Breaking the Charge Limitation Constrained by Triboelectrification through the Charge Multiplication Effect

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Enhancing the output performance of triboelectric nanogenerator (TENG), as determined by its quadratic output charge density, is crucial for its commercialization. While the latest bi‐characteristic current TENG (BC‐TENG) holds promise in overcoming the limitations of conventional alternating‐current and direct‐current TENGs, its fundamental working mechanism and source of output charge remain unclear. Here, a comprehensive investigation is conducted into the physical process behind the complicated electrostatic discharges during BC‐TENG operation, and a universal charge multiplication effect (CME) is reported. Based on the gas discharge physics, the underlying CME mechanism is established and validated it across micro‐ and macro‐perspectives. This effect enables BC‐TENGs to generate output charges exceeding the initial tribo‐charge by over threefold, effectively surpassing the triboelectrification limit in air. Further analysis identifies tribolayer–tribolayer discharge as the dominant charge source, with additional contributions from tribolayer‐electrode discharge and residual surface charge induction. By constructing a rotary‐mode BC‐TENG, an ultrahigh direct‐current output with a charge density of 16.34 mC m −2 and an average power density of 61.87 W m −2 Hz −1 is obtained, outperforming previous reports. This work redefines strategies for high‐performance TENG design, marking a significant breakthrough in the field.