In situ stress measurements during electrochemical cycling of lithium-rich cathodes

Leah Nation, Juchuan Li, Christine James, Yue Qi, Nancy Dudney, Brian W. Sheldon

Research output: Contribution to journalArticle

Abstract

Layered lithium transition metal oxides (Li1+xM1-xO2, M = Ni, Mn, Co) are attractive cathode materials for lithium-ion batteries due to their high reversible capacity. However, they suffer from structural changes that lead to substantial voltage fade. In this study, we use stress as a novel way to track irreversible changes in Li1.2Mn0.55Ni0.125Co0.125O2 (LR-NMC) cathodes. A unique and unpredicted stress signature is observed during the first delithiation. Initially, a tensile stress is observed, consistent with volume contraction from lithium removal, however, the stress reverses and becomes compressive with continued charging beyond 4 V vs Li/Li+, indicating volume expansion; this phenomenon is present in the first cycle only. This irreversible stress during delithiation is likely to be at least partially due to oxygen loss and the resulting cation rearrangement. Raman spectroscopy provides evidence of the layered-to-spinel phase transition after cycling in the LR-NMC films, as well as recovery of the original spectra upon re-annealing in an oxygen environment.

Original languageEnglish (US)
Pages (from-to)383-391
Number of pages9
JournalJournal of Power Sources
Volume364
DOIs
StatePublished - Oct 1 2017

Profile

lithium
Addison Disease
cathodes
cycles
Coumestrol
Lithium
Cathodes
oxygen
Oxygen
stress measurement
tensile stress
contraction
spinel
metal oxides
charging
electric batteries
Raman spectroscopy
transition metals
recovery
signatures

Keywords

  • Battery
  • Layered lithium-rich oxide
  • Oxygen loss
  • Thin film stress

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering

Cite this

In situ stress measurements during electrochemical cycling of lithium-rich cathodes. / Nation, Leah; Li, Juchuan; James, Christine; Qi, Yue; Dudney, Nancy; Sheldon, Brian W.

In: Journal of Power Sources, Vol. 364, 01.10.2017, p. 383-391.

Research output: Contribution to journalArticle

Nation L, Li J, James C, Qi Y, Dudney N, Sheldon BW. In situ stress measurements during electrochemical cycling of lithium-rich cathodes. Journal of Power Sources. 2017 Oct 1;364:383-391. Available from, DOI: 10.1016/j.jpowsour.2017.08.006

Nation, Leah; Li, Juchuan; James, Christine; Qi, Yue; Dudney, Nancy; Sheldon, Brian W. / In situ stress measurements during electrochemical cycling of lithium-rich cathodes.

In: Journal of Power Sources, Vol. 364, 01.10.2017, p. 383-391.

Research output: Contribution to journalArticle

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AU - Sheldon,Brian W.

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AB - Layered lithium transition metal oxides (Li1+xM1-xO2, M = Ni, Mn, Co) are attractive cathode materials for lithium-ion batteries due to their high reversible capacity. However, they suffer from structural changes that lead to substantial voltage fade. In this study, we use stress as a novel way to track irreversible changes in Li1.2Mn0.55Ni0.125Co0.125O2 (LR-NMC) cathodes. A unique and unpredicted stress signature is observed during the first delithiation. Initially, a tensile stress is observed, consistent with volume contraction from lithium removal, however, the stress reverses and becomes compressive with continued charging beyond 4 V vs Li/Li+, indicating volume expansion; this phenomenon is present in the first cycle only. This irreversible stress during delithiation is likely to be at least partially due to oxygen loss and the resulting cation rearrangement. Raman spectroscopy provides evidence of the layered-to-spinel phase transition after cycling in the LR-NMC films, as well as recovery of the original spectra upon re-annealing in an oxygen environment.

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