Rationalizing the Role of Polyoxometalate‐Based Gel–Polymer Electrolytes to Achieve Five‐Fold Increase in the Specific Capacitance of Hard‐Carbon‐Based Supercapacitors

Abstract

Boosting the charge‐transport pathways in gel–polymer electrolytes (GPEs) is important to extract their full potential for non‐Faradaic, supercapacitive energy‐storage devices. Herein, a series of polyoxometalates (POMs) ([P6W18O79]20−, [PW9O34]9− and [PW12O40]3−) as electrochemical polarization promoters is demonstrated to achieve 15‐fold enhancement in ionic conductivity of 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide‐based GPEs. Fundamentally, the three POMs offer systematically differing charge densities (200, 45, and 6.5 e− nm−3) that are linearly correlated to the observed enhancements in ionic conductivities. The charge density on the POMs contributes to the formation of additional charge‐migrative pathways across the GPE, as evidenced from facile polarization characteristics. Importantly, the presence of POM beyond a critical concentration acts as charge‐trapping centers to impede the ionic conductivity of the GPEs. The insights obtained through such detailed spectroscopic and electrochemical techniques are integrated into full‐scale supercapacitive devices with a rationally designed porous hard carbon as the electrode material. The resulting electrode–electrolyte interface synergies achieve a best‐in‐class supercapacitor exhibiting energy density of 58 Wh kg−1, power density of 14 kW kg−1, and a relaxation time constant of 0.66 s, without compromising on cycling stability for direct integration with intermittent energy‐harvesting devices. Thus, the fundamental insights presented here outline the design principles for extracting high‐performance from GPE‐based energy‐storage devices.