Solid‐state lithium–sulfur battery (SSLSB) is attractive due to its potential for providing high energy density. However, the cell chemistry of SSLSB still faces challenges such as sluggish electrochemical kinetics and prominent “chemomechanical” failure. Herein, a high‐performance SSLSB is demonstrated by using the thio‐LiSICON/polymer composite electrolyte in combination with sulfurized polyacrylonitrile (S/PAN) cathode. Thio‐LiSICON/polymer composite electrolyte, which processes high ionic conductivity and wettability, is fabricated to enhance the interfacial contact and the performance of lithium metal anodes. S/PAN is utilized due to its unique electrochemical characteristics: electrochemical and structural studies combined with nuclear magnetic resonance spectroscopy and electron paramagnetic resonance characterizations reveal the charge/discharge mechanism of S/PAN, which is the radical‐mediated redox reaction within the sulfur grafted conjugated polymer framework. This characteristic of S/PAN can support alleviating the volume change in the cathode and maintaining fast redox kinetics. The assembled SSLSB full cell exhibits excellent rate performance with 1183 mAh g⁻¹ at 0.2 C and 719 mAh g⁻¹ at 0.5 C, respectively, and can accomplish 50 cycles at 0.1 C with the capacity retention of 588 mAh g⁻¹. The superior performance of the SSLSB cell rationalizes the construction concept and leads to considerations for the innovative design of SSLSB.

中文翻译：

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Thio-LiSICON /聚合物复合电解质和硫化聚丙烯腈阴极驱动的固态锂硫电池

固态锂硫电池（SSLSB）具有潜力，可提供高能量密度。然而，SSLSB的电池化学仍然面临诸如缓慢的电化学动力学和突出的“化学机械”失效等挑战。在本文中，通过将硫代-LiSICON /聚合物复合电解质与硫化聚丙烯腈（S / PAN）阴极结合使用，证明了高性能的SSLSB。Thio-LiSICON /聚合物复合电解质具有很高的离子电导率和润湿性，其制造目的是增强界面接触和锂金属阳极的性能。利用S / PAN具有独特的电化学特性：电化学和结构研究与核磁共振波谱和电子顺磁共振表征相结合，揭示了S / PAN的充电/放电机理，这是硫接枝的共轭聚合物骨架中自由基介导的氧化还原反应。S / PAN的这一特性可以支持减轻阴极中的体积变化并保持快速的氧化还原动力学。组装后的SSLSB全电池在1183 mAh g时表现出出色的速率性能^分别在0.2 C下为^-1和在0.5 C下为719 mAh g ^-1，并且可以在0.1 C下完成50个循环，并保持588 mAh g ^-1的容量。SSLSB单元的卓越性能合理化了构造概念，并引发了SSLSB创新设计的考虑。