Enhanced Energy Storage Performance in La-Doped CaBi₄Ti₄O₁₅ Films Through the Formation of a Weakly Coupled Relaxor

Relaxor ferroelectric film capacitors exhibit high power density with ultra-fast charge and discharge rates, making them highly advantageous for consumer electronics and advanced pulse power supplies. The Aurivillius-phase bismuth layered ferroelectric films can effectively achieve a high breakdown electric field due to their unique insulating layer ((Bi₂O₂)²⁺ layer)). However, designing and fabricating Aurivillius-phase bismuth layer relaxor ferroelectric films with optimal energy storage characteristics is challenging due to their inherently stable ferroelectric properties. In this work, lead-free CaBi_4-xLa_xTi₄O₁₅ films were synthesized using the sol-gel technique and a weakly coupled relaxor design. On one hand, the introduction of La³⁺ ions weaken the dipole-dipole interactions, thereby enhancing the relaxor behavior. Alternatively, the expansion of grain size is restricted to enhance the number of grain boundaries, which possess improved insulating properties. This leads to a higher breakdown electric field. The results indicate that CaBi_4-xLa_xTi₄O₁₅ (x = 1.0) films exhibit excellent recoverable energy storage density (70 J/cm³) and high energy efficiency (73%). Moreover, the film exhibited good temperature stability and frequency stability. This study not only identifies a promising material for dielectric film capacitors but also demonstrates that the energy storage capabilities of Aurivillius-phase bismuth layer ferroelectric films can be effectively modulated through a design incorporating weakly coupled relaxor characteristics.