Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

Leon, Noel J.; Ilic, Stefan; Xie, Xiaowei; Jeong, Heonjae; Yang, Zhenzhen; Wang, Bingning; Spotte-Smith, Evan Walter Clark; Stern, Charlotte; Hahn, Nathan; Zavadil, Kevin; Cheng, Lei; Persson, Kristin A.; Connell, Justin G.; Liao, Chen

doi:10.1021/acs.jpclett.4c00969

Title: Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

Journal Article · 06 May 2024 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.4c00969 · OSTI ID:2505031

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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); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Multivalent-ion battery technologies are increasingly attractive options for meeting diverse energy storage needs. Calcium ion batteries (CIB) are particularly appealing candidates for their earthly abundance, high theoretical volumetric energy density, and relative safety advantages. Here, at present, only a few Ca-ion electrolyte systems are reported to reversibly plate at room temperature: for example, aluminates and borates, including Ca[TPFA]₂, where [TPFA]^- = [Al(OC(CF₃)₃)₄]^- and Ca[B(hfip)₄]₂, [B(hfip)₄]₂^– = [B(OCH(CF₃)₂)₄]^-. Analyzing the structure of these salts reveals a common theme: the prevalent use of a weakly coordinating anion (WCA) consisting of a tetracoordinate aluminum/boron (Al/B) center with fluorinated alkoxides. Leveraging the concept of theory-aided design, we report an innovative, one-pot synthesis of two new calcium-ion electrolyte salts (Ca[Al(tftb)₄]₂, Ca[Al(hftb)₄]₂) and two reported salts (Ca[Al(hfip)₄]₂ and Ca[TPFA]₂) where hfip = (-OCH(CF₃)₂), tftb = (-OC(CF₃)(Me)₂), hftb = (-OC(CF₃)₂(Me)), [TPFA]^- = [Al(OC(CF₃)₃)₄]^-. We also reveal the dependence of Coulombic efficiency on their inherent propensity for cation–anion coordination.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR)

Grant/Contract Number:: AC02-06CH11357; NA0003525

OSTI ID:: 2505031

Report Number(s):: SAND--2025-02604J; 188870

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 19 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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