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Pathway of in situ polymerization of 1,3-dioxolane in LiP₆ electrolyte on Li metal anode

Xie, M. and Wu, Y. and Liu, Y. and Yu, P. P. and Jia, R. and Goddard, W. A., III and Cheng, T. (2021) Pathway of in situ polymerization of 1,3-dioxolane in LiP₆ electrolyte on Li metal anode. Materials Today Energy, 21 . Art. No. 100730. ISSN 2468-6069. https://resolver.caltech.edu/CaltechAUTHORS:20210423-164850772

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Abstract

Although the lithium metal battery has been considered to be one of the most promising candidates to facilitate high-density energy storage, the practical applications of lithium metal anodes are significantly hindered by its high reactivity. Electrolytes based on 1,3-dioxolane (DOL) have been demonstrated to be one of the most effective electrolytes that can suppress side reactions, but the underlying mechanism is still far from clear. In this work, we carried out multi-scale simulations that combine density functional theory (DFT) and reactive force field (ReaxFF) to investigate the initial reactions of 1.0 M LiPF₆ salt in DOL with Li metal anode. Our simulation results reveal that PF₆⁻ anions can either fully decompose via reduction reaction when they directly in contact with Li anode or convert to PF₅ when they stay in bulk. While the decomposition products (F⁻ and Pₓ⁻) contribute to the formation of the inorganic part of the solid electrolyte interphase (SEI), the latter PF₅ can serve as an initiator of the polymerization of DOL. Such polymerization of the electrolyte provides an unexpected protective effect that resembles the polymer electrolyte but is formed in situ. The most kinetically favorable polymerization pathway is then distinguished from hybrid functional DFT calculations, which confirms that PF₅ plays an important role in activating the DOL ring for further polymerization. The insights revealed from this work should be of help to expedite the rational design of electrolytes that provide protective SEI to stabilize Li anode.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.mtener.2021.100730DOIArticle
ORCID:
AuthorORCID
Xie, M.0000-0002-9797-1449
Jia, R.0000-0002-3722-1195
Goddard, W. A., III0000-0003-0097-5716
Cheng, T.0000-0003-4830-177X
Alternate Title:Pathway of in situ polymerization of 1,3-dioxolane in LiPF6 electrolyte on Li metal anode
Additional Information:© 2021 Elsevier. Received 4 March 2021, Revised 18 March 2021, Accepted 20 March 2021, Available online 26 March 2021. T.C. and M.X. thank the National Natural Science Foundation of China (21903058 and 22003044), the Natural Science Foundation of Jiangsu Higher Education Institutions (SBK20190810), the Jiangsu Province High-Level Talents (JNHB-106), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) for financial support. WAG gratefully acknowledges support from NSF (CBET-1805022). Credit author statement. Xie Miao, Goddard III William A and Cheng Tao: Conceptualization. Xie Miao, Wu Yu, Liu Yue, Peiping: Investigation. All authors: Writing - Original Draft. All authors: Writing - Review & Editing. Goddard III William A and Cheng Tao: Supervision. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China21903058
National Natural Science Foundation of China22003044
Natural Science Foundation of Jiangsu Higher Education InstitutionsSBK20190810
Jiangsu Province High-Level TalentsJNHB-106
Priority Academic Program Development of Jiangsu Higher Education InstitutionsUNSPECIFIED
NSFCBET-1805022
Subject Keywords:Battery; SEI; Computational modeling; DFT; Electrolyte
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1426
Record Number:CaltechAUTHORS:20210423-164850772
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210423-164850772
Official Citation:M. Xie, Y. Wu, Y. Liu, P.P. Yu, R. Jia, W.A. Goddard, T. Cheng, Pathway of in situ polymerization of 1,3-dioxolane in LiPF6 electrolyte on Li metal anode, Materials Today Energy, Volume 21, 2021, 100730, ISSN 2468-6069, https://doi.org/10.1016/j.mtener.2021.100730.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108823
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:28 Apr 2021 14:15
Last Modified:06 Jun 2021 04:28

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