Stable Metal Anode enabled by Porous Lithium Foam with Superior Ion Accessibility

Abstract Lithium (Li) metal anodes have attracted much interest recently for high‐energy battery applications. However, low coulombic efficiency, infinite volume change, and severe dendrite formation limit their reliable implementation over a wide range. Here, an outstanding stability for a Li metal anode is revealed by designing a highly porous and hollow Li foam. This unique structure is capable of tackling many Li metal problems simultaneously: first, it assures uniform electrolyte distribution over the inner and outer electrode's surface; second, it reduces the local current density by providing a larger electroactive surface area; third, it can accommodate volume expansion and dissipate heat efficiently. Moreover, the structure shows superior stability compared to fully Li covered foam with low porosity, and bulky Li foil electrode counterparts. This Li foam exhibits small overpotential (≈25 mV at 4 mA cm⁻²) and high cycling stability for 160 cycles at 4 mA cm⁻². Furthermore, when assembled, the porous Li metal as the anode with LiFePO₄ as the cathode for a full cell, the battery has a high‐rate performance of 138 mAh g⁻¹ at 0.2 C. The beneficial structure of the Li hollow foam is further studied through density functional theory simulations, which confirms that the porous structure has better charge mobility and more uniform Li deposition.