Controlling the complex, multiphase sulfur/polysulfide redox process is a fundamental pathway to alleviate the cathodic passivation and unlock the high energy potentials of all-solid-state Na–S electrochemistry. Herein, by employing a confined tandem electrocatalytic approach, we successfully tune the polysulfide speciation pathway to enable energetic, low-temperature (80 °C) Na–S systems based on dense Na₃Zr₂Si₂PO₁₂ ceramic membranes. Our design features york–shell structured MnHCF/PPy@MnO₂ coaxial nanotubes endowed with a localized and confined environment. These components synergistically catalyze the conversion of encapsulated sulfur/sulfide, with MnO₂ effectively directing long-chain polysulfide transition and MnHCF nanoclusters catalyzing low-kinetic Na₂S₄ to Na₂S direct and reversible conversion. This facilitates continuous, fully controllable quasi-solid sulfur conversion, significantly enhancing battery performance. Operando investigations show that, without the mediation of these bi-catalytic centers, the electrodeposited Na₂S₂/Na₂S exhibits a much higher activation energy upon recharging, leading to the accumulation of inactive polysulfide species and exacerbated cathodic passivation. Consequently, our approach enables a low N/P ratio all-solid-state Na–S cell with a high reversible capacity of 1111 mA h g_S⁻¹ and an energy output of 880 W h kg_cathode⁻¹.

中文翻译：

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全固态Na-S电池的受限串联催化准固态硫可逆转化


控制复杂的多相硫/多硫化物氧化还原过程是减轻阴极钝化和释放全固态Na-S电化学高能潜力的基本途径。在此，通过采用受限串联电催化方法，我们成功地调整了多硫化物形态途径，以实现基于致密Na ₃ Zr ₂ PO ₁₂ 陶瓷膜。我们的设计采用约克壳结构的 MnHCF/PPy@MnO ₂ 同轴纳米管，具有局部和受限的环境。这些组分协同催化包封硫/硫化物的转化，其中MnO ₂ 有效引导长链多硫化物转变，MnHCF纳米团簇催化低动力学Na ₂ S ₄ 到 Na ₂ S 的直接和可逆转换。这有利于连续、完全可控的准固态硫转化，显着提高电池性能。操作研究表明，如果没有这些双催化中心的介导，电沉积的 Na ₂ S ₂ /Na ₂ S 在再充电，导致非活性多硫化物的积累并加剧阴极钝化。因此，我们的方法实现了低N/P比全固态Na-S电池，具有1111 mAh g的高可逆容量 _S ⁻¹ 和880 W的能量输出h 千克 _cathode ⁻¹ 。