An all‐solid‐state P‐doped graphene oxide/carbon fiber (PGO/CF)//NiCo2O4‐based graphene oxide/carbon fiber (NCGO/CF) flexible asymmetric fiber supercapacitor (AFSC) with favorable flexibility and electrochemical properties is successfully assembled based on the PGO/CF and NCGO/CF electrodes. Interestingly, the introduction of the double reference electrode system provides a promising method for the study of the electrochemical performances of two‐electrode systems. Abstract Fiber supercapacitors (FSCs) are promising energy storage devices in portable and wearable smart electronics. Currently, a major challenge for FSCs is simultaneously achieving high volumetric energy and power densities. Herein, the microscale fiber electrode is designed by using carbon fibers as substrates and capillary channels as microreactors to space‐confined hydrothermal assembling. As P‐doped graphene oxide/carbon fiber (PGO/CF) and NiCo2O4‐based graphene oxide/carbon fiber (NCGO/CF) electrodes are successfully prepared, their unique hybrid structures exhibit a satisfactory electrochemical performance. An all‐solid‐state PGO/CF//NCGO/CF flexible asymmetric fiber supercapacitor (AFSC) based on the PGO/CF as the negative electrode, NCGO/CF hybrid electrode as the positive electrode, and poly(vinyl alcohol)/potassium hydroxide as the electrolyte is successfully assembled. The AFSC device delivers a higher volumetric energy density of 36.77 mW h cm−3 at a power density of 142.5 mW cm−3. In addition, a double reference electrode system is adopted to analyze and reduce the IR drop, as well as effectively matching negative and positive electrodes, which is conducive for the optimization and improvement of energy density. For the AFSC device, its better flexibility and electrochemical properties create a promising potential for high‐performance micro‐supercapacitors. Furthermore, the introduction of the double reference electrode system provides an interesting method for the study on the electrochemical performances of two‐electrode systems.

Published in: "Small".