AbstractCarbon cloth shows potential for flexible energy storage electrodes but encounters challenges such as low specific capacitance and limited wettability. This study addresses these limitations by fabricating a highly conformal coating of poly(3,4‐ethylenedioxythiophene) (PEDOT) around 3D carbon fibers via the oxidative chemical vapor deposition (oCVD) method, employing antimony pentachloride (SbCl5) as the oxidant. The oCVD stands out as a robust manufacturing technique for fabricating highly conformal conducting polymer films on porous structures, ensuring the preservation of geometric features and the maintenance of active sites for redox reactions. The resulting PEDOT‐coated carbon cloth electrodes exhibit improved pseudocapacitance and specific capacitance compared to their pristine counterparts. Particularly, oCVD PEDOT‐coated carbon cloth fabricated at various deposition temperatures exhibit a substantial 1.5‐ to 2.3‐fold enhancement in specific capacitance compared to pristine carbon cloth. The highest specific capacitance (170.94 F g⁻¹) is attained in the oCVD PEDOT‐coated carbon cloth fabricated at a deposition temperature of 80 °C, representing a 2.3‐fold enhancement over its pristine counterpart. The PEDOT‐coated carbon cloths demonstrate lower charge transfer resistance compared to their pristine counterparts, further confirming their superior electrochemical performance. This investigation highlights oCVD's effectiveness in fabricating highly conformal PEDOT coating on carbon cloth electrodes for electrochemical energy storage devices.
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