Elementary Decomposition Mechanisms of Lithium Hexafluorophosphate in Battery Electrolytes and Interphases

Spotte-Smith, Evan Walter Clark; Petrocelli, Thea Bee; Patel, Hetal D.; Blau, Samuel M.; Persson, Kristin A.

doi:10.1021/acsenergylett.2c02351

Title: Elementary Decomposition Mechanisms of Lithium Hexafluorophosphate in Battery Electrolytes and Interphases

Journal Article · Mon Dec 05 00:00:00 EST 2022 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.2c02351· OSTI ID:1902524

^[1]; Petrocelli, Thea Bee ^[2]; Patel, Hetal D. ^[1];

^[3];

^[4]

Materials Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California94720, United States, Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California94720, United States
Materials Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California94720, United States, Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California94720, United States, Cabrillo College, 6500 Soquel Drive, Aptos, California95003, United States
Energy Storage and Distributed Resources, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California94720, United States
Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Memorial Mining Building, Berkeley, California94720, United States, Molecular Foundry, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California94720, United States

Electrolyte decomposition constitutes an outstanding challenge to long-life Li-ion batteries (LIBs) as well as emergent energy storage technologies, contributing to protection via solid electrolyte interphase (SEI) formation and irreversible capacity loss over a battery’s life. Major strides have been made to understand the breakdown of common LIB solvents; however, salt decomposition mechanisms remain elusive. In this work, we use density functional theory to explain the decomposition of lithium hexafluorophosphate (LiPF₆) salt under SEI formation conditions. Our results suggest that LiPF₆ forms POF₃ primarily through rapid chemical reactions with Li₂CO₃, while hydrolysis should be kinetically limited at moderate temperatures. We further identify selectivity in the proposed autocatalysis of POF₃, finding that POF₃ preferentially reacts with highly anionic oxygens. These results provide a means of interphase design in LIBs, indicating that LiPF₆ reactivity may be controlled by varying the abundance or distribution of inorganic carbonate species or by limiting the transport of PF₆- through the SEI.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation; Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES) Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1902524

Alternate ID(s):: OSTI ID: 1985506

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Vol. 8 Journal Issue: 1; ISSN 2380-8195

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Elementary Decomposition Mechanisms of Lithium Hexafluorophosphate in Battery Electrolytes and Interphases

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