Wang Xinyuan, Fan Yuxin, Xie Lei, He Huibing, Wang Guifang, Zhu Jinliang
School of Resources, Environment and Materials, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi University, Nanning 530004, PR China.
School of Resources, Environment and Materials, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi University, Nanning 530004, PR China.
J Colloid Interface Sci. 2025 Feb;679(Pt A):1076-1083. doi: 10.1016/j.jcis.2024.10.058. Epub 2024 Oct 12.
The shuttle effect of lithium polysulfides (LiPSs) significantly hinders the practical application of lithium-sulfur batteries (LSBs). Herein, a high-entropy hydroxyphosphate (CoNiFeCuCa(PO)(OH), denoted as HE-CHP), was synthesized by metal cation exchange with calcium hydroxyphosphate (CHP) and then coated on polypropylene (PP) separators to suppress the shuttling of LiPSs. Density functional theory calculations indicated that the various introduced metal cations could effectively modulate the binding strength of soluble polysulfides and enhance the reaction kinetics of LiPSs conversion. As a result, LSBs using the HE-CHP@PP separator exhibited an excellent discharge capacity (1297 mAh g under 0.2 C) and a slow capacity decay during long-term cycling (0.046 % per cycle at 2 C). At a sulfur loading of up to 6.5 mg cm, the LSB with HE-CHP@PP separator displayed a discharge capacity of 5.8 mAh cm. Notably, the CNT@S||Li Li-S pouch cell with HE-CHP modified separator delivered an initial energy density of 432 Wh kg.
多硫化锂（LiPSs）的穿梭效应严重阻碍了锂硫电池（LSBs）的实际应用。在此，通过金属阳离子与羟基磷酸钙（CHP）进行交换合成了一种高熵羟基磷酸盐（CoNiFeCuCa(PO)(OH)，记为HE-CHP），然后将其涂覆在聚丙烯（PP）隔膜上以抑制LiPSs的穿梭。密度泛函理论计算表明，引入的各种金属阳离子可有效调节可溶性多硫化物的结合强度，并增强LiPSs转化的反应动力学。结果，使用HE-CHP@PP隔膜的LSBs表现出优异的放电容量（在0.2 C下为1297 mAh g）以及在长期循环过程中缓慢的容量衰减（在2 C下每循环0.046%）。在硫负载量高达6.5 mg cm时，具有HE-CHP@PP隔膜的LSB显示出5.8 mAh cm的放电容量。值得注意的是，采用HE-CHP改性隔膜的CNT@S||Li锂硫软包电池的初始能量密度为432 Wh kg。
