Lithium metal batteries are booming because of their inherent preponderance, but a negative electric field from concentration dipolarization and slow solid-phase transfer at the electrode interface become blocking modules for extreme fast charging. Achieving an anion-rich solvation shell with a high dielectric constant (ε) is a feasible strategy to bootstrap an interface microenvironment for mass-transport reaction, but it is still an uncultivated field. Herein, the superposition, including the donor number values, the high ε, and the spatial potential resistance, are complementarily considered; we propose a low-cost electrolyte with an internal excluding external tactic to answer the above issue. Explanatorily, an optimized solvation shell follows the cascading exclusion relationship of nitrate ion (NO3-) → tetraglyme → ethylene carbonate → dimethyl carbonate. And the culminated bilayer structure establishes ideal conditions for Li+ transfer-reaction kinetics, of which an anion-rich internal shell facilitates solid-phase transport and a high-ε external shell slashes the negative electric field.