Publication date: 15th December 2025
In the search for advanced materials for zinc-ion batteries (AZIBs), Prussian Blue (PB) has emerged as a high-potential candidate. The optimization of its electrochemical performance is intrinsically linked to the material's morphology; therefore, this research proposes reducing the particle size from the conventional micrometric scale (1-2 µm) toward a target nanometric range of 3-5 nm. The fundamental purpose of this dimensional transition is to minimize the diffusion length of Zn 2+ cations within the PB crystal lattice, thereby facilitating more efficient charge-transfer kinetics during insertion and extraction processes (redox reactions).
To achieve this precise dimensional control, two chemical synthesis methodologies have been explored. The first involves the use of polyvinylpyrrolidone (PVP) as a capping and steric stabilizing agent. PVP encapsulates the primary crystallization nuclei, delimiting their growth and preventing agglomeration. Through this method, nanoparticles between 20 and 50 nm have been obtained, identifying the molar ratio between PVP and the precursors as the critical parameter. Currently, a 5:1 ratio is being utilized; observations indicate that higher polymer concentrations favor a decrease in particle diameter, showing potential for achieving even smaller dimensions.
Simultaneously, a microemulsion technique based on the surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) has been implemented. This system allows the chemical reaction to be confined within inverse micelles, which act as nanoreactors that mechanically restrict crystal growth. Through this approach, particles of approximately 10 nm have been synthesized, offering a promising route not only for size reduction but also for enhancing the crystallinity of the material—a determining factor for structural stability and the cycle life of the cathode.
the authors thank the financing from projects BIZI: Bipolar electrochemistry enabling the development of Combined Chemistry Cells for improved Zinc batteries (PID2024-157199OB-C21, financiado por MCIN/ AEI/10.13039/501100011033 and NANION: Development of Free-Standing Nanostructured Prussian Blue Electrodes for High Performance Zinc-ion Supercapacitors. Women Talent Senior Grants Award (Women Talent Programm ICN2, funded by Severo Ochoa CEX2021-002325-S (MCIU/AEI/10.13039/501100011033).
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