RESUMEN
The widespread adoption of aqueous Zn ion batteries is hindered by the instability of the Zn anode. Herein, an elegant strategy is proposed to enhance the stability of Zn anode by incorporating nicotinic acid (NA), an additive with a unique molecule-ion conversion mechanism, to optimize the anode/electrolyte interface and the typical ZnSO4 electrolyte system. Experimental characterization and theoretical calculations demonstrate that the NA additive preferentially replaces H2O in the original solvation shell and adsorbs onto the Zn anode surface upon conversion from molecule to ion in the electrolyte environment, thereby suppressing side reactions arising from activated H2O decomposition and stochastic growth of Zn dendrites. Simultaneously, such a molecule-to-ion conversion mechanism may induce preferential deposition of Zn along the (002) plane. Benefiting from it, the Zn||Zn symmetric battery cycles stably for 2500 h at 1 mA cm-2, 1 mAh cm-2. More encouragingly, the Zn||AC full batteries and the Zn||AC full batteries using NA electrolyte and Zn||VO2 full batteries also exhibit excellent performance improvements. This work emphasizes the role of variation in the form of additives (especially weak acid-based additives) in fine-tuning the solvation structure and the anode/electrolyte interface, hopefully enhancing the performance of various aqueous metal batteries.
RESUMEN
Aqueous zinc ion batteries (AZIBs) are considered promising energy storage devices because of their high theoretical energy density and cost-effectiveness. However, the ongoing side reactions and zinc dendrite growth during cycling limit their practical application. Herein, trisodium methylglycine diacetate (Na3MGDA) additive containing the additional inert group methyl is introduced for Zn anode protection, and the contribution of methyl as an inert group to the Zn anode stability is discussed. Experimental results reveal that the methyl group with various effects enhances the interaction between the polar groups in Na3MGDA and the Zn2+/Zn anode. Thus, the polar carboxylate negative ions in MGDA anions can more easily modify the solvation structure and adsorb on the anode surface in situ to establish a hydrophobic electrical double layer (EDL) layer with steric hindrance effects. Such the EDL layer exhibits a robust selectivity for Zn deposition and a significant inhibition of parasitic reactions. Consequently, the Zn||Zn symmetric battery presents 2375 h at 1 mA cm-2, 1 mAh cm-2, and the Zn||V6O13 full battery provides 91% capacity retention after 1300 cycles at 3 A g-1. This study emphasizes the significant role of inert groups of the additive on the interfacial stability during the plating/stripping of high-performance AZIBs.
RESUMEN
Zn-Ni batteries have garnered considerable attention due to their high specific energy, consistent discharge voltage, favorable performance at low temperatures, and environmentally benign nature. Nevertheless, anode interface issues such as dendrite growth, hydrogen evolution, and interfacial side reactions lead to poor cycling stability of Zn-Ni batteries, significantly limiting their further commercial applications. In this study, we propose a facile electrolyte engineering strategy to optimize the Zn anode interfacial environment and stabilize the Zn anode by introducing tannic acid (TA) into the KOH electrolyte. The incorporated TA complexing agent addition will be used to prevent the direct contact of H2O with the anode surface and promote the desolvation of Zn2+ through complexation, thus suppressing the interfacial corrosion. Consequently, the Zn symmetric battery using TA electrolyte cycles stably for 178 h at 1 mA cm-2. The Zn-Ni full batteries with TA electrolyte maintain 98.08 % capacity retention after 2000 cycles at 20C. This study will be of immediate benefit in commercializing large-scale, practical energy storage applications.