Mechanistic Understanding of the Underlying Energy Storage Mechanism of α‐MnO2‐based Pseudo‐Supercapacitors

Abstract Manganese dioxide (α‐MnO 2 ) has attracted significant research interest in supercapacitors recently. However, the reaction mechanism of α‐MnO 2 in supercapacitors remains unclear. Therefore, a nano‐supercapacitor using Environmental transmission electron microscopy (ETEM) is conducted and investigated the reaction mechanism of α‐MnO 2 based on three ionic liquids (ILs). It found that in the aprotic ionic liquid (AIL) 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate (EMIMOTF), α‐MnO 2 nanowires (NWs) undergo an oxidation reaction due to the presence of an active proton at the second position (H2) of the imidazole ring. As a result, α‐MnO 2 NWs undergo a phase transition and transform into Mn 3 O 4 , exhibiting pseudo‐capacitive properties. Furthermore, characterization of the macroscopic α‐MnO 2 electrodes after cycling reveals that after the initial charging cycles, the dominant energy storage mechanism of the supercapacitor transitions from pseudo‐capacitance to a dual‐layer capacitance formed by the combination of Mn 3 O 4 and unreacted α‐MnO 2 . Simultaneously, due to the coexistence of these two energy storage mechanisms, the specific capacitance of the supercapacitor in EMIMOTF electrolyte reaches up to 80 F g −1 , and the cycle number reaches as high as 1000 cycles. The results are expected to provide insights into the selection of electrolytes in supercapacitors and offer a fundamental understanding of the internal reaction mechanisms in capacitors.