Grain-boundary modulation doping for high-power-density thermoelectric generation in ZrNiSn composites

ZrNiSn-based half-Heusler compounds are promising thermoelectric materials for mid-to-high temperature power generation, but their widespread application is hindered by the costly reliance on hafnium for performance optimization. Herein, we present a cost-effective, Hf-free strategy that simultaneously enhances the power factor and figure of merit zT in n-type ZrNiSn via grain-boundary-engineered modulation doping. Metallic tungsten (W) nanoparticles are introduced as a secondary phase, where they spontaneously segregate to grain boundaries during consolidation. This microstructure creates a network of internal heterojunctions that perform two synergistic functions: charge injection from the low-work-function W elevates electrical conductivity, while interfacial energy-filtering barriers enhance the Seebeck coefficient. Consequently, the optimized composite achieves a peak power factor of 44 μW cm^-1 K^-2 and a zT of 0.76 at 910 K. Beyond intrinsic transport improvements, the practical viability of this material system is validated at the device level. When integrated into a thermoelectric unicouple, the material delivers an exceptional power density of 2.1 W cm^-2 and a conversion efficiency of 5.2% at a temperature difference of 307 K. Crucially, this approach eliminates expensive Hf, reducing material costs by over 95%. This work establishes grain‑boundary modulation doping as a cost‑effective route to enhance the power factor and zT of Hf‑free ZrNiSn, offering a pragmatic balance between performance and economic viability for mid‑temperature waste‑heat recovery.