Physics

Kinetics

Nanotechnology

Electrode

Organic chemistry

Anode

Engineering

Faraday efficiency

Intercalation (chemistry)

Transmission electron microscopy

Physical chemistry

Inorganic chemistry

Chemistry

Materials science

Ether

Quantum mechanics

Electrolyte

Chemical engineering

Advanced Materials

The sodium storage performance of a hard carbon (HC) anode in ether electrolytes exhibits a higher initial Coulombic efficiency (ICE) and better rate performance compared to conventional ester electrolytes. However, the mechanism behind faster Na storage kinetics for HC in ether electrolytes remains unclear. Herein, a unique solvated Na + and Na + co‐intercalation mechanism in ether electrolytes is reported using designed monodispersed HC nanospheres. In addition, a thin solid electrolyte interphase film with a high inorganic proportion formed in an ether electrolyte is visualized by cryo transmission electron microscopy and depth‐profiling X‐ray photoelectron spectroscopy, which facilitates Na + transportation, and results in a high ICE. Furthermore, the fast solvated Na + diffusion kinetics in ether electrolytes are also revealed via molecular dynamics simulation. Owing to the contribution of the ether electrolytes, an excellent rate performance (214 mAh g −1 at 10 A g −1 with an ultrahigh plateau capacity of 120 mAh g −1 ) and a high ICE (84.93% at 1 A g −1 ) are observed in a half cell; in a full cell, an attractive specific capacity of 110.3 mAh g −1 is achieved after 1000 cycles at 1 A g −1 .

Elucidating the Mechanism of Fast Na Storage Kinetics in Ether Electrolytes for Hard Carbon Anodes