Polyrotaxane-engineered dynamically adaptive slide-crosslinked polymer electrolyte enabling high-performance solid-state lithium metal batteries

Xiaoyue Zeng; Huirong Zhu; Haocheng Yuan; Xuewei Liu; Jiaxing Zhu; Jinghao Hua; Jinle Lan; Yunhua Yu; Young-Seak Lee; Xiaoping Yang

doi:10.1016/j.jcis.2025.138153

Polyrotaxane-engineered dynamically adaptive slide-crosslinked polymer electrolyte enabling high-performance solid-state lithium metal batteries

J Colloid Interface Sci. 2025 Jun 11;699(Pt 1):138153. doi: 10.1016/j.jcis.2025.138153. Online ahead of print.

Authors

Affiliations

¹ State Key Laboratory of Organic-Inorganic Composites, College of Materials Science and Engineering, Beijing University of Chemical Technology, North Third Ring Road 15, Chaoyang District, Beijing 100029, PR China.
² State Key Laboratory of Organic-Inorganic Composites, College of Materials Science and Engineering, Beijing University of Chemical Technology, North Third Ring Road 15, Chaoyang District, Beijing 100029, PR China. Electronic address: lanjl@mail.buct.edu.cn.
³ State Key Laboratory of Organic-Inorganic Composites, College of Materials Science and Engineering, Beijing University of Chemical Technology, North Third Ring Road 15, Chaoyang District, Beijing 100029, PR China. Electronic address: yuyh@mail.buct.edu.cn.
⁴ Department of Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon 34134, Republic of Korea; Institute of Carbon Fusion Technology (InCFT), Chungnam National University, Daejeon 34134, Republic of Korea.

PMID: 40527144
DOI: 10.1016/j.jcis.2025.138153

Abstract

The electrolyte of solid-state lithium metal batteries (LMBs) is challenged by lithium dendrites growth and repeated volume expansion and contraction of Li anodes. Conventional crosslinked polymer electrolytes struggle to meet the requirements of high-safety and long-cycling due to the inherent compromise between mechanical rigidity and ion transport. Herein, we report a dynamically adaptive slide-crosslinked polymer electrolyte (PPRx-PVC) synthesized via in-situ copolymerization of vinyl-functionalized pseudopolyrotaxane (PPRx=, x represents the molecular weight of PEG in PPRx=) and vinylene carbonate (VC). The molecular pulley mechanism of polyrotaxane enables synergistic enhancement of mechanical robustness (Young's modulus >2 GPa) and energy dissipation capacity via reversible sliding of threaded cyclodextrin rings along the guest polymer. Systematic optimization of PPRx= molecular weight (Mn ≈ 20,000 g mol^-1) reveals a critical interplay between ion interaction and network dynamics, achieving an exceptional Li⁺ transference number of 0.78 and electrochemical stability window of 4.85 V. The optimized PPR20000-PVC electrolyte demonstrates suppressed dendrite growth through adaptive stress redistribution during 1300 h Li plating/stripping at 0.5 mA cm^-2, enhanced interfacial durability against Li anode volume changes via dynamic network reconfiguration, and superior performance in Li||LiFePO₄ (LFP) with 93.2 % capacity retention over 200 cycles at 0.5C.This work provides new design of polymer electrolyte for high-performance LMBs that concurrently address mechanical durability, interfacial compatibility, and ion transport challenges in LMBs.

Keywords: Energy dissipation; Robust-flexible; Simplified synthesis; Slide-crosslinked polymer; Vinyl modified pseudopolyrotaxane.