Constructing ingenious microstructures, such as core–shell, laminate, microcapsule and porous microstructures, is an efficient strategy for tuning the combustion behaviors and thermal stability of energetic materials (EMs). Electrohydrodynamic atomization (EHDA), which includes electrospray and electrospinning, is a facile and versatile technique that can be used to process bulk materials into particles, fibers, films and three-dimensional (3D) structures with nanoscale feature sizes. However, the application of EHDA in preparing EMs is still in its initial development. This review summarizes the progress of research on EMs prepared by EHDA over the last decade. The morphology and internal structure of the produced materials can be easily altered by varying the operation and precursor parameters. The prepared EMs composed of zero-dimensional (0D) particles, one-dimensional (1D) fibers and two-dimensional (2D) films possess precise microstructures with large surface areas, uniformly dispersed components and narrow size distributions and show superior energy release rates and combustion performances. We also explore the reasons why the fabrication of 3D EM structures by EHDA is still lacking. Finally, we discuss development challenges that impede this field from moving out of the laboratory and into practical application.

Nanothermites are widely applied as specific power sources for microscale initiators and pyrotechnics. Increasing the charge density enhances energy storage within a confined combustion chamber, but it also alters the reaction kinetics. To systemically explore this phenomenon, the combustion and pressurization characteristics of electrosprayed nanothermite-based hybrid energetic materials (THEMs) with different metallic oxides (Fe₂O₃, CuO, and Bi₂O₃) and various energetic additives (nitrocellulose (NC), octogen (HMX), ammonium perchlorate (AP), and hexanitrohexaazaisowurtzitane (CL-20)) across various loading densities were tested. The results showed that increasing the loading density decreased the porosity of the loaded nanothermites and then rapidly decreased the convective heat transfer efficiency during the combustion propagation process. When the loading density exceeded a critical value, a dramatic decrease in the peak pressure, several orders-of-magnitude decrease in the pressurization rate, and an order-of-magnitude increase in the combustion duration occurred. Due to the dual effects of the porous microstructure on heat and mass transfer, the critical density of both the electrosprayed Al/CuO/NC/CL-20 composites and their physically mixed counterparts is between 37.9 and 43.9% theoretical maximum density (TMD). Because of the different synergistic catalytic effects, the fast reactivity at the high-loading-density maintaining capacity of the applied additives was AP > HMX ≈ CL-20 > NC. Owing to their intrinsic properties of low ignition temperature and high gas yield, the Bi₂O₃-THEMs could maintain high-speed reactivity even at 59.7% TMD. These results provide valuable insights into the rational design and tailoring of the reactivity of nanothermites for specific applications.