The simultaneous engineering of sulfur cathode and Li anode is critical for electrolyte-starved high-energy-density Li-S batteries. Herein, we challenge the conventional wisdom of heterogeneous and homogeneous catalyses in Li-S batteries, the concept of anti-heterogeneous catalysis is proposed to synchronously realize effective LiPS trapping/conversion and protection of Li anode through employing a small amount of non-nucleophilic electrolyte additive of an amidomagnesium halide, hexamethyldisilazide magnesium chloride (HMC). Regulated by the amidomagnesium halide chemistry, over 1000 hours of cycling is realized in Li/Li symmetric cells, revealing superb compatibility of the HMC-incorporated electrolyte with lithium metal. Meanwhile, via elevating the dissociation free-energy barrier of Li⁺ in LiPS, the liquid HMC catalysts significantly decrease the solubility of lithium ploysulfides and promote the multistep conversion of sulfur electrochemistry, which enable a quasi-solid-state reaction and minimal shuttle effect. Practically, a high energy density of 423 Wh kg^-1 with decent cycling stability is achieved in electrolyte-starved pouch cells.

硫正极和锂负极的同步设计对于缺乏电解质的高能量密度锂硫电池至关重要。在此，我们挑战了锂硫电池中多相和均相催化的传统观念，提出了反多相催化的概念，通过使用少量非亲核电解质，同步实现有效的 LiPS 捕获/转化和锂负极的保护一种氨基镁卤化物，六甲基二硅叠氮镁氯化物（HMC）的添加剂。在氨基镁卤化物化学的调控下，Li/Li 对称电池实现了超过 1000 小时的循环，揭示了掺入 HMC 的电解质与锂金属的极好相容性。同时，通过提高 Li ⁺的解离自由能垒在 LiPS 中，液态 HMC 催化剂显着降低了多硫化锂的溶解度并促进了硫电化学的多步转化，从而实现了准固态反应和最小的穿梭效应。实际上，在缺乏电解质的软包电池中实现了 423 Wh kg ^-1的高能量密度和良好的循环稳定性。