Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Yap, Kyra M. K. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:000000018861993X); Abdo, Emily E. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000278117837); Aramaki, Hiroki [University of California, Santa Barbara, CA (United States)] (ORCID:0009000056234402); Sugisawa, Hiroki [University of California, Santa Barbara, CA (United States); Mitsubishi Chemical Corporation, Yokohama (Japan)]; Hamamura, Tomofumi [University of California, Santa Barbara, CA (United States); Mitsubishi Chemical Corporation, Yokohama (Japan)]; Mukunoki, Kazunori [University of California, Santa Barbara, CA (United States); Mitsubishi Chemical Corporation, Yokohama (Japan)]; Im, Julia [University of California, Berkeley, CA (United States)] (ORCID:0000000266332513); Celik, Hasan [University of California, Berkeley, CA (United States)]; Hesse, Sarah A. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)] (ORCID:0000000223834476); Paul, Partha P. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)]; Balsara, Nitash P. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000201065565)

doi:10.1021/acs.chemmater.6c00803

DOE OSTI · 3391123

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

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Abstract

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.

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Yap, Kyra M. K. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:000000018861993X), Abdo, Emily E. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000278117837), Aramaki, Hiroki [University of California, Santa Barbara, CA (United States)] (ORCID:0009000056234402), Sugisawa, Hiroki [University of California, Santa Barbara, CA (United States); Mitsubishi Chemical Corporation, Yokohama (Japan)], Hamamura, Tomofumi [University of California, Santa Barbara, CA (United States); Mitsubishi Chemical Corporation, Yokohama (Japan)], Mukunoki, Kazunori [University of California, Santa Barbara, CA (United States); Mitsubishi Chemical Corporation, Yokohama (Japan)], Im, Julia [University of California, Berkeley, CA (United States)] (ORCID:0000000266332513), Celik, Hasan [University of California, Berkeley, CA (United States)], Hesse, Sarah A. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)] (ORCID:0000000223834476), Paul, Partha P. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)], Balsara, Nitash P. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000201065565). 2026-06-11. Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields. https://doi.org/10.1021/acs.chemmater.6c00803

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