Designing of zwitterionic proline hydrogel electrolytes for anti-freezing supercapacitors

Hydrogel electrolytes containing a large amount of freezable water tend to freeze at subzero temperatures, which catastrophically reduces their ionic conductivity and thus limits their practical applications. In this work, we propose a new type anti-freezing hydrogel electrolyte based on an additive of zwitterionic proline, which can maintain high ionic conductivities of hydrogel electrolytes at subzero temperatures. The unique zwitterionic structure leads to several interesting characters like strong hydration, strong ionic interactions and low self-associations, which is proved to be the keys for the high performance of hydrogel electrolytes under low temperatures. As a result, the proline hydrogel electrolytes show a high ionic conductivity of 4.2 mS cm^-1 even at -40 °C. The activated carbon electrode of supercapacitors based on proline hydrogel electrolytes delivers high specific capacitances of 145.8 (at 0.5 A g^-1) and 116.1 F g^-1 (at 0.5 A g^-1) at 25 and -30 °C, respectively. Furthermore, the specific capacitance still shows a high retention of 71% after 12,000 charge/discharge cycles at -30 °C, confirming the good low-temperature adaptability. Such anti-freezing electrolytes with high ionic conductivity will open up a new avenue for anti-freezing energy storage devices, not limited to supercapacitors.