Efficient Ni2Co4P3 Nanowires Catalysts Enhance Ultrahigh‐Loading Lithium–Sulfur Conversion in a Microreactor‐Like Battery

High‐loading lithium–sulfur (Li–S) batteries suffer from poor electrochemical properties. Electrocatalysts can accelerate polysulfides conversion and suppress their migration to improve battery cyclability. However, catalysts for Li–S batteries usually lack a rational design. A d‐band tuning strategy is reported by alloying cobalt to metal sites of Ni₂P to enhance the interaction between polysulfides and catalysts. A molecular or atomic level analysis reveals that Ni₂Co₄P₃ is able to weaken the S? S bonds and lower the activation energy of polysulfides conversion, which is confirmed with temperature‐dependent experiments. Ni₂Co₄P₃ nanowires are further fabricated on a porous nickel scaffold to unfold the catalytic activity by its large surface area. Using a simple ion‐selective filtration shell, a microreactor‐like S cathode (MLSC) is constructed to realize ultrahigh S loading (25 mg cm^?2). As such, a microreactor design integrates reaction and separation in one cell and can effectively address the polysulfide issues, the MLSC cell demonstrates excellent properties of cyclability and high capacity (1223 mAh g^?1 at 0.1 C). More importantly, the catalyst's designs and microreactor strategies provide new approaches for addressing the complicated issues of Li–S batteries.