An asymmetric MnO₂|activated carbon supercapacitor with highly soluble choline nitrate-based aqueous electrolyte for sub-zero temperatures

MnO₂|activated carbon supercapacitors are attractive power devices that rival the electric double-layer capacitors (EDLCs) due to high reachable voltage. However, they greatly suffer from performance loss at low temperature as most of aqueous electrolytes freeze below ca. -10°C. Here, a concentrated choline nitrate-based (5 mol/L aqueous ChNO₃) electrolyte is applied to extend the working temperature range due to its eutectic-like properties. In such electrolyte, water acts as hydrogen bond donor for nitrate anion and low hydration energy for large choline cations favors ionic transport. The MnO₂/CNT composite electrode with a hierarchical structure has been synthesized by hydrothermal process. The presence of CNTs as core component facilitates the electron conduction, while the two-dimensional MnO₂ flakes grown on the surface provide electrolyte transport pathways and improve the interfacial processes (pseudocapacitive charge/discharge). Thanks to the low hydration of choline cation, the individual activated carbon (AC, negative) and MnO₂/CNT (positive) electrodes are charged symmetrically up to a cell voltage of 1.8 V. Overall, due to the wide electrochemical stability window (∼2.0 V) and anti-freezing properties of ChNO₃-based aqueous electrolyte and the hierarchical design of the MnO₂/CNT composite, the asymmetric supercapacitor operates down to -40 °C and displays excellent energy and coulombic efficiency with no loss of performance after several thousand cycles. This work provides a new possibility on the low temperature application of high voltage supercapacitors.