An Anode‐Free Zn–Graphite Battery

Abstract The anode‐free battery concept is proposed to pursue the aspiration of energy‐dense, rechargeable metal batteries, but this has not been achieved with dual‐ion batteries. Herein, the first anode‐free Zn–graphite battery enabled by efficient Zn plating–stripping onto a silver‐coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode‐free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI⁻) intercalation without anodic corrosion. An extra high‐potential TFSI⁻ intercalation plateau is recognized at 2.75 V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating–stripping and TFSI⁻ intercalation–deintercalation, an anode‐free Zn–graphite dual‐ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79 Wh kg⁻¹ based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn–graphite batteries (<30 Wh kg⁻¹).