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Self-Limiting Covalent Ligation Mechanism Enabling Anomalously High Interfacial Compatibility in Organic-in-Sulfide
Yan Zhang1,2, Yuxi Zhong1, Ruiqi Guo1,2
1Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, People's Republic of China.
Angewandte Chemie (International Ed. in English)
|May 26, 2026
Summary
A new self-limiting covalent ligation mechanism explains the compatibility of polymer-in-sulfide electrolytes in all-solid-state lithium batteries. This discovery enhances stability and performance for advanced battery development.
Area of Science:
- Materials Science
- Electrochemistry
- Solid-State Chemistry
Background:
- Polymer-in-sulfide composite electrolytes are key for all-solid-state lithium batteries (ASSLBs), offering processability and fast ion transport.
- Ethylene oxide-tethered polyacrylates (EO-PAs) show unexpected compatibility with sulfides, despite their reactivity, posing a mechanistic puzzle.
- Understanding this polymer-sulfide interface is crucial for developing stable and efficient ASSLBs.
Purpose of the Study:
- To elucidate the mechanism behind the high compatibility of EO-PAs with sulfide electrolytes.
- To identify the interfacial interactions that prevent degradation and enhance stability.
- To provide insights for designing next-generation polymer-in-sulfide electrolytes for ASSLBs.
Main Methods:
- Density functional theory (DFT) calculations to model interfacial interactions.
- Solid-state nuclear magnetic resonance (31P NMR) spectroscopy to probe chemical environments.
- X-ray computed tomography (CT) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) for structural and chemical analysis.
- Electrochemical testing of lithium plating/stripping and cycling stability in ASSLBs.
Main Results:
- A self-limiting covalent ligation mechanism was identified between EO-PA terminal methyl groups and PS43- anions in Li6PS5Cl.
- This interaction suppresses nucleophilic attack by EO ligands, enhancing sulfide electrolyte stability and air stability.
- The validated interface enabled dendrite-free Li plating/stripping for over 1200 hours and 100% capacity retention over 1000 cycles.
Conclusions:
- The study reveals a novel self-limiting ligation mechanism governing polymer-sulfide electrolyte interfaces.
- This mechanism explains the paradox of high compatibility despite inherent reactivity.
- Findings offer critical guidance for engineering stable and high-performance polymer-in-sulfide electrolytes for ASSLBs.
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