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DFT-ReaxFF Hybrid Reactive Dynamics Method with Application to the Reductive Decomposition Reaction of the TFSI and DOL Electrolyte at a Lithium–Metal Anode Surface

Liu, Yue and Yu, Peiping and Wu, Yu and Yang, Hao and Xie, Miao and Huai, Liyuan and Goddard, William A., III and Cheng, Tao (2021) DFT-ReaxFF Hybrid Reactive Dynamics Method with Application to the Reductive Decomposition Reaction of the TFSI and DOL Electrolyte at a Lithium–Metal Anode Surface. Journal of Physical Chemistry Letters, 12 (4). pp. 1300-1306. ISSN 1948-7185. https://resolver.caltech.edu/CaltechAUTHORS:20210127-103705997

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Abstract

The high energy density and suitable operating voltage make rechargeable lithium ion batteries (LIBs) promising candidates to replace such conventional energy storage devices as nonrechargeable batteries. However, the large-scale commercialization of LIBs is impeded significantly by the degradation of the electrolyte, which reacts with the highly reactive lithium metal anode. Future improvement of the battery performance requires a knowledge of the reaction mechanism that is responsible for the degradation and formation of the solid-electrolyte interphase (SEI). In this work, we develop a hybrid computational scheme, Hybridab initiomolecular dynamics combined with reactive force fields, denoted HAIR, to accelerate Quantum Mechanics-based reaction dynamics (QM-MD or AIMD, for ab initio RD) simulations. The HAIR scheme extends the time scale accessible to AIMD by a factor of 10 times through interspersing reactive force field (ReaxFF) simulations between the AIMD parts. This enables simulations of the initial chemical reactions of SEI formation, which may take 1 ns, far too long for AIMD. We apply the HAIR method to the bis(trifluoromethanesulfonyl)imide (TFSI) electrolyte in 1,3-dioxolane (DOL) solvent at the Li metal electrode, demonstrating that HAIR reproduces the initial reactions of the electrolyte (decomposition of TFSI) previously observed in AIMD simulation while also capturing solvent reactions (DOL) that initiate by ring-opening to form such stable products as CO, CH₂O, and C₂H₄, as observed experimentally. These results demonstrate that the HAIR scheme can significantly increase the time scale for reactive MD simulations while retaining the accuracy of AIMD simulations. This enables a full atomistic description of the formation and evolution of SEI.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpclett.0c03720DOIArticle
ORCID:
AuthorORCID
Yang, Hao0000-0002-8241-6231
Xie, Miao0000-0002-9797-1449
Goddard, William A., III0000-0003-0097-5716
Cheng, Tao0000-0003-4830-177X
Additional Information:© 2021 American Chemical Society. Received: December 18, 2020; Accepted: January 15, 2021; Publication Date: January 27, 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 for financial support. H.Y. thanks China Postdoctoral Science Foundation (2019M660128) for financial support. This work was partly supported by the Collaborative Innovation Center of Suzhou Nano Science & Technology. W.A.G. received support from the United States National Science Foundation (CBET-1805022 and CBET-2005250). 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
Jiangsu Higher Education InstitutionsUNSPECIFIED
China Postdoctoral Science Foundation2019M660128
Suzhou Nano Science and TechnologyUNSPECIFIED
NSFCBET-1805022
NSFCBET-2005250
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1409
Issue or Number:4
Record Number:CaltechAUTHORS:20210127-103705997
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210127-103705997
Official Citation:The DFT-ReaxFF Hybrid Reactive Dynamics Method with Application to the Reductive Decomposition Reaction of the TFSI and DOL Electrolyte at a Lithium–Metal Anode Surface. Yue Liu, Peiping Yu, Yu Wu, Hao Yang, Miao Xie, Liyuan Huai, William A Goddard, and Tao Cheng. The Journal of Physical Chemistry Letters 2021 12 (4), 1300-1306; DOI: 10.1021/acs.jpclett.0c03720
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107772
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Jan 2021 18:48
Last Modified:27 Mar 2021 08:06

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