A Hierarchical Silver‐Nanowire–Graphene Host Enabling Ultrahigh Rates and Superior Long‐Term Cycling of Lithium‐Metal Composite Anodes

Metallic lithium (Li) is a promising anode for next-generation high-energy-density batteries, but its applications are still hampered due to the limited charging/discharging rate and poor cycling performance. Here, a hierarchical 3D porous architecture is designed with a binary network of continuous silver nanowires assembled on an interconnected 3D graphene skeleton as the host for Li-metal composite anodes, which offers a significant boost in both charging/discharging rates and long-term cycling performance for Li-metal batteries. This unique hierarchical binary network structure in conjunction with optimized material combination provides ultrafast, continuous, and smooth electron transportation channel and non-nucleation barrier sites to direct and confine Li deposition. It also offers outstanding mechanical strength and toughness to support massive Li deposition and buffer the internal stress fluctuations during long-term repeated Li stripping/plating thereby minimizing fundamental issues of dendrite formation and volume change even under ultrafast charging/discharging rates. As a result, the composite anode using this hierarchical host can work smoothly at an unprecedented high current density of 40 mA cm^-2 over 1000 plating/stripping cycles with low overpotential (<120 mV) in symmetric cells. The as-constructed full cell, paired with LiNi_0.5 Co_0.2 Mn_0.3 O₂ cathode, also exhibits excellent rate capability and high-rate cycling stability.