Cation solvation is well understood in the bulk solution phase, but knowledge is limited regarding the electrode–electrolyte interface. The process by which cation solvation conforms to the interfacial field to form interphases remains unclear. Here we examine the synergistic effects of external and intramolecular fields on accommodating Li⁺ solvates to the Li-metal anode, leading to dielectric-mediated transfer dynamics on the interface. At charged interfaces, cation–anion pairs arrange in a periodic oscillatory distribution. A low-oscillation amplitude exacerbates the electrolyte decomposition and increases surface impedance. We propose a dielectric protocol that maintains cation–anion coordination with a high oscillation amplitude at the interfaces, addressing these issues. Accordingly, we demonstrate a Li-metal pouch cell with an energy density of 500 Wh kg⁻¹ at the Ah level using an ultra-lean electrolyte (1 g Ah⁻¹). Our study offers insights into solid/liquid interfaces that are crucial in advancing battery technologies.

本体溶液相中的阳离子溶剂化作用已被很好地理解，但有关电极-电解质界面的知识有限。阳离子溶剂化符合界面场形成界面的过程仍不清楚。在这里，我们研究了外部和分子内场对将 Li ⁺溶剂化物容纳到锂金属阳极的协同效应，从而导致界面上介电介导的转移动力学。在带电界面处，阳离子-阴离子对以周期性振荡分布排列。低振荡幅度会加剧电解质分解并增加表面阻抗。我们提出了一种介电协议，可以在界面处保持阳离子-阴离子协调并具有高振荡幅度，从而解决这些问题。因此，我们展示了使用超贫电解液（1 g Ah ^-1 ）在 Ah 水平下能量密度为 500 Wh kg ^-1的锂金属软包电池。我们的研究提供了对固体/液体界面的见解，这对于推进电池技术至关重要。