Li‐Rich Li₂[Ni_0.8Co_0.1Mn_0.1]O₂ for Anode‐Free Lithium Metal Batteries

Abstract Anode‐free lithium metal batteries can maximize the energy density at the cell level. However, without the Li compensation from the anode side, it faces much more challenging to achieve a long cycling life with a competitive energy density than Li metal‐based batteries. Here, we prolong the lifespan of an anode‐free Li metal battery by introducing Li‐rich Li 2 [Ni 0.8 Co 0.1 Mn 0.1 ]O 2 into the cathode as a Li‐ions extender. The Li 2 [Ni 0.8 Co 0.1 Mn 0.1 ]O 2 can release a large amount of Li‐ions during the first charging process to supplement the Li loss in the anode, then convert into NCM811, thus extending the lifespan of the battery without the introduction of inactive elements. By the benefit of Li‐rich cathode and high reversibility of Li metal on Cu foil, the anode‐free pouch cells enable to achieve 447 Wh kg −1 energy density and 84 % capacity retention after 100 cycles in the condition of limited electrolyte addition (E/C ratio of 2 g Ah −1 ).