High-energy-density
lithium–metal batteries (LMBs) coupling
lithium–metal anodes and high-voltage cathodes are hindered
by unstable electrode/electrolyte interphases (EEIs), which calls
for the rational design of efficient additives. Herein, we analyze
the effect of electron structure on the coordination ability and energy
levels of the additive, from the aspects of intramolecular electron
cloud density and electron delocalization, to reveal its mechanism
on solvation structure, redox stability, as-formed EEI chemistry,
and electrochemical performances. Furthermore, we propose an electron
reconfiguration strategy for molecular engineering of additives, by
taking sorbide nitrate (SN) additive as an example. The lone pair
electron-rich group enables strong interaction with the Li ion to
regulate solvation structure, and intramolecular electron delocalization
yields further positive synergistic effects. The strong electron-withdrawing
nitrate moiety decreases the electron cloud density of the ether-based
backbone, improving the overall oxidation stability and cathode compatibility,
anchoring it as a reliable cathode/electrolyte interface (CEI) framework
for cathode integrity. In turn, the electron-donating bicyclic-ring-ether
backbone breaks the inherent resonance structure of nitrate, facilitating
its reducibility to form a N-contained and inorganic Li2O-rich solid electrolyte interface (SEI) for uniform Li deposition.
Optimized physicochemical properties and interfacial biaffinity enable
significantly improved electrochemical performance. High rate (10
C), low temperature (−25 °C), and long-term stability
(2700 h) are achieved, and a 4.5 Ah level Li||NCM811 multilayer pouch
cell under harsh conditions is realized with high energy density (462
W h/kg). The proof of concept of this work highlights that the rational
ingenious molecular design based on electron structure regulation
represents an energetic strategy to modulate the electrolyte and interphase
stability, providing a realistic reference for electrolyte innovations
and practical LMBs.