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Vol. 18 (2026)

Engineering Dynamic Electrolyte Microenvironments via Double-Shell Hosts for Practical Lithium–Sulfur Batteries

https://doi.org/10.1007/s40820-026-02260-2
Ziqing Yao
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Yulu Zou
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Shuqi Zhang
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Wei Xie
School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, People’s Republic of China
Yujie Li
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Shuangke Liu
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Xingyu Chen
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Kun Zhang
Department of Chemistry, National University of Singapore, Singapore 117543, Singapore
Chunman Zheng
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China
Weiwei Sun
College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, People’s Republic of China

Corresponding Author: Weiwei Sun

wwsun@nudt.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 406

Abstract

The practical deployment of lithium–sulfur (Li–S) batteries is hampered by the shuttle effect of lithium polysulfides (LiPSs) and sluggish kinetics of sulfur redox reaction. While prevailing research focuses on maximizing the intrinsic activity of catalysts, the critical role of the host architecture in modulating the local reaction microenvironment remains overlooked. Herein, we report a facile ion-exchange strategy to synthesize double-shell hollow Prussian blue analogue derivative (Co2.5Fe/NC) as advanced sulfur hosts by precisely controlling the Co/Fe molar ratio at 2.5. Finite element simulations and in situ diagnostics reveal that the double-shell structure orchestrates a self-propelled electrolyte flow within the nanoreactor during operation. This dynamic flow effectively mitigates the spatial concentration heterogeneity of LiPSs, especially near the catalysts, thereby preventing active material passivation and ensuring sustained high catalytic efficiency. Consequently, even with a catalyst of moderate intrinsic activity, the Co2.5Fe/NC cathode achieves exceptional stability under lean electrolyte conditions (0.016% decay per cycle over 1000 cycles at 2 C). More importantly, an Ah-level pouch cell delivers a high energy density of 454.7 Wh kg⁻1. This work shifts the paradigm from solely pursuing catalytic activity to designing host structures that intelligently manage the electrochemical microenvironment, offering a new avenue toward practical Li–S batteries.


Highlights:
1 The efficient preparation of sulfur hosts derived from Prussian blue analogues with double-shell hollow structure was achieved through ion exchange with precisely controlled elemental ratios.
2 The double-shell structure alters the microenvironment of sulfur redox reaction through self-driven dynamic migration of electrolyte, preventing the local enrichment of lithium polysulfides around catalysts.
3 The double-shell sulfur cathode enhances the cycling stability and practical application of lithium–sulfur batteries, enabling an Ah-level pouch cell with an energy density of 454.7 Wh kg–1.

Keywords

Lithium–sulfur batteries Prussian blue analogues derivatives Double-shell structure Dynamic electrolyte microenvironments
Yao, Ziqing, Yulu Zou, Shuqi Zhang, Wei Xie, Yujie Li, Shuangke Liu, Xingyu Chen, Kun Zhang, Chunman Zheng, and Weiwei Sun. 2026. “Engineering Dynamic Electrolyte Microenvironments via Double-Shell Hosts for Practical Lithium–Sulfur Batteries”. Nano-Micro Letters 18 (June):406. https://doi.org/10.1007/s40820-026-02260-2.
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