PVDF polymer dielectrics, renowned for their ultra-high-power density, ultra-fast response times, remarkable toughness, and lightweight properties, constitute the essential material foundation for the development of dielectric capacitors. Nevertheless, the low-energy density of these dielectrics presents a challenge to the advancement of dielectric capacitors. In this paper, in the process of preparing monolayer pure PVDF dielectric films by the solution casting method, a fixed-direction magnetic field and a rotating magnetic field were introduced in the horizontal direction, respectively, and this investigation explores the impact of magnetic field modulation on the polymer films' free-volume pore size, grain size, phase structure, dielectric properties, and energy storage capabilities by altering the duration and orientation of the magnetic field's influence. This study also discusses how microscopic alterations, particularly in the free-volume pore size, affect the macroscopic dielectric properties. Polymer films treated with a magnetic field of constant orientation for 3 min were obtained with the smallest free-volume hole size of 2.91 Å, the highest γ-phase contents of 54.8%, the smallest grain size of 68 Å, the largest electrical displacement of 10.64 and a very high discharge energy density of 12.68 J/cm3 (a 200% enhancement over pure PVDF).
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