Interfacial polarization and lattice hydrogenation enable accelerated aluminum combustion with hydrogen-rich fluoropolymers

Aluminum (Al) particles are attractive high-enthalpy fuels, but their reactivity is impeded by a passivating aluminum oxide (Al₂O₃) shell. Here, we show that hydrogen-rich fluoropolymers markedly accelerate Al combustion via a dual mechanism involving interfacial polarization and lattice hydrogenation. High-throughput quantum mechanical calculations and molecular dynamics simulations reveal that hydrogen incorporation enhances polymer polarity and interfacial adhesion, facilitating oxygen abstraction from Al₂O₃. Concurrently, hydrogen diffusion into the Al lattice lowers effective atomic coordination, depresses the melting point, and disrupts lattice integrity, thereby reducing diffusion barriers for reactive species. Theory-guided composites were fabricated and characterized, and combustion experiments on hydrogen-rich composite Al/poly(vinylidene fluoride) validate the proposed mechanisms, yielding combustion rates up to 31.9 mm/s, over sixfold higher than those with poly(tetrafluoroethylene). These findings uncover a previously underappreciated role of hydrogen in modulating interfacial reactivity and offer a generalizable strategy for designing high-performance metal–polymer energetic materials.