Predicted Operando Polymerization at Lithium Anode via Boron Insertion
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...
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| Published in | ACS energy letters Vol. 6; no. 6; pp. 2320 - 2327 |
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| Main Authors | , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
American Chemical Society
11.06.2021
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| Online Access | Get full text |
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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. |
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| AbstractList | 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. |
| Author | Sun, Qintao Xie, Miao Wu, Yu Yu, Peiping Liu, Yue Yang, Hao Goddard, William A Cheng, Tao |
| AuthorAffiliation | Institute of Functional Nano and Soft Materials (FUNSOM) Materials and Process Simulation Center, Department of Chemistry |
| AuthorAffiliation_xml | – name: Materials and Process Simulation Center, Department of Chemistry – name: Institute of Functional Nano and Soft Materials (FUNSOM) |
| Author_xml | – sequence: 1 givenname: Yue surname: Liu fullname: Liu, Yue organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 2 givenname: Peiping surname: Yu fullname: Yu, Peiping organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 3 givenname: Qintao surname: Sun fullname: Sun, Qintao organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 4 givenname: Yu surname: Wu fullname: Wu, Yu organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 5 givenname: Miao orcidid: 0000-0002-9797-1449 surname: Xie fullname: Xie, Miao organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 6 givenname: Hao orcidid: 0000-0002-8241-6231 surname: Yang fullname: Yang, Hao organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 7 givenname: Tao orcidid: 0000-0003-4830-177X surname: Cheng fullname: Cheng, Tao email: tcheng@suda.edu.cn organization: Institute of Functional Nano and Soft Materials (FUNSOM) – sequence: 8 givenname: William A orcidid: 0000-0003-0097-5716 surname: Goddard fullname: Goddard, William A organization: Materials and Process Simulation Center, Department of Chemistry |
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| Title | Predicted Operando Polymerization at Lithium Anode via Boron Insertion |
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