AbstractTo address the need for efficient, flexible, and wearable power sources for portable electronics, a high performance triboelectric nanogenerator (TENG) was proposed by incorporating vertically‐aligned barium titanate (BaTiO3)/antimony tin oxide (ATO) nanofibers in polydimethylsiloxane (PDMS) negative triboelectric layer, where BaTiO3 served as piezoelectric material, and ATO served as conductive filler. Silver‐coated conductive fabric was used as electrode to ensure integrability and wearability. By strategically coupling the triboelectric effect of PDMS, the piezoelectric effect of BaTiO3 nanofibers, and the charge transfer effect of ATO nanofibers, the TENG exhibited the optimum output voltage and current of approximately 119 V and 28 μA, and power density of 11.74 μW/cm2, respectively. This device demonstrates its potential applications in energy supply by effectively illuminating 174 commercial green LEDs and charging capacitors for powering electronics. Additionally, the successful integration of the TENG into a smart fencing jacket highlights its utility in practical applications.Highlights TENGs with vertically‐aligned BaTiO3/ATO composite nanofibers was constructed. The output performance of TENGs were enhanced by coupling triboelectric and piezoelectric effects. Conductive ATO nanofibers were incorporated to enhance charge transfer for performance enhancement. A smart fencing jacket with scoring system was developed using the wearable TENG.
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