Lithium (Li) metal anode is proposed to take on the heavy responsibility for high-energy Li metal batteries (LMBs). However, some severe obstacles such as uncontrolled growth of Li dendrites, infinite volume variation of Li deposition and low Coulombic efficiency are still big challenges. Herein, a copper foam covered with dense and rigid organic supramolecular protective layer (OSPL) with rearranged and defensive Li deposition is reported to effectively inhibit the formation of dendritic Li and suppress the depletion of Li metal and electrolyte, which is evidenced by optical/electron microscopy, in situ FTIR spectra, electrochemical probing and theoretical calculation. The composite matrix performs high Coulombic efficiencies of 98% for 250 cycles at 1 ​mA ​cm⁻² and enhanced cycling lifespan of 1300 ​h with low potential polarization (20 ​mV) for symmetric cell. Moreover, small nucleation overpotential (27.1 ​mV) benefits from attracting Li ions by massive polar functional groups in the organic supramolecular structure. When coupled with LiFePO₄, full-cells display ultrahigh retention ratio (96.2%) and slow decay of specific capacity after 250 cycles at 0.5 ​C. Low voltage hysteresis reflects the improved kinetics and fast charge-transfer behavior during Li charging/discharging process. The strategy using OSPL provides a new insight for exploring high performance LMBs.

锂（Li）金属阳极被提议承担高能锂金属电池（LMB）的重任。然而，诸如锂树枝状晶体的不受控制的生长，锂沉积的无限体积变化和低库仑效率等一些严重的障碍仍然是巨大的挑战。在本文中，据报道，覆盖有致密且刚性的有机超分子保护层（OSPL）且具有重新排列且具有防御性的Li沉积的泡沫铜能够有效抑制树枝状Li的形成并抑制Li金属和电解质的消耗，这可以通过光学/电子证明显微镜，原位FTIR光谱，电化学探测和理论计算。复合基质在1 mA cm ^-2的250个循环中执行98％的高库仑效率对称电池的低电势极化（20 mV）以及1300 h的增强循环寿命。此外，小的成核超电势（27.1 mV）得益于有机超分子结构中大量的极性官能团吸引锂离子。当与LiFePO ₄结合使用时，全电池在0.5 C的250个循环后显示出超高的保留率（96.2％）和比容量的缓慢衰减。低压磁滞反映出在Li充电/放电过程中改善的动力学和快速的电荷转移行为。使用OSPL的策略为探索高性能LMB提供了新的见解。