Proton is Essential or Not: A Fresh Look on Pseudocapacitive Energy Storage of PANI Composites

Protonation has been considered essential for the pseudocapacitive energy storage of polyaniline (PANI) for years, as proton doping in PANI chains not only activates electron transport pathways, but also promotes the proceeding of redox reactions. Rarely has the ability for PANI of storing energy without protonation been investigated, and it remains uncertain whether PANI has pseudocapacitive charge storage properties in an alkaline electrolyte. Here, this work first demonstrates the pseudocapacitive energy storage for PANI without protonation using a PANI/graphene composite as a model material in an alkaline electrolyte. Using in situ Raman spectroscopy coupled with electrochemical quartz crystal microbalance (EQCM) measurements, this work determines the formation of -N= group over potential on a PANI chain and demonstrates the direct contribution of OH- in the nonprotonation type of oxidation reactions. This work finds that the PANI/graphene composite in an alkaline electrolyte has excellent cycling stability with a wider operation voltage of 1 V as well as a slightly higher specific capacitance than that in an acidic electrolyte. The findings provide a new perspective on pseudocapacitive energy storage of PANI-based composites, which will influence the selection of electrolytes for PANI materials and expand their application in energy storage fields. Efficient pseudocapacitive energy storage of polyaniline (PANI) in alkaline electrolytes and its energy storage mechanism are demonstrated by using PANI/rGO (reduced graphene oxide) composite as electrode material. In alkaline electrolytes, the fabricated supercapacitor has greater cycling stability with capacitance retention of 87% after 30 000 cycles in a wider cell voltage of 1 V and a slightly higher capacitance than that in acidic electrolytes.image