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

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. Additionally, 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of [(3,4,5‐F 3 C 6 H 2 )(4‐ n BuC 6 H 4 ) 2 C][HCB 11 Cl 11 ]: A Much More Soluble Version of the Trityl Cation with Slightly Higher Lewis Acidity

A new triarylmethyl cation (*Tr + ), designed to closely mimic Ph 3 C + in reactivity, has been prepared as a [HCB 11 Cl 11 ] − salt. *Tr + very slightly exceeds the Lewis acidity of Ph 3 C + in chloride and hydride transfer reactions, but possesses two orders of magnitude higher solubility in organic solvents of low polarity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗