Dynamic Phase Transformations of Prussian Blue Analogue Crystals in Hydrotherms.

Prussian blue analogue (PBA)/metal-organic frameworks (MOFs) are multifunctional precursors for the synthesis of metal/metal compounds, carbon, and their derived composites (P/MDCs) in chemical, medical, energy, and other applications. P/MDCs combine the advantages of both the high specific surface area of PBA/MOF and the electronic conductivity of metal compound/carbon. Although the calcination under different atmospheres has been extensively studied, the transformation mechanism of PBA/MOF under hydrothermal conditions remains unclear. The qualitative preparation of P/MDCs in hydrothermal conditions remains a challenge. Here, we select PBA to construct a machine-learning model and measure its hydrothermal phase diagram. The architecture-activity relationship of substances among nine parameters was analyzed for the hydrothermal phase transformation of PBA. Excitingly, we established a universal qualitative model to accurately fabricate 31 PBA derivates. Additionally, we performed three-dimensional reconstructed transmission electron microscopy, X-ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy, in situ X-ray powder diffraction, and theoretical calculation to analyze the advantages of hydrothermal derivatives in the oxygen evolution reaction and clarify their reaction mechanisms. We uncover the unified principles of the hydrothermal phase transformation of PBA, and we expect to guide the design for a wide range of composites.

Enhancing Zinc Electrode Stability Through Pre-Desolvation and Accelerated Charge Transfer via a Polyimide Interface for Zinc-Ion Batteries.

Aqueous zinc-based energy storage devices possess superior safety, cost-effectiveness, and high energy density; however, dendritic growth and side reactions on the zinc electrode curtail their widespread applications. In this study, these issues are mitigated by introducing a polyimide (PI) nanofabric interfacial layer onto the zinc substrate. Simulations reveal that the PI nanofabric promotes a pre-desolvation process, effectively desolvating hydrated zinc ions from Zn(H2O)6 2+ to Zn(H2O)4 2+ before approaching the zinc surface. The exposed zinc ion in Zn(H2O)4 2+ provides an accelerated charge transfer process and reduces the activation energy for zinc deposition from 40 to 21 kJ mol-1. The PI nanofabric also acts as a protective barrier, reducing side reactions at the electrode. As a result, the PI-Zn symmetric cell exhibits remarkable cycling stability over 1200 h, maintaining a dendrite-free morphology and minimal byproduct formation. Moreover, the cell exhibits high stability and low voltage hysteresis even under high current densities (20 mA cm-2, 10 mAh cm-2) thanks to the 3D porous structure of PI nanofabric. When integrated into full cells, the PI-Zn||AC hybrid zinc-ion capacitor and PI-Zn||MnVOH@SWCNT zinc-ion battery achieve impressive lifespans of 15000 and 600 cycles with outstanding capacitance retention. This approach paves a novel avenue for high-performance zinc metal electrodes.

Enhanced oxygen evolution and power density of Co/Zn@NC@MWCNTs for the application of zinc-air batteries.

Rechargeable zinc-air batteries (ZABs) are viewed as a promising solution for electric vehicles due to their potential to provide a clean, cost-effective, and sustainable energy storage system for the next generation. Nevertheless, sluggish kinetics of the oxygen evolution reaction (OER), the oxygen reduction reaction (ORR) at the air electrode, and low power density are significant challenges that hinder the practical application of ZABs. The key to resolving the development of ZABs is developing an affordable, efficient, and stable catalyst with bifunctional catalytic. In this study, we present a series of bifunctional catalysts composed of Co/Zn nanoparticles uniformly embedded in nitrogen-doped carbon (NC) and multi-walled carbon nanotubes (MWCNTs) denoted as Co/Zn@NC@MWCNTs. The incorporation of MWCNTs using a facile and non-toxic method significantly decreased the overpotential of the OER from 570 to 430 mV at 10 mA cm-2 and the peak power density from 226 to 263 mW cm-2. Besides, the electrochemical surface area measurements and electrochemical impedance spectroscopy indicate that the three-dimensional (3D) network structure of MWCNTs facilitates mass transport for ORR and reduces electron transfer resistance during OER, leading to a small potential gap of 0.86 V between OER and ORR, high electron transfer number (3.92-3.98) of the ORR, and lowest Tafel slope (47.8 mV dec-1) of the OER in aqueous ZABs. In addition, in-situ Raman spectroscopy revealed a notable decrease in the ID/IG ratio for the optimally configured Co/Zn@NC@MWCNTs (75:25), indicating a reduction in defect density and improved structural ordering during the electrochemical process, which directly contributes to enhanced ORR activity. Hence, this study provides an excellent strategy for constructing a bifunctional catalyst material with a 3D MWCNTs conductive network for the development of advanced ZAB systems for sustainable energy applications.