Although lithium-metal anode is regarded as the most promising candidate for high-energy-density batteries, the uncontrollable Li dendrite growth and large volumetric change have severely inhibited its practical application. Herein, a three-dimensional (3D)-printed graphene oxide framework was constructed as a lithium-metal host to modulate the plating behavior of Li+ on the interfaces. Owing to the specially designed architecture, the 3D-printed GO framework can effectively reduce the local current density and supply large space for the accommodation of Li to buffer the volume change. As a result, the 3D-GO@Li anode enables a dendrite-free Li plating/stripping with a small overpotential of 9 mV and a long-term cycling stability of 1600 h at 1 mA cm–2. Moreover, the stable 3D-GO@Li anode is further corroborated via a full battery with a LiFePO4 cathode with a superior long cycle lifespan and capacity retention in comparison to the pristine Li anode. This work would pave a promising way for 3D printing technology to construct high-energy-density energy storage devices.

Lithium ion capacitors (LICs) as promising energy storage devices are receiving lots of attention recently. However, anodes with high rate performance are urgently needed to balance the thermodynamics and kinetics...

Lithium metal batteries are emerging as a strong candidate in the future energy storage market due to its extremely high energy density. However, the uncontrollable lithium dendrites and volume change of lithium metal anodes severely hinder its application. In this work, the porous Cu skeleton modified with Cu6Sn5 layer is prepared via dealloying brass foil following a facile electroless process. The porous Cu skeleton with large specific surface area and high electronic conductivity effectively reduces the local current density. The Cu6Sn5 can react with lithium during the discharge process to form lithiophilic Li7Sn2 in situ to promote Li‐ions transport and reduce the nucleation energy barrier of lithium to guide the uniform lithium deposition. Therefore, more than 300 cycles at 1 mA cm−2 are achieved in the half‐cell with an average Coulombic efficiency of 97.5%. The symmetric cell shows a superior cycle life of more than 1000 h at 1 mA cm−2 with a small average hysteresis voltage of 16 mV. When coupled with LiFePO4 cathode, the full cell also maintains excellent cycling and rate performance.