Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High‐Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode Materials

Abstract

In the spinel oxide cathode family, LiNi0.5Mn1.5O4 (LNMO) shows a high operating voltage (≈4.7 V vs Li/Li+) and excellent Li-ion mobility with stable 3D conducting channels. Ni/Mn cation disordered and ordered phases usually coexist in LNMO materials, and they have distinct structural and electrochemical properties, resulting in different battery performances for LNMO materials with different phase compositions. Identifying the correlation between phase compositions and electrochemical properties is of significance to the improvement of battery performance and understanding of degradation mechanisms. Herein, the disordered/ordered phase compositions in LNMO materials are tailored by post-annealing strategies and their impacts on electrochemical performance and degradation mechanisms from the surface to the bulk are systematically investigated. The ordered phase increases rapidly as Mn3+ is oxidized to Mn4+ through a post-annealing process. LNMO with an intermediate fraction of disordered and ordered phases gives rise to improved cycling stability. This article further reports that a high ordered phase fraction can preferentially protect Ni from dissolution during cycling. However, these results suggest that the transition metal dissolution and surface structural change of LNMO do not exhibit a direct correlation with cycling stability. These results indicate the capacity fading mainly correlates with the bulk structural distortion, leading to decreasedmore » Li-ion kinetics.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [2];  [2];  [3];  [4];  [4];  [5];  [6];  [7];  [7]; ORCiD logo [2]
+ Show Author Affiliations
  1. Department of Chemistry Virginia Tech Blacksburg VA 24061 USA, Institute of New Energy for Vehicles School of Materials Science and Engineering Tongji University Shanghai 201804 China
  2. Department of Chemistry Virginia Tech Blacksburg VA 24061 USA
  3. Neutron Scattering Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA
  4. Advanced Photon Source Argonne National Laboratory Argonne IL 60439 USA
  5. Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Menlo Park CA 94025 USA, Microelectronics Research Unit Faculty of Information Technology and Electrical Engineering University of Oulu P.O. Box. 4500 Oulu 90570 Finland
  6. Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Menlo Park CA 94025 USA
  7. Institute of New Energy for Vehicles School of Materials Science and Engineering Tongji University Shanghai 201804 China
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; Walter Ahlstrom Foundation; European Union's Horizon 2020
OSTI Identifier:
1846701
Alternate Identifier(s):
OSTI ID: 1846703; OSTI ID: 1867418; OSTI ID: 1902253
Grant/Contract Number:  
AC02-76SF00515; AC05-00OR22725; AC02-06CH11357; AC02-05CH11231; 841621
Resource Type:
Published Article
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Name: Advanced Functional Materials Journal Volume: 32 Journal Issue: 21; Journal ID: ISSN 1616-301X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English
Subject:
36 MATERIALS SCIENCE; cycle life; disorder-to-order transition; fading mechanism; metal; dissolution; spinel cathodes; metal dissolution; spinel cathode

Citation Formats

Sun, Huabin, Hu, Anyang, Spence, Stephanie, Kuai, Chunguang, Hou, Dong, Mu, Linqin, Liu, Jue, Li, Luxi, Sun, Chengjun, Sainio, Sami, Nordlund, Dennis, Luo, Wei, Huang, Yunhui, and Lin, Feng. Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High‐Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode Materials. Germany: N. p., 2022. Web. doi:10.1002/adfm.202112279.
Copy to clipboard
Sun, Huabin, Hu, Anyang, Spence, Stephanie, Kuai, Chunguang, Hou, Dong, Mu, Linqin, Liu, Jue, Li, Luxi, Sun, Chengjun, Sainio, Sami, Nordlund, Dennis, Luo, Wei, Huang, Yunhui, & Lin, Feng. Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High‐Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode Materials. Germany. https://doi.org/10.1002/adfm.202112279
Copy to clipboard
Sun, Huabin, Hu, Anyang, Spence, Stephanie, Kuai, Chunguang, Hou, Dong, Mu, Linqin, Liu, Jue, Li, Luxi, Sun, Chengjun, Sainio, Sami, Nordlund, Dennis, Luo, Wei, Huang, Yunhui, and Lin, Feng. Sat . "Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High‐Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode Materials". Germany. https://doi.org/10.1002/adfm.202112279.
Copy to clipboard
@article{osti_1846701,
title = {Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High‐Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode Materials},
author = {Sun, Huabin and Hu, Anyang and Spence, Stephanie and Kuai, Chunguang and Hou, Dong and Mu, Linqin and Liu, Jue and Li, Luxi and Sun, Chengjun and Sainio, Sami and Nordlund, Dennis and Luo, Wei and Huang, Yunhui and Lin, Feng},
abstractNote = {In the spinel oxide cathode family, LiNi0.5Mn1.5O4 (LNMO) shows a high operating voltage (≈4.7 V vs Li/Li+) and excellent Li-ion mobility with stable 3D conducting channels. Ni/Mn cation disordered and ordered phases usually coexist in LNMO materials, and they have distinct structural and electrochemical properties, resulting in different battery performances for LNMO materials with different phase compositions. Identifying the correlation between phase compositions and electrochemical properties is of significance to the improvement of battery performance and understanding of degradation mechanisms. Herein, the disordered/ordered phase compositions in LNMO materials are tailored by post-annealing strategies and their impacts on electrochemical performance and degradation mechanisms from the surface to the bulk are systematically investigated. The ordered phase increases rapidly as Mn3+ is oxidized to Mn4+ through a post-annealing process. LNMO with an intermediate fraction of disordered and ordered phases gives rise to improved cycling stability. This article further reports that a high ordered phase fraction can preferentially protect Ni from dissolution during cycling. However, these results suggest that the transition metal dissolution and surface structural change of LNMO do not exhibit a direct correlation with cycling stability. These results indicate the capacity fading mainly correlates with the bulk structural distortion, leading to decreased Li-ion kinetics.},
doi = {10.1002/adfm.202112279},
journal = {Advanced Functional Materials},
number = 21,
volume = 32,
place = {Germany},
year = {Sat Feb 26 00:00:00 EST 2022},
month = {Sat Feb 26 00:00:00 EST 2022}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/adfm.202112279
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
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:

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, October 2015

Stabilization of a High-Capacity and High-Power Nickel-Based Cathode for Li-Ion Batteries
journal, April 2018

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015

Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides
journal, September 2020

Mapping Lattice Distortions in LiNi 0.5 Mn 1.5 O 4 Cathode Materials
journal, January 2022

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes
journal, January 2020

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018

A comparative study of Fd-3m and P4332 “LiNi0.5Mn1.5O4”
journal, June 2011

Stability and Li+ extraction/adsorption properties of LiMxMn2−xO4 (M=Ni, Al, Ti; 0≤x≤1) in aqueous solution
journal, October 2010

  • Ma, Li-Wen; Chen, Bai-Zhen; Shi, Xi-Chang
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 369, Issue 1-3
  • DOI: 10.1016/j.colsurfa.2010.08.016

Nanoscale Ni/Mn Ordering in the High Voltage Spinel Cathode LiNi 0.5 Mn 1.5 O 4
journal, September 2016

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
  • DOI: 10.1021/cm301148d

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
  • DOI: 10.1021/cm501203r

Oxygen Vacancies and Ordering of d-levels Control Voltage Suppression in Oxide Cathodes: the Case of Spinel LiNi 0.5 Mn 1.5 O 4- δ
journal, June 2013

  • Sushko, Peter V.; Rosso, Kevin M.; Zhang, Ji-Guang
  • Advanced Functional Materials, Vol. 23, Issue 44
  • DOI: 10.1002/adfm.201301205

High Rate Micron-Sized Ordered LiNi[sub 0.5]Mn[sub 1.5]O[sub 4]
journal, January 2010

  • Ma, Xiaohua; Kang, Byoungwoo; Ceder, Gerbrand
  • Journal of The Electrochemical Society, Vol. 157, Issue 8
  • DOI: 10.1149/1.3439678

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
  • DOI: 10.1039/C6CS00875E

Crystal structure and cathode performance dependence on oxygen content of LiMn1.5Ni0.5O4 as a cathode material for secondary lithium batteries
journal, June 2003

Challenges and Strategies to Advance High‐Energy Nickel‐Rich Layered Lithium Transition Metal Oxide Cathodes for Harsh Operation
journal, September 2020

  • Xu, Gui‐Liang; Liu, Xiang; Daali, Amine
  • Advanced Functional Materials, Vol. 30, Issue 46
  • DOI: 10.1002/adfm.202004748

Reversible Mn/Cr dual redox in cation-disordered Li-excess cathode materials for stable lithium ion batteries
journal, June 2021

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries
journal, September 2017

Unravelling the Impact of Reaction Paths on Mechanical Degradation of Intercalation Cathodes for Lithium-Ion Batteries
journal, October 2015

  • Li, Juchuan; Zhang, Qinglin; Xiao, Xingcheng
  • Journal of the American Chemical Society, Vol. 137, Issue 43
  • DOI: 10.1021/jacs.5b06178

Cycling and storage performance at elevated temperatures of LiNi0.5Mn1.5O4 positive electrodes for advanced 5 V Li-ion batteries
journal, August 2004

EXPGUI , a graphical user interface for GSAS
journal, April 2001

30 Years of Lithium-Ion Batteries
journal, June 2018

Ab Initio Modeling of Transition Metal Dissolution from the LiNi 0.5 Mn 1.5 O 4 Cathode
journal, May 2019

  • Intan, Nadia N.; Klyukin, Konstantin; Alexandrov, Vitaly
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 22
  • DOI: 10.1021/acsami.9b06010

Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials
journal, January 2020

Role of Cation Ordering and Surface Segregation in High-Voltage Spinel LiMn 1.5 Ni 0.5– x M x O 4 (M = Cr, Fe, and Ga) Cathodes for Lithium-Ion Batteries
journal, September 2012

  • Shin, Dong Wook; Bridges, Craig A.; Huq, Ashfia
  • Chemistry of Materials, Vol. 24, Issue 19
  • DOI: 10.1021/cm301844w

High-Performance LiNi 0.5 Mn 1.5 O 4 Spinel Controlled by Mn 3+ Concentration and Site Disorder
journal, March 2012

The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • DOI: 10.1016/j.nimb.2012.05.037

Prospect and Reality of Ni-Rich Cathode for Commercialization
journal, November 2017

  • Kim, Junhyeok; Lee, Hyomyung; Cha, Hyungyeon
  • Advanced Energy Materials, Vol. 8, Issue 6
  • DOI: 10.1002/aenm.201702028

Research progress in high voltage spinel LiNi0.5Mn1.5O4 material
journal, September 2010

Impact of P-Doped in Spinel LiNi 0.5 Mn 1.5 O 4 on Degree of Disorder, Grain Morphology, and Electrochemical Performance
journal, November 2015

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
  • DOI: 10.1021/cm301825h

Synthesis and Electrochemistry of LiNi[sub x]Mn[sub 2−x]O[sub 4]
journal, January 1997

  • Zhong, Qiming
  • Journal of The Electrochemical Society, Vol. 144, Issue 1
  • DOI: 10.1149/1.1837386

Design of Nickel-rich Layered Oxides Using d Electronic Donor for Redox Reactions
journal, September 2015

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
  • DOI: 10.1021/cm035050s

A High‐Performance Li–Mn–O Li‐rich Cathode Material with Rhombohedral Symmetry via Intralayer Li/Mn Disordering
journal, March 2020

The Formation Mechanism of Fluorescent Metal Complexes at the Li x Ni 0.5 Mn 1.5 O 4−δ /Carbonate Ester Electrolyte Interface
journal, March 2015

  • Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang
  • Journal of the American Chemical Society, Vol. 137, Issue 10
  • DOI: 10.1021/ja5116698

Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials
journal, April 2021

Understanding Transition-Metal Dissolution Behavior in LiNi 0.5 Mn 1.5 O 4 High-Voltage Spinel for Lithium Ion Batteries
journal, July 2013

  • Pieczonka, Nicholas P. W.; Liu, Zhongyi; Lu, Peng
  • The Journal of Physical Chemistry C, Vol. 117, Issue 31
  • DOI: 10.1021/jp405158m

Preparation of a new crystal form of manganese dioxide: λ-MnO2
journal, September 1981

Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives
journal, October 2015

  • Manthiram, Arumugam; Knight, James C.; Myung, Seung-Taek
  • Advanced Energy Materials, Vol. 6, Issue 1
  • DOI: 10.1002/aenm.201501010

A review of Ni-based layered oxides for rechargeable Li-ion batteries
journal, January 2017

  • Xu, Jing; Lin, Feng; Doeff, Marca M.
  • Journal of Materials Chemistry A, Vol. 5, Issue 3
  • DOI: 10.1039/C6TA07991A

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
  • DOI: 10.1039/C2TA00212D
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: