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Predicted Operando Polymerization at Lithium Anode via Boron Insertion

Liu, Yue and Yu, Peiping and Sun, Qintao and Wu, Yu and Xie, Miao and Yang, Hao and Cheng, Tao and Goddard, William A., III (2021) Predicted Operando Polymerization at Lithium Anode via Boron Insertion. ACS Energy Letters, 6 (6). pp. 2320-2327. ISSN 2380-8195. doi:10.1021/acsenergylett.1c00907. https://resolver.caltech.edu/CaltechAUTHORS:20210604-111532154

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Abstract

Concentrated dual-salt/ester systems have been demonstrated as an effective method in regulating the solid electrolyte interphase (SEI) formation that facilitates the long-term cycling stability of lithium metal batteries (LMBs). However, the atomic mechanism of the dual-salt enabling the stable SEI formation remains unclear. In this work, a hybrid scheme, combining ab initio and reactive force field methods (HAIR), is employed to investigate the initial reaction of SEI formation by monitoring 1 ns molecular dynamics (MD) simulation. The simulation results reveal that lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is subject to a sacrificial decomposition to protect lithium difluoro(oxalato)borate (LiDFOB) from being over-reduced by Li metal. The boron (B) released from LiDFOB can initiate a polymerization reaction by cutting the C–O bond. Such unexpected reaction turns dimethoxyethane (DME), a previously considered stable solvent, into a radical that can facilitate the propagation of polymerization. These insights from simulation provide atomic understanding about the complex reaction in SEI.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acsenergylett.1c00907DOIArticle
ORCID:
AuthorORCID
Xie, Miao0000-0002-9797-1449
Yang, Hao0000-0002-8241-6231
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2021 American Chemical Society. Received: May 2, 2021; Accepted: May 27, 2021; Published: June 1, 2021. T.C. and M.X. thank the National Natural Science Foundation of China (Grants 21903058 and 22003044), the Natural Science Foundation of Jiangsu Higher Education Institutions (Grant SBK20190810), the Jiangsu Province High-Level Talents (Grant JNHB-106), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) for financial support. H.Y. thanks China Postdoctoral Science Foundation (Grant 2019M660128) for financial support. This work was partly supported by the Collaborative Innovation Center of Suzhou Nano Science & Technology. W.A.G. gratefully acknowledges support from NSF (Grant CBET-1805022). We thank Dr. Shuhong Jiao and Ruiguo Cao for fruitful discussions about the experiments. The authors declare no competing financial interest.
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
China Postdoctoral Science Foundation2019M660128
Collaborative Innovation Center of Suzhou Nano Science and TechnologyUNSPECIFIED
NSFCBET-1805022
Subject Keywords:Organic reactions, Surface chemistry, Boron, Electrolytes, Ab initio molecular dynamics
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1467
Issue or Number:6
DOI:10.1021/acsenergylett.1c00907
Record Number:CaltechAUTHORS:20210604-111532154
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210604-111532154
Official Citation:Predicted Operando Polymerization at Lithium Anode via Boron Insertion. Yue Liu, Peiping Yu, Qintao Sun, Yu Wu, Miao Xie, Hao Yang, Tao Cheng, and William A. Goddard. ACS Energy Letters 2021 6 (6), 2320-2327; DOI: 10.1021/acsenergylett.1c00907
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109376
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:07 Jun 2021 15:22
Last Modified:23 Jun 2021 18:05

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