Quenched polyampholytes provide a novel class of tough hydrogel that has self-healing ability, strong adhesion, and mechanical flexibility. Understanding the structure of polymer chains in the hydrogel and the phase behavior of water therein has broad impact on various applications, such as lubrication, adhesion, and electrical conductivity, as well as the hydrogel’s low temperature properties. In this paper, the structure of polymer chains of hydrogels made of a model charge-balanced polyampholyte, a random copolymer of poly(4-vinylbenzenesulfonate-co-[3-(methacryloylamino) propyl] trimethylammonium chloride), was investigated by small- and wide-angle x-ray scattering (SAXS and WAXS). The SAXS results suggested a networked globule structure in the charge-balanced polyampholyte hydrogels prevented freezing of water in the hydrogel, while the evidence of non-frozen water at low temperatures, such as –45 °C was monitored by solid-state 2H NMR. Correspondingly, we observed high ionic conductivity at low temperatures using electrochemical impedance spectroscopy (EIS). Interestingly, multiple freezing-thawing cycles did not impact the phase behavior of water in the hydrogel. We also found evidence that the crosslinked network structure of the polyampholyte chains disrupts the crystalline growth of ice, resulting in ‘slush-like’ ice formation.
Utilizing the scientific investigations, a flexible and self-healing supercapacitor with high energy density in low temperature operation was fabricated using a polyampholyte hydrogel electrolyte. The electrode material was a biochar (produced from the low-temperature pyrolysis of biological wastes) bound by self-assembled reduced graphene oxide. At the room temperature, the fabricated supercapacitor showed high energy density of 30 Wh/kg with 90% capacitance retention after 5000 charge-discharge cycles at room temperature at a power density of 50 W/kg. At –30 °C, the supercapacitor exhibited an energy sensity of 10.5 Wh/kg at a power density of 500 W/kg.
We also harnessed the tunable optical property of the polyampholyte hydrogel to fabricate a smart window. Specifically, we modulated the overall hydrophilicity/phobicity of polyampholyte chains when synthesizing the random copolymer and adjusted the upper critical solution temperature (UCST) at high precision, thus achieved a fine-tuning of UCST between 15 and 65 °C. Finally, we developed a stretchable, high-contrast, optically tunable stretchable window which consists of the PA hydrogel and a printed stretchable electric heater by our own ink recipe.
In summary, we performed fundamental studies on the phase behavior of polymer chains and water molecules in quenched polyampholyte hydrogels by using synchrotron SAXS/WAXS, solid-state NMR, EIS, and DSC. We utilized the understanding in energy storage and smart window applications, both of which are unconventional for the application of tough hydrogels.