, J. D.; Orgel, L. E.
- Journal of Physics and Chemistry of Solids, Vol. 3, Issue 3-4
Solid state synthesis of LiFePO4 studied by in situ high energy X-ray diffraction
journal, January 2011
- Chen, Zonghai; Ren, Yang; Qin, Yan
- Journal of Materials Chemistry, Vol. 21, Issue 15
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries
journal, December 2012
- Gu, Meng; Belharouak, Ilias; Zheng, Jianming
- ACS Nano, Vol. 7, Issue 1
Works referencing / citing this record:
Challenges in Developing Electrodes, Electrolytes, and Diagnostics Tools to Understand and Advance Sodium-Ion Batteries
journal, February 2018
- Xu, Gui-Liang; Amine, Rachid; Abouimrane, Ali
- Advanced Energy Materials, Vol. 8, Issue 14