Thiophilic-Lithiophilic Hierarchically Porous Membrane-Enabled Full Lithium-Sulfur Battery with a Low N/P Ratio

Lithium-sulfur batteries stand out as the next-generation batteries because of their high energy density and low cost. However, the shuttle effect of lithium polysulfides (LiPSs), growth of lithium dendrites, and overuse of lithium resources still hinder their further application. To address these problems, we constructed a porous network structure in which Sn is melted and coated on a frame that has a carbon nanotube (CNT) core and a nitrogen-doped carbon (NC) coating as cross-linking shell (CNT@NC@Sn). This hierarchically porous membrane electrode, which has an ultrahigh porosity of approximately 90%, works as a matrix to strengthen the conductivity of Li⁺ and electrons and provides enough space for the conversion between sulfur and LiPSs. Moreover, the in situ thin coating of Sn not only promotes the adsorption and catalytic conversion of LiPSs but also provides lithiophilic binding sites and induces uniform lithium deposition. Thus, the thiophilic-lithiophilic porous membrane electrode with lithium loaded on the frame (in the form of Sn-Li alloy) by electroplating can replace lithium sheets, reduce the use of Li, and improve the safety performance of the battery. Additionally, these dual-functional membranes boost the reaction kinetics and conductivity of the cathode by dispersing the sulfur slurry in the porous membrane framework. As a result, the lithium-sulfur full battery assembled with the CNT@NC@Sn integrated membrane electrode exhibits stable cycling with a reversible capacity of 617.1 mAh g^-1 after 200 cycles at 1 C. The capacity decay rate per cycle is 0.105%, and the N/P ratio is as low as 2.98.