Highly Flexible, Freestanding Supercapacitor Electrode with Enhanced Performance Obtained by Hybridizing Polypyrrole Chains with MXene

Though polypyrrole (PPy) is widely used in flexible supercapacitors owing to its high electrochemical activity and intrinsic flexibility, limited capacitance and cycling stability of freestanding PPy films greatly reduce their practicality in real‐world applications. Herein, we report a new approach to enhance PPy's capacitance and cycling stability by forming a freestanding and conductive hybrid film through intercalating PPy into layered Ti ₃ C ₂ (l‐Ti ₃ C ₂ , a MXene material). The capacitance increases from 150 (300) to 203 mF cm ⁻² (406 F cm ⁻³ ). Moreover, almost 100% capacitance retention is achieved, even after 20 000 charging/discharging cycles. The analyses reveal that l‐Ti ₃ C ₂ effectively prevents dense PPy stacking, benefiting the electrolyte infiltration. Furthermore, strong bonds, formed between the PPy backbones and surfaces of l‐Ti ₃ C ₂ , not only ensure good conductivity and provide precise pathways for charge‐carrier transport but also improve the structural stability of PPy backbones. The freestanding PPy/l‐Ti ₃ C ₂ film is further used to fabricate an ultra‐thin all‐solid‐state supercapacitor, which shows an excellent capacitance (35 mF cm ⁻² ), stable performance at any bending state and during 10 000 charging/discharging cycles. This novel strategy provides a new way to design conductive polymer‐based freestanding flexible electrodes with greatly improved electrochemical performances.