Improved Plating/Stripping in Anode-Free Lithium Metal Batteries through Electrodeposition of Lithiophilic Zinc Thin Films

The new concept of anode-free Li batteries (AFLBs) with no excess lithium, while retaining numerous strengths, does come with certain challenges, such as high capacity loss and low coulombic efficiency. These challenges can be addressed through the utilization of modified lithiophilic current collectors to enhance the electrochemical performances. Herein, we investigated the surface modification of the Cu current collector by zinc electrodeposition to provide a lithiophilic thin layer. This process aims to facilitate a smoother plating/stripping process, leading to a uniform and dendrite-free lithium deposition on the LixZny phase formed at the first stages of plating. The zinc-modified current collectors improved cell's performances, including smooth and dense lithium deposition, reduced overpotential at various applied current densities (44.5 mV to 16.8 mV @0.25 mA cm−2), prolonged cycling stability for about 300 cycles and provided high coulombic efficiency of 95 % when compared to bare Cu electrodes. These improvements are attributed to a favorable lithium alloying reaction on the Zn-coated surface. Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) revealed high diffusion coefficients for lithium (ranging from 10−9 to 10−6 cm²/s), despite of the solid-state Li diffusion in the Zn film coating. We anticipate that implementing this modified current collector in a half-cell configuration could lead to the realization of a high-performance, anode-free lithium battery. This holistic approach proposes a scalable and cost-effective technique for boosting the performance of AFLBs.