Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress

Zachary W. Lebens-Higgins, Shawn Sallis, Nicholas V. Faenza, Fadwa Badway, Nathalie Pereira, David M. Halat, Matthew Wahila, Christoph Schlueter, Tien Lin Lee, Wanli Yang, Clare P. Grey, Glenn Amatucci, Louis F.J. Piper

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode-electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li2CO3, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques, we study the evolution of these CEI species as a function of electrochemical and thermal stress for LiNi0.8Co0.15Al0.05O2 (NCA) particle electrodes using a LiPF6 ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li2CO3 and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF6 breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling.

Original languageEnglish (US)
Pages (from-to)958-969
Number of pages12
JournalChemistry of Materials
Volume30
Issue number3
DOIs
StatePublished - Feb 13 2018

Fingerprint

Thermal stress
Electrolytes
Cathodes
Electrodes
Carbonates
Salts
Electric potential
Oxides
Nuclear magnetic resonance spectroscopy
Metal ions
Ethylene
Metals
Decomposition
Degradation
X rays
Temperature

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Lebens-Higgins, Z. W., Sallis, S., Faenza, N. V., Badway, F., Pereira, N., Halat, D. M., ... Piper, L. F. J. (2018). Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress. Chemistry of Materials, 30(3), 958-969. https://doi.org/10.1021/acs.chemmater.7b04782
Lebens-Higgins, Zachary W. ; Sallis, Shawn ; Faenza, Nicholas V. ; Badway, Fadwa ; Pereira, Nathalie ; Halat, David M. ; Wahila, Matthew ; Schlueter, Christoph ; Lee, Tien Lin ; Yang, Wanli ; Grey, Clare P. ; Amatucci, Glenn ; Piper, Louis F.J. / Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress. In: Chemistry of Materials. 2018 ; Vol. 30, No. 3. pp. 958-969.
@article{8a4524c0ab4d43c69f404ce3bcf50838,
title = "Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress",
abstract = "For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode-electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li2CO3, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques, we study the evolution of these CEI species as a function of electrochemical and thermal stress for LiNi0.8Co0.15Al0.05O2 (NCA) particle electrodes using a LiPF6 ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li2CO3 and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF6 breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling.",
author = "Lebens-Higgins, {Zachary W.} and Shawn Sallis and Faenza, {Nicholas V.} and Fadwa Badway and Nathalie Pereira and Halat, {David M.} and Matthew Wahila and Christoph Schlueter and Lee, {Tien Lin} and Wanli Yang and Grey, {Clare P.} and Glenn Amatucci and Piper, {Louis F.J.}",
year = "2018",
month = "2",
day = "13",
doi = "https://doi.org/10.1021/acs.chemmater.7b04782",
language = "English (US)",
volume = "30",
pages = "958--969",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "3",

}

Lebens-Higgins, ZW, Sallis, S, Faenza, NV, Badway, F, Pereira, N, Halat, DM, Wahila, M, Schlueter, C, Lee, TL, Yang, W, Grey, CP, Amatucci, G & Piper, LFJ 2018, 'Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress', Chemistry of Materials, vol. 30, no. 3, pp. 958-969. https://doi.org/10.1021/acs.chemmater.7b04782

Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress. / Lebens-Higgins, Zachary W.; Sallis, Shawn; Faenza, Nicholas V.; Badway, Fadwa; Pereira, Nathalie; Halat, David M.; Wahila, Matthew; Schlueter, Christoph; Lee, Tien Lin; Yang, Wanli; Grey, Clare P.; Amatucci, Glenn; Piper, Louis F.J.

In: Chemistry of Materials, Vol. 30, No. 3, 13.02.2018, p. 958-969.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Evolution of the Electrode-Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress

AU - Lebens-Higgins, Zachary W.

AU - Sallis, Shawn

AU - Faenza, Nicholas V.

AU - Badway, Fadwa

AU - Pereira, Nathalie

AU - Halat, David M.

AU - Wahila, Matthew

AU - Schlueter, Christoph

AU - Lee, Tien Lin

AU - Yang, Wanli

AU - Grey, Clare P.

AU - Amatucci, Glenn

AU - Piper, Louis F.J.

PY - 2018/2/13

Y1 - 2018/2/13

N2 - For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode-electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li2CO3, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques, we study the evolution of these CEI species as a function of electrochemical and thermal stress for LiNi0.8Co0.15Al0.05O2 (NCA) particle electrodes using a LiPF6 ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li2CO3 and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF6 breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling.

AB - For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode-electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li2CO3, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques, we study the evolution of these CEI species as a function of electrochemical and thermal stress for LiNi0.8Co0.15Al0.05O2 (NCA) particle electrodes using a LiPF6 ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li2CO3 and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF6 breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling.

UR - http://www.scopus.com/inward/record.url?scp=85042036558&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042036558&partnerID=8YFLogxK

U2 - https://doi.org/10.1021/acs.chemmater.7b04782

DO - https://doi.org/10.1021/acs.chemmater.7b04782

M3 - Article

VL - 30

SP - 958

EP - 969

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 3

ER -