To address the limited lithium (Li) storage of graphite anode, Li metal has been explored as a high-capacity alternative. However, its practical use is hindered by dendritic Li growth, leading to rapid degradation and safety risks. Although 3D host structures have been proposed to suppress Li dendritic growth by controlling Li+ flux, precise regulation at the sub-nanoscale remains a challenge. In this study, we introduce a porous electrode‒reinforced electric double-layer (PERE) structure featuring sub-nanoscale pores that focus the electric double layer (EDL) within the pore channels. This EDL focusing enables spontaneous Li+ accumulation, enabling stable Li deposition. When practically implemented in a battery with a LiFePO4 (LFP) cathode, the PERE afforded a high specific capacity of 123 mAh g−1 for 250 cycles at 4.0 C. Our approach solved the fundamental problem only by controlling the structure without using anode active materials, thereby improving the sustainability of the battery.
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