Prolonged lifespan of initial-anode-free lithium-metal battery by pre-lithiation in Li-rich Li2Ni0.5Mn1.5O4 spinel cathode

Abstract

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 Li₂Ni_0.5Mn_1.5O₄ cathodes as a Li-ion extender; the Li₂Ni_0.5Mn_1.5O₄ 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 Li₂Ni_0.5Mn_1.5O₄ cathode, the further fabricated anode-free pouch cells achieve 350 W h kg^-1 energy density and 97% capacity retention after 50 cycles.