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In situ tribocorrosion utilizing a scan probe tip is a practicable system to solve components of failure that originate during the nanoscale on actively passivated metal surfaces.Exploring efficient electrocatalysts for lithium-sulfur (Li-S) batteries is of great importance for the sulfur/polysulfide/sulfide multiphase conversion. Herein, we report nickel-iron intermetallic (Ni3Fe) as a novel electrocatalyst to trigger the extremely efficient poly