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Published June 11, 2021 | Supplemental Material
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Predicted Operando Polymerization at Lithium Anode via Boron Insertion

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.

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.

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August 20, 2023
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