Triboelectric charge density and energy density are two crucial factors to assess the output capability of dielectric materials in a triboelectric nanogenerator (TENG). However, they are commonly limited by the breakdown effect, structural parameters, and environmental factors, failing to reflect the intrinsic triboelectric behavior of these materials. Moreover, a standardized strategy for quantifying their maximum values is needed. Here, by circumventing these limitations, we propose a standardized strategy employing a contact-separation TENG for assessing a dielectric material’s maximum triboelectric charge and energy densities based on both theoretical analyses and experimental results. We find that a material’s vacuum triboelectric charge density can be far higher than previously reported values, reaching a record-high of 1250 µC m−2 between polyvinyl chloride and copper. More importantly, the obtained values for a dielectric material through this method represent its intrinsic properties and correlates with its work function. This study provides a fundamental methodology for quantifying the triboelectric capability of dielectric materials and further highlights TENG’s promising applications for energy harvesting.

Direct-current triboelectric nanogenerators arising from electrostatic breakdown can eliminate the bottleneck problem of air breakdown in conventional triboelectric nanogenerators, offering critical benefits of constant-current output, resistance to electromagnetic interference, and high output power density. Previous understanding is that its output characteristics are described by a capacitor-breakdown model or dictated by one or two discharge domains in direct-current triboelectric nanogenerators. Here, we demonstrate that the former holds only for ideal conditions and the latter cannot fully explain the dynamic process and output performance. We systematically image, define, and regulate three discharge domains in direct-current triboelectric nanogenerators, then a “cask model” is developed to bridge the cascaded-capacitor-breakdown dynamic model in ideal conditions and real outputs. Under its guidance, the output power is increased by an order of magnitude within a wide range of resistive loads. These unexplored discharge domains and optimization methods revolutionize the output performance and potential applications of direct-current triboelectric nanogenerators.