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Title: Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides

Abstract

Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2 ) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dVdxLi) is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand and quantify the voltage slope of cation-disordered LiMO 2 . We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of high-voltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for high-voltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. Finally, our analysismore » shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Li-excess compounds than in stoichiometric LiMO 2 compounds.« less

Authors:
 [1];  [2];  [1];  [2]
  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02141, United States
  2. Department of Materials Science and Engineering, UC Berkeley, Berkeley, California 94720, United States, Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1275964
Alternate Identifier(s):
OSTI ID: 1288659; OSTI ID: 1454481
Grant/Contract Number:  
SC0012583; SC0001294; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Name: Chemistry of Materials Journal Volume: 28 Journal Issue: 15; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Abdellahi, Aziz, Urban, Alexander, Dacek, Stephen, and Ceder, Gerbrand. Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.chemmater.6b01438.
Abdellahi, Aziz, Urban, Alexander, Dacek, Stephen, & Ceder, Gerbrand. Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides. United States. https://doi.org/10.1021/acs.chemmater.6b01438
Abdellahi, Aziz, Urban, Alexander, Dacek, Stephen, and Ceder, Gerbrand. Mon . "Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides". United States. https://doi.org/10.1021/acs.chemmater.6b01438.
@article{osti_1275964,
title = {Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides},
author = {Abdellahi, Aziz and Urban, Alexander and Dacek, Stephen and Ceder, Gerbrand},
abstractNote = {Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2 ) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dVdxLi) is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand and quantify the voltage slope of cation-disordered LiMO 2 . We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of high-voltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for high-voltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. Finally, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Li-excess compounds than in stoichiometric LiMO 2 compounds.},
doi = {10.1021/acs.chemmater.6b01438},
journal = {Chemistry of Materials},
number = 15,
volume = 28,
place = {United States},
year = {2016},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.chemmater.6b01438

Citation Metrics:
Cited by: 4 works
Citation information provided by
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Works referencing / citing this record:

Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials
journal, October 2017

  • Richards, William D.; Dacek, Stephen T.; Kitchaev, Daniil A.
  • Advanced Energy Materials, Vol. 8, Issue 5
  • DOI: 10.1002/aenm.201701533

Reversible Delithiation of Disordered Rock Salt LiVO 2
journal, April 2018

  • Baur, Christian; Chable, Johann; Klein, Franziska
  • ChemElectroChem, Vol. 5, Issue 11
  • DOI: 10.1002/celc.201800189

Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials
journal, April 2018


Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes
journal, January 2018

  • Kitchaev, Daniil A.; Lun, Zhengyan; Richards, William D.
  • Energy & Environmental Science, Vol. 11, Issue 8
  • DOI: 10.1039/c8ee00816g

Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes
journal, January 2020

  • Clément, R. J.; Lun, Z.; Ceder, G.
  • Energy & Environmental Science, Vol. 13, Issue 2
  • DOI: 10.1039/c9ee02803j

Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes
journal, January 2019

  • Baur, Christian; Källquist, Ida; Chable, Johann
  • Journal of Materials Chemistry A, Vol. 7, Issue 37
  • DOI: 10.1039/c9ta06291b

Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes
journal, January 2019

  • Naylor, Andrew J.; Makkos, Eszter; Maibach, Julia
  • Journal of Materials Chemistry A, Vol. 7, Issue 44
  • DOI: 10.1039/c9ta09019c

CLEASE: a versatile and user-friendly implementation of cluster expansion method
journal, May 2019

  • Chang, Jin Hyun; Kleiven, David; Melander, Marko
  • Journal of Physics: Condensed Matter, Vol. 31, Issue 32
  • DOI: 10.1088/1361-648x/ab1bbc