TY - JOUR
T1 - Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes
AU - Leon, Noel J.
AU - Ilic, Stefan
AU - Xie, Xiaowei
AU - Jeong, Heonjae
AU - Yang, Zhenzhen
AU - Wang, Bingning
AU - Spotte-Smith, Evan Walter Clark
AU - Stern, Charlotte
AU - Hahn, Nathan
AU - Zavadil, Kevin
AU - Cheng, Lei
AU - Persson, Kristin A.
AU - Connell, Justin G.
AU - Liao, Chen
N1 - Publisher Copyright:
© 2024 UChicago Argonne, LLC, Operator of Argonne National Laboratory. Published by American Chemical Society
PY - 2024/5/16
Y1 - 2024/5/16
N2 - 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. 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.
AB - 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. 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.
UR - http://www.scopus.com/inward/record.url?scp=85192856960&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.4c00969
DO - 10.1021/acs.jpclett.4c00969
M3 - Article
C2 - 38709010
AN - SCOPUS:85192856960
SN - 1948-7185
VL - 15
SP - 5096
EP - 5102
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 19
ER -