Advanced Redox Electrochemical Capacitor Diode (CAPode) Based on Parkerite (Ni3Bi2S2) with High Rectification Ratio for Iontronic Applications

Recently, electrochemical capacitor diodes (CAPodes) have been introduced as a new type of capacitive diode analogues. This device realizes unidirectional charging of ultracapacitors based on ion sieving mechanisms. Here, a new redox CAPode system is presented in which hydroxide ions react with nickel bismuth sulfide on nickel foam as a battery‐like electrode. This redox reaction leads to a high capacitance in a specific polarization window. However, for reversed bias this Faradaic electrode becomes inactive as it does not react with potassium cations, resulting in efficient blocking. By adapting counter electrode materials, mass loading, utilized substrates, and electrolyte concentrations a very high rectification ratio (RI = 37 and RII = 0.96 at 10 mV s−1) is achieved, significantly surpassing the performance of other reported redox‐type CAPodes. Moreover, this system shows an outstanding long‐term stability of a rectification retention of 90% for RII over 5000 repolarization cycles. Additionally, operando electrochemical measurements provide deep insights into the charge/discharge mechanism leading to a rationalization of the proposed concept. The integrated device, tested in logic gate circuits such as AND and OR gates, shows prospective results in ionologic applications. The redox CAPode system utilizing hydroxide ions and nickel bismuth sulfide on nickel foam demonstrates high capacity within specific polarization limits. The electrode adaptions yield remarkable rectification ratios (RI = 37, RII = 0.96), surpassing prior performances. Exceptional long‐term stability (90% retention over 5000 cycles) and unidirectional charge/discharge mechanisms make it promising for ionologic applications, including logic gates.