Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium–sulfur batteries

A rechargeable lithium anode requires a porous structure for a high capacity, and a stable electrode/electrolyte interface against dendrite formation and polysulfide crossover when used in a lithium-sulfur battery. Here, we design two simple steps of spontaneous reactions for protecting porous lithium electrodes. First, a reaction between molten lithium and sulfur-impregnated carbon nanofiber forms a fibrous network with a lithium shell and a carbon core. Second, we coat the surface of this porous lithium electrode with a composite of lithium bismuth alloys and lithium fluoride through another spontaneous reaction between lithium and bismuth trifluoride, solvated with phosphorous pentasulfide, which also polymerizes with lithium sulfide residual in the electrode to form a solid electrolyte layer. This protected porous lithium electrode enables stable operation of a lithium-sulfur battery with a sulfur loading of 10.2 mg cm(−2) at 6.0 mA cm(−2) for 200 cycles.