The utilization of alkali metal anodes is hindered by an inherent instability in organic electrolytes. Sodium is of growing interest due to its high natural abundance, but the carbonate electrolytes popular in lithium systems cannot form a stable solid electrolyte interphase (SEI) with a sodium electrode. Using half-cell and symmetric-cell analysis, we identify specific glyme (chain ether) electrolytes that produce thin, predominantly inorganic SEI at the sodium metal interface, and we study the effect of ethylene carbonate and fluoroethylene carbonate (FEC) additives on the SEI formed in these systems via X-ray photoelectron spectroscopy. Through in situ optical microscopy, we observe the onset and growth of sodium dendrites in these electrolytes. We determine that the SEI formed by glyme alone may not support extensive or extreme cycling conditions, but the addition of FEC provides a more robust SEI to facilitate numerous consistent sodium plating and stripping cycles.
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A Carboranyl Electrolyte Enabling Highly Reversible Sodium Metal Anodes via a “Fluorine‐Free” SEI
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 [HCB 11 H 11 ] 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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- Award ID(s):
- 2004497
- PAR ID:
- 10446645
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 61
- Issue:
- 51
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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