Click Chemistry-Enabled Ionic Monomers for High-Performance Single-Ion Conducting Lithium Battery Electrolytes
5 affiliations
- 1Politecnico di Torino , , Corso Duca Degli Abruzzi 24 , ,
- 2National Reference Center for Electrochemical Energy Storage (GISEL)INSTM , Via G. Giusti 9 , ,
- 3Luxembourg Institute of Science and Technology (LIST) , , 5 Avenue des Hauts-Fourneaux , ,
- 4University of Luxembourg , , 2 Avenue de l’Université , ,
- 5Luxembourg Institute of Science and Technology (LIST) , , 41 Rue du Brill , ,
Abstract
Single-ion-conducting polymer electrolytes (SICPs) are attractive candidates for all-solid-state lithium-metal batteries because their immobilized anionic groups enable lithium-ion transference numbers approaching unity, thereby suppressing concentration polarization and promoting uniform lithium deposition. However, their widespread application remains limited by insufficient ionic conductivity and the lack of synthetically accessible ionic liquid monomers (ILMs) combining long, flexible spacers with high electrochemical stability. Herein, we report a modular thiol-Michael click strategy for the synthesis of a new family of TFSI-based ILMs incorporating thioether-containing spacers. The proposed approach requires only three reaction steps from readily available starting materials and enables straightforward structural tuning through the selection of commercially available mercapto alcohols. RAFT copolymerization of the resulting ILMs with poly(ethylene glycol) methacrylate, followed by cation exchange, affords a series of SICPs with tunable compositions and properties. The optimized electrolyte exhibits a glass-transition temperature of −45 °C, ionic conductivities of 1.1 × 10−6 and 1.8 × 10−5 S cm−1 at 25 and 70 °C, respectively, a lithium-ion transference number of 0.96, and an anodic stability approaching 5.0 V vs. Li+/Li at 70 °C. Symmetric Li|SICP|Li cells demonstrate stable lithium plating/stripping for more than 1400 h, while all-solid-state Li∥LiFePO4 cells deliver reversible specific capacities of up to 150 and >135 mAh g−1 at C/15 and C/5 rates, with capacity retention over 95% after 200 cycles, and exhibit markedly suppressed lithium dendrite formation compared with previously reported SICPs. These results demonstrate that thioether spacer engineering effectively enhances ion transport while preserving the intrinsic advantages of single-ion conduction, and establish thiol-Michael click chemistry as a simple, scalable platform for next-generation single-ion polymer electrolytes for high-energy lithium-metal batteries.
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BibTeX
@article{gambino2026click,
title = {{Click Chemistry-Enabled Ionic Monomers for High-Performance Single-Ion Conducting Lithium Battery Electrolytes}},
author = {Francesco Gambino and Vladislav Y. Shevtsov and Matteo Milanesi and Victor Benito Olmos and Jean-Nicolas Audinot and Giuseppe A. Elia and Claudio Gerbaldi and Alexander S. Shaplov},
journal = {JACS Au},
year = {2026},
month = nov,
doi = {10.1021/jacsau.6c01209},
url = {https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01209/5465171/Click-Chemistry-Enabled-Ionic-Monomers-for-High},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Click Chemistry-Enabled Ionic Monomers for High-Performance Single-Ion Conducting Lithium Battery Electrolytes
AU - Francesco Gambino
AU - Vladislav Y. Shevtsov
AU - Matteo Milanesi
AU - Victor Benito Olmos
AU - Jean-Nicolas Audinot
AU - Giuseppe A. Elia
AU - Claudio Gerbaldi
AU - Alexander S. Shaplov
PY - 2026
DA - 2026/11/05
JO - JACS Au
DO - 10.1021/jacsau.6c01209
UR - https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01209/5465171/Click-Chemistry-Enabled-Ionic-Monomers-for-High
AB - Single-ion-conducting polymer electrolytes (SICPs) are attractive candidates for all-solid-state lithium-metal batteries because their immobilized anionic groups enable lithium-ion transference numbers approaching unity, thereby suppressing concentration polarization and promoting uniform lithium deposition. However, their widespread application remains limited by insufficient ionic conductivity and the lack of synthetically accessible ionic liquid monomers (ILMs) combining long, flexible spacers with high electrochemical stability. Herein, we report a modular thiol-Michael click strategy for the synthesis of a new family of TFSI-based ILMs incorporating thioether-containing spacers. The proposed approach requires only three reaction steps from readily available starting materials and enables straightforward structural tuning through the selection of commercially available mercapto alcohols. RAFT copolymerization of the resulting ILMs with poly(ethylene glycol) methacrylate, followed by cation exchange, affords a series of SICPs with tunable compositions and properties. The optimized electrolyte exhibits a glass-transition temperature of −45 °C, ionic conductivities of 1.1 × 10−6 and 1.8 × 10−5 S cm−1 at 25 and 70 °C, respectively, a lithium-ion transference number of 0.96, and an anodic stability approaching 5.0 V vs. Li+/Li at 70 °C. Symmetric Li|SICP|Li cells demonstrate stable lithium plating/stripping for more than 1400 h, while all-solid-state Li∥LiFePO4 cells deliver reversible specific capacities of up to 150 and >135 mAh g−1 at C/15 and C/5 rates, with capacity retention over 95% after 200 cycles, and exhibit markedly suppressed lithium dendrite formation compared with previously reported SICPs. These results demonstrate that thioether spacer engineering effectively enhances ion transport while preserving the intrinsic advantages of single-ion conduction, and establish thiol-Michael click chemistry as a simple, scalable platform for next-generation single-ion polymer electrolytes for high-energy lithium-metal batteries.
SN - 2691-3704
ER -