Solid-State Transformations of Active Materials in the Pores of Sulfurized-Polyacrylonitrile Fiber Membranes via Nucleophilic Reactions for High-Loading and Free-Standing Lithium–Sulfur Battery Cathodes

IF 17.2 1区工程技术 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Advanced Fiber Materials Pub Date : 2024-03-14 DOI:10.1007/s42765-024-00391-y

Hao Liu, Yun Zhang, Yongbing Li, Na Han, Haihui Liu, Xingxiang Zhang

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Abstract

Sulfurized polyacrylonitrile (SPAN) has emerged as an excellent cathode material for lithium–sulfur batteries (LiSBs), and it addresses the shuttle effect through a solid‒solid reaction. However, the actual sulfur loadings in SPAN often remain below 40 wt%. Due to the susceptibility of polysulfides-to-nucleophilic reactions with electrolytes, achieving physical encapsulation of elemental sulfur is a challenging task. In this study, a free-standing cathode material with a high sulfur/selenium (S/Se) loading of 55 wt% was fabricated by introducing SeS_x into the unique lotus root-like pores of porous SeS_xPAN nanofiber membranes by electrospinning and a two-step heat treatment. Insoluble compounds were formed due to nucleophilic interactions between lithium polyselenosulfides (LiSeS_x) and the electrolyte, which potently blocked the existing lotus root-like pores and facilitated the creation of a thin cathode–electrolyte interphase on the fiber surface. This dual functionality of LiSeS_x safeguarded the active material embedded within the porous structure. The SeS₁₅PAN cathode exhibited remarkable cycling stability with almost no degradation after 200 cycles at 0.2 C, along with a high discharge capacity of 580 mAh/g. This approach presents a solution for addressing the insufficient sulfur content in SPAN.

Graphical Abstract

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通过亲核反应实现硫化聚丙烯腈纤维膜孔隙中活性材料的固态转化，用于高装载和独立式锂硫电池阴极

硫化聚丙烯腈（SPAN）已成为锂硫电池（LiSBs）的一种优秀正极材料，它通过固-固反应解决了穿梭效应问题。然而，SPAN 中的实际硫含量往往低于 40 wt%。由于多硫化物容易与电解质发生亲核反应，因此实现元素硫的物理封装是一项具有挑战性的任务。在本研究中，通过电纺丝和两步热处理，将 SeSx 引入多孔 SeSxPAN 纳米纤维膜独特的莲藕状孔隙中，制造出了硫/硒（S/Se）负载量高达 55 wt% 的独立阴极材料。由于锂多硒硫化物（LiSeSx）与电解质之间的亲核相互作用，形成了不溶性化合物，从而有效地阻塞了现有的莲藕状孔隙，并促进了在纤维表面形成薄薄的阴极-电解质间相。LiSeSx 的这种双重功能保护了嵌入多孔结构中的活性材料。SeS15PAN 阴极表现出显著的循环稳定性，在 0.2 C 下循环 200 次后几乎没有降解，同时还具有 580 mAh/g 的高放电容量。这种方法为解决 SPAN 中硫含量不足的问题提供了一种解决方案。

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来源期刊

Advanced Fiber Materials Multiple-

CiteScore

18.70

自引率

11.20%

发文量

109

期刊介绍： Advanced Fiber Materials is a hybrid, peer-reviewed, international and interdisciplinary research journal which aims to publish the most important papers in fibers and fiber-related devices as well as their applications.Indexed by SCIE, EI, Scopus et al. Publishing on fiber or fiber-related materials, technology, engineering and application.