In Situ Studies of Ion Transport in Microporous Supercapacitor Electrodes at Ultralow Temperatures

The ability to quickly store and deliver a significant amount of electrical energy at ultralow temperatures is critical for the energy‐efficient operation of high altitude aircraft and spacecraft, exploration of natural resources in polar regions and extreme altitudes, and astronomical observatories exposed to ultralow temperatures. Commercial high‐power electrochemical capacitors fail to operate at temperatures below –40 °C. According to conventional wisdom, mesoporous electrochemical capacitor electrodes with pores large enough to accommodate fully solvated ions are needed for sufficiently rapid ion transport at lower temperatures. It is demonstrated that strictly microporous carbon electrodes with much higher volumetric capacitance can be efficiently used at temperatures as low as –70 °C. The critical parameters, with respect to electrolyte properties and electrode porosity and microstructure, needed for achieving both rapid ion transport and efficient ion electroadsorption in porous carbons are discussed. As an example, the fabrication of an electrochemical capacitor with an outstanding performance at temperatures as low as –60 and –70 °C is demonstrated. At such low temperatures the capacitance of the synthesized electrodes is up to 123 F g−1 (≈76 F cm−3), which is 50–100% higher than that of the most common commercial electrochemical capacitor electrode at room temperature. At –60 °C selected cells based on ≈0.2 mm electrodes exhibited characteristic charge–discharge time constants of less than 9 s, which is faster than the majority of commercial devices at room temperature. The achieved combination of high energy and power densities at such ultralow temperatures is unprecedented and extremely promising for the advancement of energy storage systems. Uniform, microporous, zeolite‐templated carbons produced at low pressures demonstrate excellent ion transport and electroadsorption in pores at low temperatures. When used with a carefully designed electrolyte, these properties allow for fabrication of supercapacitors with an unprecedented combination of high specific capacitance, rapid charging ability, and high energy density characteristics at ultralow temperatures.