Dual-Phase Lithium Metal Anode Containing a Polysulfide-Induced Solid Electrolyte Interphase and Nanostructured Graphene Framework for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries, with a theoretical energy density of 2600 Wh kg^–1, are a promising platform for high-energy and cost-effective electrochemical energy storage. However, great challenges such as fast capacity degradation and safety concerns prevent it from widespread application. With the adoption of Li metal as the anode, dendritic and mossy metal depositing on the negative electrode during repeated cycles leads to serious safety concerns and low Coulombic efficiency. Herein, we report a distinctive graphene framework structure coated by an <i>in situ</i> formed solid electrolyte interphase (SEI) with Li depositing in the pores as the anode of Li–S batteries. The graphene-based metal anode demonstated a superior dendrite-inhibition behavior in 70 h of lithiation, while the cell with a Cu foil based metal anode was short-circuited after only 4 h of lithiation at 0.5 mA cm^–2. The graphene-modified Li anode with SEI induced by the polysulfide-containing electrolyte improved the Coulombic efficiency to ∼97% for more than 100 cycles, while the control sample with Cu foil as the current collector exhibited huge fluctuations in Coulombic efficiency. The unblocked ion pathways and high electron conductivities of frameworks in the modified metal anode led to the rapid transfer of Li ions through the SEI and endowed the anode framework with an ion conductivity of 7.81 × 10^–2 mS cm^–1, nearly quintuple that of the Cu foil based Li metal anode. Besides, the polarization in the charge–discharge process was halved to 30 mV. The stable and efficient Li deposition was maintained after 2000 cycles. Our results indicated that nanoscale interfacial electrode engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes, thus improving the safety of Li–S cells