Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

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

doi:10.1021/acs.jpclett.4c00969

Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

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

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	5096-5102
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	15
Issue number	19
DOIs	https://doi.org/10.1021/acs.jpclett.4c00969
State	Published - May 16 2024
Externally published	Yes

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10.1021/acs.jpclett.4c00969

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@article{1680df3ab698406e82624dc9e8b2bced,

title = "Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes",

abstract = "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.",

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

note = "Publisher Copyright: {\textcopyright} 2024 UChicago Argonne, LLC, Operator of Argonne National Laboratory. Published by American Chemical Society",

year = "2024",

month = may,

day = "16",

doi = "10.1021/acs.jpclett.4c00969",

language = "English",

volume = "15",

pages = "5096--5102",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

number = "19",

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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

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 - https://www.scopus.com/pages/publications/85192856960

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 -

Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

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