Achieving positive temperature-dependent thermal conductivity in multicomponent nitrides via phonon–electron synergistic regulation

Advanced thermal management for extreme environments urgently demands materials that combine robust environmental stability with adaptive thermal conductivity (<em>κ</em>), specifically the highly desirable but rare positive temperature dependence of <em>κ</em>. While ceramics typically show phonon-dominated heat transfer with decreasing thermal conductivity at elevated temperatures, achieving an alloy-like positive <em>κ</em>-T relationship in ceramics holds a significant scientific and technological challenge with immense application value. To address this, we fabricated fully dense (&gt;98%) multicomponent nitride bulks via hot-press sintering using AlN as the matrix. Notably, the TiAlN system achieved a high room-temperature <em>κ</em> of 48.38 W/(m·K). Counterintuitively, increased diversity of metallic element induces severe lattice distortion that suppresses phonon thermal conduction, while simultaneously forming metallic nitride conductive networks that significantly enhance electronic thermal conductivity. This synergistic electron-phonon regulation successfully transforms the <em>κ</em>-T dependence from negative to positive. Remarkably, TiZrVCrAlN demonstrates a linear 112% <em>κ</em> increase from 8.65 W/(m·K) at -60 °C to 18.34 W/(m·K) at 900 °C, outperforming all known positive-κ ceramics in both operational temperature range and conductivity values. Moreover, it maintains robust mechanical integrity (24.5 GPa hardness, 273 MPa bending strength). This work elucidates the fundamental mechanism for achieving anomalous positive <em>κ</em>-T dependence in ceramics through electron-phonon synergistic regulation. These multicomponent nitrides, combining unprecedented positive <em>κ</em>-T behavior with excellent mechanical properties, present a breakthrough solution for intelligent thermal management, specifically enabling the development of structural-functional integrated components operating under extreme and varying thermal conditions.