Mechanisms of Polarity‐Driven and Material‐Dependent Charge Transfer at PVDF/Polymer Interfaces for High‐Performance Triboelectric Nanogenerators

ABSTRACT Understanding the microscopic mechanism of interfacial charge transfer is crucial for optimizing the performance of triboelectric nanogenerators (TENGs). Here, a combined first‐principles density‐functional theory and experimental study reveals how polymer polarity and chemical composition regulate charge transfer at PVDF/polymer interfaces, including Nylon, PDMS, PVC, PE, PTFE, and FEP. The results demonstrate that polar β‐PVDF/polymer heterostructures exhibit substantially stronger interfacial charge transfer than nonpolar systems, driven by the intrinsic built‐in electric field of β‐PVDF. The transferred charges primarily originate from the functional groups of the polymers, and the charge transfer magnitude follows the sequence β‐PVDF/Nylon > β‐PVDF/PDMS > β‐PVDF/PVC > β‐PVDF/PE > β‐PVDF/PTFE > β‐PVDF/FEP, corresponding to electron flow from low work function polymers toward the high work function β‐PVDF. Furthermore, these theoretical trends are supported by experimental results, which confirm that β‐PVDF‐based TENGs deliver higher electrical outputs than α‐PVDF‐based systems and follow the same material‐dependent sequence. This work elucidates the polarization‐driven and material‐dependent mechanisms of interfacial charge redistribution, providing design principles for high‐output and controllable TENGs.