Shuttling-free redox electrolyte locks proton-conductive polyoxometalates in porous carbon for high-performance pseudocapacitors

Redox electrolytes are highly attractive to bring conventional carbon-based supercapacitors the additional pseudocapacitance; however, shuttling of redox species remains a severe issue restricting the potential applications of redox electrolytes. Here, we report a new phosphotungstic acid-containing redox electrolyte for carbon-based supercapacitors, which shows the shuttling-free feature by locking the polyoxometalate mediators in the porous carbon electrode. Impressively, the porous carbon electrode affords a remarkable specific capacitance of 885.7 F g−1 at 5 mV s−1 in the phosphotungstic acid-added electrolyte, triple that in the additive-free H2SO4 electrolyte (290.2 F g−1). Profiting from the unique Grotthuss proton conduction of phosphotungstic acid, the porous carbon electrode achieves the dramatic rate capability in our redox electrolyte (i.e., 567.7 F g−1 at 200 mV s−1). Moreover, the assembled supercapacitor device affords a specific energy of 52.3 Wh kg−1 and long-term cycling stability (93.7% over 5000 cycles). This study highlights the superiority of the polyoxometalate additive for redox electrolytes in developing advanced supercapacitors integrating high energy density, excellent rate performance, and electrochemical durability.