Recently, Associate Professor Yunwen Wu from the School of Materials Science and Engineering at Shanghai Jiao Tong University published a paper titled "Crystal plane shielding and D-band modulation synergistically achieve durable (100) textured zinc anodes" in the internationally top-tier journal 《Energy & Environmental Science》 (Impact Factor: 32.5) in the field of materials and energy. Ph.D. student Xiangyu Ren from the School of Materials Science and Engineering at Shanghai Jiao Tong University is the sole first author of the paper, and Associate Professor Yunwen Wu is the corresponding author. In this study, researchers integrated 2-butene-1,4-diol (BED) into a ZnSO4 electrolyte to enhance the electrodeposition stability of zinc anodes. The selective adsorption of BED restructured the Zn2+ deposition process, forming a smooth array-structured (100) textured coating. Additionally, BED modified the electronic structure of zinc, limiting the conversion of H+ to Had, thereby suppressing hydrogen evolution reactions (HER). Due to the altered coating texture and electronic structure, the growth of zinc dendrites and side reactions were significantly inhibited. As a result, the prepared AZIB demonstrated exceptional cycling performance. This novel discovery provides fresh insights into the mechanistic roles of additives.
In recent years, driven by growing global energy demands, next-generation energy storage technologies "beyond lithium-ion" have achieved remarkable progress. Aqueous zinc-ion batteries (AZIBs) are considered promising next-generation energy storage devices due to their inherent reliability, environmental friendliness, affordability, and high theoretical specific capacity (820 mAh g⁻¹ or 5854 mAh mL⁻¹). However, challenges such as dendrite formation, hydrogen evolution reactions (HER), and metal corrosion remain inevitable due to the low redox potential of zinc anodes (-0.762 V vs. SHE). To date, optimizing electrolyte composition with additives has demonstrated significant advantages in simplicity, efficiency, and cost-effectiveness.
Most additive engineering efforts focus on constructing Zn coatings with (002) texture, yet recent studies highlight that the sluggish reaction kinetics of the (002) crystal plane hinder metal ion stripping. In contrast, the (100) crystal plane not only exhibits faster reaction kinetics but also minimizes electrochemical reaction active areas. While researchers have employed various additives to tune the electrolyte chemistry and electrode surface states for HER suppression, few studies address the impact of additive molecular adsorption on the substrate's electronic structure—a critical factor governing HER occurrence. This emerging perspective underscores the need to explore dual modulation strategies targeting both crystallographic orientation and electronic configuration for advanced AZIB development.
Figure 1 illustrates the mechanism of BED. As shown, BED induces the formation of a (100)-textured structure, while the modification of the electronic structure suppresses the hydrogen evolution reaction (HER). Additionally, the dynamic adsorption-desorption behavior prevents the formation of inactive zinc (dead Zn).
Figure 1. Mechanism of BED during electrodeposition/stripping processes
Figure 2. SEM, XRD, and TEM results of zinc coatings under different electrodeposition/stripping cycles. The SEM images reveal the formation of an array-structured zinc coating. XRD analysis indicates a significant enhancement in the (100) crystallographic orientation. Theoretical calculations and TEM results elucidate the mechanism behind the texture formation.
Figure 2. Investigation of coating texture and its formation mechanism
Experimental results demonstrate that the introduction of additives significantly suppresses side reactions. A novel mechanism is proposed to explain how additives mitigate HER, supported by theoretical calculations. In situ monitoring reveals reduced hydrogen gas evolution during electrodeposition/stripping processes.
Figure 3. Characterization of side reaction suppression, mechanistic exploration, and in situ observations
In full-cell and pouch-cell configurations, BED significantly enhances the cycling stability of metal batteries. The full-cell demonstrates stable operation for over 1,000 cycles at 5 A/g, while the pouch-cell exhibits promising practical applicability. This achievement inspires researchers to re-examine the mechanistic roles of additives in aqueous batteries from a fresh perspective.
Figure 4. Full-cell and pouch-cell application validation
Paper website：https://doi.org/10.1039/D4EE04025B