The interfacial chemistry of solid electrolyte interphases (SEI) on lithium (Li) electrode is directly determined by the structural chemistry of the electric double layer (EDL) at the interface. Herein, a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed (p-hydroxybenzoic acid (pHA) is selected as proof-of-concept). According to the molecular dynamics (MD) simulation and density functional theory (DFT) calculation results, the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL, reduces the lowest unoccupied molecular orbital (LUMO) energy level of anions in the EDL, and the number of free solvent molecules, which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition. Based on this strategy, Li||Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm⁻², and the long-term cycle stability of Li||Li cells is increased to 1200 h. In addition, the full cell pairing with the commercial LiFePO₄ (LFP) cathodes exhibits stable cycling performance at 1C, with a capacity retention close to 90% after 200 cycles.

Metallic lithium is deemed as the “Holy Grail” anode in high-energy-density secondary batteries. Uncontrollable lithium dendrite growth and related issues originated from uneven concentration distribution of Li⁺ in the vicinity of the anode, however, induce severe safety concerns and poor cycling efficiency, dragging lithium metal anode out of practical application. Herein we address these issues by using cross-linked lithiophilic amino phosphonic acid resin as the effective host with the ion-transport-enhancement feature. Based on theoretical calculations and multiphysics simulation, it is found that this ion-transport-enhancement feature is capable of facilitating the self-concentration kinetics of Li⁺ and accelerating Li⁺ transfer at the electrolyte/electrode interface, leading to uniform bulk lithium deposition. Experimental results show that the proposed lithium-hosting resin decreases the irreversible lithium capacity and improves lithium utilization (with the Coulombic efficiency (CE) of 98.8% over 130 cycles). Our work demonstrates that inducing the self-concentrating distribution of Li⁺ at the interface can be an effective strategy for improving the interfacial ion concentration gradient and optimizing lithium deposition, which opens a new avenue for the practical development of next-generation lithium metal batteries.