Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich LiNiMnO spinel cathode.

Anode-free lithium metal batteries (AF-LMBs) can deliver the maximum energy density. However, achieving AF-LMBs with a long lifespan remains challenging because of the poor reversibility of Li plating/stripping on the anode. Here, coupled with a fluorine-containing electrolyte, we introduce a cathode pre-lithiation strategy to extend the lifespan of AF-LMBs. The AF-LMB is constructed with Li-rich LiNiMnO cathodes as a Li-ion extender; the LiNiMnO can deliver a large amount of Li in the initial charging process to offset the continuous Li consumption, which benefits the cycling performance without sacrificing energy density. Moreover, the cathode pre-lithiation design has been practically and precisely regulated using engineering methods (Li-metal contact and pre-lithiation Li-biphenyl immersion). Benefiting from the highly reversible Li metal on the Cu anode and LiNiMnO cathode, the further fabricated anode-free pouch cells achieve 350 W h kg energy density and 97% capacity retention after 50 cycles.