In vacuo XPS investigation of surface engineering for lithium metal anodes with plasma treatment

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Lithium (Li) metal is an attractive anode material with high capacity (3860 mAh g−1) and low potential (−3.04 V vs. standard hydrogen electrode) that shows highly promising for applications requiring high energy density. However, the low electrochemical potential of Li metal makes it extremely reactive and inevitably forming a native oxidized layer in the ambient environment and repeatedly being consumed when exposed to liquid electrolytes. It is therefore beneficial to replace the poorly controlled native passivation layer with a tailored artificial SEI to improve interface management between Li and electrolyte and enhance the stability of Li metal battery. Here, we use an integrated glovebox-atomic layer deposition (ALD)- X-ray photoelectron spectroscopy (XPS) setup to in-situ investigating the pristine Li surface and the surface composition after Ar, H2, O2, N2 and NH3 plasma treatment processes. We find that the pristine Li foil is naturally being covered with a native oxidized layer, which is mainly composed of LiOH, Li2O and Li2CO3. These investigated plasmas can efficiently remove the oxidized layer from the Li metal surface, in which metallic Li surface is obtained after Ar or H2 plasma treatments, where Ar plasma is more efficient. While O2 plasma treatment produces a Li2O layer, and N2 or NH3 plasma treatment leads to a Li3N (including a certain amount of LiON) layer on the Li surface. When employing the representative metallic Li (by Ar plasma treatment), Li2O layer coated Li (by O2 plasma treatment) and Li3N layer coated Li (by N2 plasma treatment) foils as electrodes in symmetric Li metal batteries, the Li3N coated Li electrode exhibits much higher stability than that of metallic and Li2O layer coated Li foils. Improved electrochemical performance has also been achieved in LiMn2O4 (LMO)||Li full cells using Li anode with Li3N protective coating layer. Our work reveals the detailed process of surface engineering of Li metal anodes with plasma treatments by in vacuo XPS, which may also be extended to other gas-treatment or plasma-treatment for stabilization of high energy density Li metal anodes and other metal-based anodes.