Stable Li metal anode by crystallographically oriented plating through in-situ surface doping

Lithium (Li) metal is regarded as the holy grail anode material for high-energy-density batteries owing to its ultrahigh theoretical specific capacity. However, its practical application is severely hindered by the high reactivity of metallic Li against the commonly used electrolytes and uncontrolled growth of mossy/dendritic Li. Different from widely-used approaches of optimization of the electrolyte and/ or interfacial engineering, here, we report a strategy of in-situ cerium (Ce) doping of Li metal to promote the preferential plating along the [200] direction and remarkably decreased surface energy of metallic Li. The in-situ Ce-doped Li shows a significantly reduced reactivity towards a standard electrolyte and, uniform and dendrite-free morphology after plating/ stripping, as demonstrated by spectroscopic, morphological and electrochemical characterizations. In symmetric half cells, the in-situ Ce-doped Li shows a low corrosion current density against the electrolyte and drastically improved cycling even at a lean electrolyte condition. Furthermore, we show that the stable Li LiCoO₂ full cells with improved coulombic efficiency and cycle life are also achieved using the Ce-doped Li metal anode. This work provides an inspiring approach to bring Li metal towards practical application in high energy-density batteries.