Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

Sha Tan; Dacheng Kuai; Zhiao Yu; Saul Perez-Beltran; Muhammad Mominur Rahman; Kangxuan Xia; Nan Wang; Yuelang Chen; Xiao Qing Yang; Jie Xiao; Jun Liu; Yi Cui; Zhenan Bao; Perla B. Balbuena; Enyuan Hu

doi:10.1021/jacs.3c14232

Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

Sha Tan
, Dacheng Kuai
, Zhiao Yu
, Saul Perez-Beltran
, Muhammad Mominur Rahman
, Kangxuan Xia
, Nan Wang
, Yuelang Chen
, Xiao Qing Yang
, Jie Xiao
, Jun Liu
, Yi Cui
, Zhenan Bao
, Perla B. Balbuena
, Enyuan Hu

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li₂O and LiF first increases and then decreases during cycling, suggesting suppressed Li₂O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li₂O encourages solvent decomposition by facilitating solvent adsorption on Li₂O which is followed by concurrent depletion of both. This work highlights the important role of Li₂O in transitioning from an anion-derived interphase to a solvent-derived one.

Original language	English
Pages (from-to)	11711-11718
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	146
Issue number	17
DOIs	https://doi.org/10.1021/jacs.3c14232
State	Published - May 1 2024
Externally published	Yes

Funding

The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract no. DE-SC0012704. This research used beamlines 28-ID-2, 23-ID-2, and 8-BM of the National Synchrotron Light Source II, a US DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. The cathode electrodes were provided by Cell Analysis, Modeling, and Prototyping (CAMP) Facility at Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office. The computational studies were supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium phase 2) under DOE contract no. DE-AC05-76RL01830 from the Pacific Northwest National Laboratory (PNNL). Computational resources from the Texas A&M University High Performance Research Computing are gratefully acknowledged.

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10.1021/jacs.3c14232

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Tan, S., Kuai, D., Yu, Z., Perez-Beltran, S., Rahman, M. M., Xia, K., Wang, N., Chen, Y., Yang, X. Q., Xiao, J., Liu, J., Cui, Y., Bao, Z., Balbuena, P. B., & Hu, E. (2024). Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies. Journal of the American Chemical Society, 146(17), 11711-11718. https://doi.org/10.1021/jacs.3c14232

@article{0c7817a552cb4692b490c58934af6ee9,

title = "Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies",

abstract = "Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li2O and LiF first increases and then decreases during cycling, suggesting suppressed Li2O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li2O encourages solvent decomposition by facilitating solvent adsorption on Li2O which is followed by concurrent depletion of both. This work highlights the important role of Li2O in transitioning from an anion-derived interphase to a solvent-derived one.",

author = "Sha Tan and Dacheng Kuai and Zhiao Yu and Saul Perez-Beltran and Rahman, \{Muhammad Mominur\} and Kangxuan Xia and Nan Wang and Yuelang Chen and Yang, \{Xiao Qing\} and Jie Xiao and Jun Liu and Yi Cui and Zhenan Bao and Balbuena, \{Perla B.\} and Enyuan Hu",

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doi = "10.1021/jacs.3c14232",

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Tan, S, Kuai, D, Yu, Z, Perez-Beltran, S, Rahman, MM, Xia, K, Wang, N, Chen, Y, Yang, XQ, Xiao, J, Liu, J, Cui, Y, Bao, Z, Balbuena, PB & Hu, E 2024, 'Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies', Journal of the American Chemical Society, vol. 146, no. 17, pp. 11711-11718. https://doi.org/10.1021/jacs.3c14232

TY - JOUR

T1 - Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

AU - Tan, Sha

AU - Kuai, Dacheng

AU - Yu, Zhiao

AU - Perez-Beltran, Saul

AU - Rahman, Muhammad Mominur

AU - Xia, Kangxuan

AU - Wang, Nan

AU - Chen, Yuelang

AU - Yang, Xiao Qing

AU - Xiao, Jie

AU - Liu, Jun

AU - Cui, Yi

AU - Bao, Zhenan

AU - Balbuena, Perla B.

AU - Hu, Enyuan

PY - 2024/5/1

Y1 - 2024/5/1

N2 - Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li2O and LiF first increases and then decreases during cycling, suggesting suppressed Li2O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li2O encourages solvent decomposition by facilitating solvent adsorption on Li2O which is followed by concurrent depletion of both. This work highlights the important role of Li2O in transitioning from an anion-derived interphase to a solvent-derived one.

AB - Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of the lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron X-ray, which has the unique capability of analyzing crystalline/amorphous phases quantitatively with statistical significance, we study the composition and dynamics of the LMB interphase for a newly developed important LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential roles of the anion and solvent in interphase formation during cycling. The relative ratio between Li2O and LiF first increases and then decreases during cycling, suggesting suppressed Li2O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barriers in many-electron transfer. In long extended cycles, the anion decomposition product Li2O encourages solvent decomposition by facilitating solvent adsorption on Li2O which is followed by concurrent depletion of both. This work highlights the important role of Li2O in transitioning from an anion-derived interphase to a solvent-derived one.

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EP - 11718

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 17

ER -

Evolution and Interplay of Lithium Metal Interphase Components Revealed by Experimental and Theoretical Studies

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