A Silk Protein-Based Eutectogel as a Freeze-Resistant and Flexible Electrolyte for Zn-Ion Hybrid Supercapacitors

A eutectogel (ETG) based on immobilizing a zinc salt deep eutectic solvent (DES) in a silk protein backbone is prepared by a coagulating bath method as a solid electrolyte for Zn-ion hybrid supercapacitors (ZHSCs). The Zn salt DES is composed by ethylene glycol (EG), urea, choline chloride (ChCl), and zinc chloride (ZnCl₂) with a molar ratio of 6:10:3:3. A strong bonding of the DES liquid to the silk protein backbone is formed between protein macromolecules and the DES due to plenty of hydrogen bonds in both materials. The as-prepared ETG membrane is dense and has no obvious void defects, which possesses a fracture strength of 7.58 MPa and environmental stability. As a solid electrolyte, the ETG membrane exhibits a higher Zn²⁺ transference number of about 0.60 and a high ionic conductivity (12.31 mS cm^-1 at room temperature and 3.63 mS cm^-1 at -20 °C). A ZHSC (Zn∥ETG∥C) with the silk protein-based ETG electrolyte is assembled by Zn and active carbon as the anode and the cathode, respectively, which delivers a specific capacitance of 342.8 F g^-1 at a current density of 0.2 A g^-1 and maintains excellent cycling stability with 80% capacitance retention after 20,000 cycles at a high current rate (5 A g^-1) at room temperature. Moreover, the Zn∥ETG∥C device can safely work under a lower temperature of about -18 °C and damaging situations, such as folding states and even cutting tests. The interface evolutions between the Zn anode and the ETG electrolyte are explored, and it was found that a ZnCO₃/Zn(CH₂OCO₂)₂ solid electrolyte interphase is in situ formed on the Zn anode, which can inhibit the growth of Zn dendrites. This work provides a new way to fabricate advanced electrolytes for applications in Zn-ion hybrid supercapacitors.