Phase Stability and Kinetics of Topotactic Dual Ca2+–Na+ Ion Electrochemistry in NaSICON NaV2(PO4)3

Blanc, Lauren E.; Choi, Yunyeong; Shyamsunder, Abhinandan; Key, Baris; Lapidus, Saul H.; Li, Chang; Yin, Liang; Li, Xiang; Gwalani, Bharat; Xiao, Yihan; Bartel, Christopher J.; Ceder, Gerbrand; Nazar, Linda F.

doi:10.1021/acs.chemmater.2c02816

Title: Phase Stability and Kinetics of Topotactic Dual Ca²⁺–Na⁺ Ion Electrochemistry in NaSICON NaV₂(PO₄)₃

Journal Article · Fri Dec 30 00:00:00 EST 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c02816· OSTI ID:1960511

Blanc, Lauren E. ^[1]; Choi, Yunyeong ^[2]; Shyamsunder, Abhinandan ^[1];

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^[4]; Li, Chang ^[1];

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^[2]; Bartel, Christopher J. ^[2];

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University of Waterloo, ON (Canada); Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Materials Sciences Division; Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Laboratory (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Recent reports of reversible calcium plating and stripping have rekindled interest in the development of Ca-ion batteries (CIBs) as next-generation energy storage devices. This technology has the potential to overcome the limitations of conventional Li-ion batteries, but CIBs are plagued by a paucity of suitable cathode materials. To date, NaSICON-structured NaV₂(PO₄)₃ has been demonstrated as a successful cathode candidate, exhibiting reversible (de)intercalation of 0.6 mol Ca²⁺ along with stable cycling performance. However, a complex multiphase mixture forms on discharge so the Ca-ion charge storage mechanism in the NaSICON framework is poorly understood. Here in this work, we report on an investigation of the structure and/or Na⁺/Ca²⁺ environment(s) of a variety of chemically prepared NaSICON Ca_xNa_yV₂(PO₄)₃ phases which were characterized using synchrotron XRD, SEM-EDS, ²³Na NMR, and TEM. Highly calciated CaV₂(PO₄)₃, Ca_1.5V₂(PO₄)₃, and CaNaV₂(PO₄)₃ phases can be prepared at high temperature, but -unlike Ca_0.6NaV₂(PO₄)₃-these materials are electrochemically inactive. To better understand the fundamental factors impacting successful Ca²⁺ electrochemistry in this system, DFT was employed to examine the Ca_xNa_yV₂(PO₄)₃ phase diagram and Ca²⁺ diffusion mechanism. Theoretical insights show that phase separation into Na-rich and Ca-rich phases is a reason for the capacity limitation and demonstrate that Na⁺ ions in the host materials assist the migration of neighboring Ca²⁺ ions, enabling reversible electrochemistry in Ca_xNa_yV₂(PO₄)₃. This investigation of fundamental principles affecting reversible Ca²⁺ (de)intercalation in Ca_xNa_yV₂(PO₄)₃ allows for the development of design principles to enable the discovery of a variety of successful cathodes for CIBs.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231; ACI1053575

OSTI ID:: 1960511

Journal Information:: Chemistry of Materials, Vol. 35, Issue 2; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Phase Stability and Kinetics of Topotactic Dual Ca²⁺–Na⁺ Ion Electrochemistry in NaSICON NaV₂(PO₄)₃