Key Takeaways & Executive Findings
- •• Cationic benzyltriethylammonium chloride enables high (002)-textured Zn via selective adsorption, outperforming prior additives. • In situ homogenization converts commercial Zn foil into highly (002)-textured Zn anodes without pretreatments. • Cl−-induced pitting corrosion mechanism uncovered, leading to a breakthrough in performance limits of Zn anodes. • TEBA+-modified Zn||VO2 full cell demonstrates high specific capacity and robust cycle stability at 10.0 A g−1.
Abstract
Crystallographic engineering of Zn anodes to favor the exposure of (002) planes is an effective approach for improving stability in aqueous electrolytes. However, achieving non-epitaxial electrodeposition with a pronounced (002) texture and maintaining this orientation during extended cycling remains challenging. This study questions the prevailing notion that a single (002)-textured Zn anode inherently ensures superior stability, showing that such anodes cannot sustain their texture in ZnSO4 electrolytes. We then introduced a novel electrolyte additive, benzyltriethylammonium chloride (TEBAC), which preserves the (002) texture over prolonged cycling. Furthermore, we successfully converted commercial Zn foils into highly crystalline (002)-textured Zn without any pretreatment. Experiments and theoretical calculations revealed that the cationic TEBA+ selectively adsorbs onto the anode surface, promoting the exposure of the Zn(002) plane and suppressing dendrite formation. A critical discovery was the pitting corrosion caused by chloride ions from TEBAC, which we mitigated by anion substitution. This modification leads to a remarkable lifespan of 375 days for the Zn||Zn symmetric cells at 1 mA cm−2 and 1 mAh cm−2. Furthermore, a TEBA+-modified Zn||VO2 full cell demonstrates high specific capacity and robust cycle stability at 10.0 A g−1. These results provide valuable insights and strategies for developing long-life Zn ion batteries.
1. Introduction
Rechargeable aqueous zinc-ion batteries (ZIBs) have emerged as a promising solution for large-scale energy storage due to their low cost, non-flammability, and high theoretical capacity of 820 mAh g−1 [1–4]. However, their practical application is hindered by challenges such as short cycle life and low reversibility, primarily caused by the hydrogen evolution reaction (HER), corrosion, and dendrite growth on Zn anodes [5–7]. HER leads to electrolyte consumption and by-product formation, adversely affecting Zn electrodeposition and resulting in porous Zn [8, 9]. Dendritic growth further increases the risk of short circuits [10, 11], highlighting the need for strategies to enhance the stability and performance of Zn anodes for ZIBs.
To address these challenges, stabilizing Zn metal anodes has become a central focus in ZIBs development. Various strategies have been proposed electrolyte optimization [12–14], crystallographic texture control [15–17], interface engineering [18–20], Zn host structure design [21–23], and separator modification [24–26]. Among these, crystallographic texture control of Zn metal substrates stands out as a practical and effective method to intrinsically improve Zn reversibility. Zn possesses a hexagonal close-packed (HCP) structure, in which the (002) plane is the closed-packed plane. This plane, characterized by minimal surface energy and a compact morphology, is particularly resistant to hydrogen evolution, corrosion, and dendrite formation, making it a desirable orientation for Zn anodes [27–29].
Several methods have been developed to achieve a high (002) texture in Zn anodes, including plastic deformation [30], annealing [31], and electrodeposition [32]. These techniques have successfully produced Zn anodes with highly aligned or even single (002)-textured structures, which effectively suppress side reactions and promote uniform Zn deposition. However, during repeated plating/stripping cycles, the (002) texture tends to degrade, leading to randomly oriented Zn deposition, reduced reversibility, and eventually lead to short circuit. However, most existing studies have primarily focused on fabricating Zn anodes with high (002) texture during initial preparation, with limited attention given to obtaining and maintaining high (002) texture throughout battery cycling, particularly when starting from commercially available Zn foils.
Electrolyte optimization, particularly through the use of specific additives, offers a cost-effective and scalable strategy for controlling Zn electrodeposition and promoting the development of high (002) texture Zn anodes during cycling. For instance, 1-butyl-3-methylimidazolium cation (BMIm+) has been reported to selectively adsorb on the (100) and (101) planes, facilitating Zn2+ deposition o
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Zhaoxu Mai, Yuexing Lin, Jingying Sun, Chenhui Wang, Gongzheng Yang, Chengxin Wang (2025). Breaking Performance Limits of Zn Anodes in Aqueous Batteries by Tailoring Anion and Cation Additives. Nano-Micro Letters. https://doi.org/10.1007/s40820-025-01773-6
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Frequently Asked Questions
What is the main challenge in achieving stable Zn anodes in aqueous batteries?
The main challenge is maintaining a (002) crystallographic texture during cycling, as it tends to degrade, leading to dendrite growth and reduced reversibility.
How does the additive TEBAC improve Zn anode performance?
TEBAC's cationic TEBA+ selectively adsorbs on the anode surface, promoting (002) plane exposure and suppressing dendrite formation, while chloride ions are substituted to avoid pitting corrosion.
What is the significance of the 375-day lifespan achieved in Zn||Zn symmetric cells?
The 375-day lifespan at 1 mA cm−2 and 1 mAh cm−2 demonstrates exceptional stability, far exceeding typical performance, and highlights the effectiveness of the additive strategy.
Can commercial Zn foils be directly used without pretreatment?
Yes, the study successfully converted commercial Zn foils into highly crystalline (002)-textured Zn without any pretreatment, making the approach practical and scalable.
What is the role of anion substitution in this study?
Anion substitution mitigates pitting corrosion caused by chloride ions from TEBAC, which is critical for achieving long-term cycling stability.
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