A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine-Free” SEI

Anton W. Tomich; Jehee Park; Seoung Bum Son; Ethan P. Kamphaus; Xingyi Lyu; Fulya Dogan; Veronica Carta; Jihyeon Gim; Tao Li; Lei Cheng; Eungje Lee; Vincent Lavallo; Christopher S. Johnson

doi:10.1002/anie.202208158

A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine-Free” SEI

Anton W. Tomich
, Jehee Park
, Seoung Bum Son
, Ethan P. Kamphaus
, Xingyi Lyu
, Fulya Dogan
, Veronica Carta
, Jihyeon Gim
, Tao Li
, Lei Cheng
, Eungje Lee
, Vincent Lavallo
, Christopher S. Johnson

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

50 Scopus citations

Abstract

Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid-electrolyte interphase (SEI) are ideal to enable sodium metal and anode-free cells. Herein we present advanced characterization of a novel fluorine-free electrolyte utilizing the [HCB₁₁H₁₁]¹⁻ anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm⁻² and a high coulombic efficiency of 99.5 % in half-cell configurations. Surface characterization of electrodes post-operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine-free SEI. Furthermore, weak ion-pairing is identified as key towards the successful development of fluorine-free sodium electrolytes.

Original language	English
Article number	e202208158
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	51
DOIs	https://doi.org/10.1002/anie.202208158
State	Published - Dec 19 2022
Externally published	Yes

Funding

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under contract number DE-SC0014664. All opinions expressed in this paper are the author's and do not necessarily reflect the policies and views of DOE, ORAU, or ORISE. Support from the Advanced Battery Materials Research (BMR) Program, in particular David Howell and Tien Duong, of the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. Argonne, a U.S. Department of Energy Office of Science Laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publication. This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. AC02-06CH11357. We are grateful to the NSF (DMR-2004497) for partial support of this work. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under contract number DE‐SC0014664. All opinions expressed in this paper are the author's and do not necessarily reflect the policies and views of DOE, ORAU, or ORISE. Support from the Advanced Battery Materials Research (BMR) Program, in particular David Howell and Tien Duong, of the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. Argonne, a U.S. Department of Energy Office of Science Laboratory, is operated under Contract No. DE‐AC02‐06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid‐up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publication. This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. AC02‐06CH11357. We are grateful to the NSF (DMR‐2004497) for partial support of this work.

Keywords

Anode-Free Batteries
Carboranes
Electrochemistry
Electrolyte Engineering
Sodium Metal Anodes

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10.1002/anie.202208158

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Tomich, A. W., Park, J., Son, S. B., Kamphaus, E. P., Lyu, X., Dogan, F., Carta, V., Gim, J., Li, T., Cheng, L., Lee, E., Lavallo, V., & Johnson, C. S. (2022). A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine-Free” SEI. Angewandte Chemie - International Edition, 61(51), Article e202208158. https://doi.org/10.1002/anie.202208158

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abstract = "Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid-electrolyte interphase (SEI) are ideal to enable sodium metal and anode-free cells. Herein we present advanced characterization of a novel fluorine-free electrolyte utilizing the [HCB11H11]1− anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm−2 and a high coulombic efficiency of 99.5 \% in half-cell configurations. Surface characterization of electrodes post-operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine-free SEI. Furthermore, weak ion-pairing is identified as key towards the successful development of fluorine-free sodium electrolytes.",

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AU - Carta, Veronica

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AB - Realization of practical sodium metal batteries (SMBs) is hindered due to lack of compatible electrolyte components, dendrite propagation, and poor understanding of anodic interphasial chemistries. Chemically robust liquid electrolytes that facilitate both favorable sodium metal deposition and a stable solid-electrolyte interphase (SEI) are ideal to enable sodium metal and anode-free cells. Herein we present advanced characterization of a novel fluorine-free electrolyte utilizing the [HCB11H11]1− anion. Symmetrical Na cells operated with this electrolyte exhibit a remarkably low overpotential of 0.032 V at a current density of 2.0 mA cm−2 and a high coulombic efficiency of 99.5 % in half-cell configurations. Surface characterization of electrodes post-operation reveals the absence of dendritic sodium nucleation and a surprisingly stable fluorine-free SEI. Furthermore, weak ion-pairing is identified as key towards the successful development of fluorine-free sodium electrolytes.

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A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine-Free” SEI

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