Within the era of battery technology, the urgent demand for improved and safer electrolytes is immanent. In this work, novel electrolytes, based on pyrrolidinium-bistrifluoromethanesulfonyl-imide polymeric ionic liquids (POILs), equipped with quadrupolar hydrogen-bonding moieties of ureido-pyrimidinone (UPy) to mediate self-healing properties were synthesized. Reversible addition–fragmentation chain-transfer (RAFT) polymerization was employed using S,S-dibenzyl trithiocarbonate as the chain transfer agent to produce precise POILs with a defined amount of UPy and POIL-moieties. Kinetic studies revealed an excellent control over molecular weight and polydispersity in all polymerizations, with a preferable incorporation of UPy monomers in the copolymerizations together with the ionic monomers. Thermogravimetric analysis proved an excellent thermal stability of the polymeric ionic liquids up to 360 °C. By combining the results from differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS), and rheology, a decoupled conductivity of the POILs from glass transition was revealed. While the molecular weight was found to exert the main influence on ionic conductivity, the ultimate strength and the self-healing efficiency (of up to 88 %) were also affected, as quantified by tensile tests for both pristine and self-healed samples, evidencing a rational design of self-healing electrolytes bearing both hydrogen bonding moieties and low-molecular-weight polymeric ionic liquids.

Vitrimers have been widely employed in self-healing, recyclable, and shape-shifting materials. However, the application of catalyst-free vitrimers to create self-healable and mechanically robust gel polymer electrolytes (GPEs) remains a challenge, often limiting the potential of vitrimer-based materials. Herein, we utilized a catalyst-free dynamic covalent bond (silyl ether) as a linkage to prepare self-healable and mechanically robust GPEs, which are fully reprocessable. By incorporating polymeric ionic liquids into the dynamically cross-linked networks, both ion conductivity and mechanical properties can be flexibly tuned. The dynamic property of the network was demonstrated through frequency sweep rheology, which revealed a rubbery-like behavior at high frequencies and a liquidlike behavior at low frequencies. This dynamic feature enables self-healing and allows for reprocessing via embedding of such dynamic covalent networks into the GPEs. The GPEs containing 80 wt % of a bis(trifluoro­methansulfonamide) lithium/ionic liquid (LiTFSI/IL) mixture exhibited good ion conductivites of 0.13 mS/cm at 20 °C and 1.88 mS/cm at 80 °C. Furthermore, the elastic modulus of the GPEs could reach a value of 0.24 MPa and was able to persist through electrode-volume expansions during charging/discharging.The tunable dynamic properties, coupled with high ion conductivity and a high modulus, indicate promising applications for this type of dynamic bond in sustainable solid electrolytes.