Luyi Xiao, Wei Ding, Daniel Crespy, Li‐Ping Lv, Yong Wang
Abstract Traditional gel electrolytes based on weak interactions possess insufficient self‐healing property and also tend to rigidify during usage, which largely compromises the electrochemical performances of flexible supercapacitors (FSCs). Herein, a multifunctional ionic gel electrolyte, formed by the polymerization of limonene (LIM) and lipoic acid (LA) is proposed, displaying a collaborative self‐healing mechanism based on dual dynamic bonds, i.e., hydrogen bonds and disulfide bonds, and excellent persistence when combined with ionic liquids (ILs). In situ characterizations verify the exceptional self‐healing capabilities arising from dynamic disulfide and H‐bonds, which maintain structural integrity of the device upon deformation and even mechanical defects. ILs with electrostatic interactions and low saturation vapor pressure further strengthen the internal forces of the gel, meanwhile providing high ionic conductivity and durability upon varied temperature. Subsequently, the assembled FSCs with N‐doped carbon electrodes and P(LA‐LIM)‐IL electrolyte exhibit an impressive energy density of 22 µWh cm −2 and cyclability without attenuation of capacitance after 10 000 cycles. It also maintains 85% of capacitance after 100 cycles of mechanical deformation and a remarkable recovery of capacitance (92%) after 20 cutting/healing cycles. This multifunctional ionic gel electrolyte may broaden the way to design flexible SCs with superior self‐healing and resistant properties toward long lifespan.