Scalable fabrication of ultra-fine lithiophilic nanoparticles encapsulated in soft buffered hosts for long-life anode-free Li2S-based cells

Abstract

Minimizing the amount of metallic lithium (Li) to zero excess to achieve an anode-free configuration can help achieve safer, higher energy density, and more economical Li metal batteries. Nevertheless, removal of excess Li creates challenges for long-term cycling performance in Li metal batteries due to the lithiophobic copper foils as anodic current collectors. Here, we improve the long-term cycling performance of anode-free Li metal batteries by modifying the anode-free configuration. Specifically, a lithiophilic Au nanoparticle-anchored reduced graphene oxide (Au/rGO) film is used as an anodic modifier to reduce the Li nucleation overpotential and inhibit dendrite growth by forming a lithiophilic Li_xAu alloy and solid solution, which is convincingly evidenced by density functional theory calculations and experimentally. Meanwhile, the flexible rGO film can also act as a buffer layer to endure the volume expansion during repeated Li plating/stripping processes. In addition, the Au/rGO film promotes a homogeneous distribution of the electric field over the entire anodic surface, thus ensuring a uniform deposition of Li during the electrodeposition process, which is convincingly evidenced by finite element simulations. As expected, the Li||Au/rGO-Li half-cell shows a highly stable long-term cycling performance for at least 500 cycles at 0.5 mA cm⁻² and 0.5 mA h cm⁻². A Li₂S-based anode-free full cell allows achieving a stable operation life of up to 200 cycles with a capacity retention of 63.3%. This work provides a simple and scalable fabrication method to achieve anode-free Li₂S-based cells with high anodic interface stability and a long lifetime.