Lithium-ion hopping weakens thermal stability of LiPF6 carbonate electrolytes

Han, Kee Sung; Lee, Mal-Soon; Kim, Namhyung; Choi, Daiwon; Chae, Sujong; Ryu, Jaegeon; Piccini, GiovanniMaria; Rousseau, Roger; Thomsen, Edwin C.

doi:10.1016/j.xcrp.2023.101768

Title: Lithium-ion hopping weakens thermal stability of LiPF₆ carbonate electrolytes

Journal Article · 04 January 2024 · Cell Reports Physical Science

DOI: https://doi.org/10.1016/j.xcrp.2023.101768 · OSTI ID:2348911

^[1];

^[1]; Kim, Namhyung ^[2];

^[1]; Chae, Sujong ^[2];

^[3]; Piccini, GiovanniMaria ^[4]; Rousseau, Roger ^[5]; Thomsen, Edwin C. ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Pukyong National University, Busan (Korea, Republic of)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Sogang Univ. Seoul (Korea, Republic of)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of Modena and Reggio Emilia, Modena (Italy)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Lithium hexafluorophosphate (LiPF₆)-based carbonate electrolytes are widely used in commercial lithium-ion batteries (LIBs), but their thermal instability limits the cycle life and safety of LIBs at elevated temperatures. Few studies have yielded insight into the initial PF₆^— decomposition reaction that promotes thermal instability of LiPF6-based electrolytes. Here, we find that lithium-ion hopping assisted by the overall reorientational motion of propylene carbonate molecules facilitates PF₆^— decomposition at elevated temperatures in 1 M LiPF₆/propylene carbonate electrolyte. Further, we demonstrate that urea additives, by preventing lithium-ion hopping, suppress the initial LiPF₆ decomposition reaction and enhance the thermal stability of the electrolyte. LIB cell tests with LiNi_0.6Mn_0.2Co_0.2O₂||Li₄Ti₅O₁₂ show improved LIB performance at elevated temperatures with the thermally stabilized electrolyte. This study provides key insights into the design of thermally stable LiPF₆-based carbonate electrolytes for improving the cycle life, calendar life, and safety of LIBs in elevated-temperature applications.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Environmental Molecular Sciences Laboratory (EMSL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Electricity (OE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2348911

Report Number(s):: PNNL-SA--189727

Journal Information:: Cell Reports Physical Science, Journal Name: Cell Reports Physical Science Journal Issue: 1 Vol. 5; ISSN 2666-3864

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Lithium-ion hopping weakens thermal stability of LiPF6 carbonate electrolytes

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Title: Lithium-ion hopping weakens thermal stability of LiPF₆ carbonate electrolytes