Simultaneous Regulation of Coordination Environment and Electrode Interface for Highly Stable Zinc Anode Using a Bifunctional Citrulline Additive
Simultaneous Regulation of Coordination Environment and Electrode Interface for Highly Stable Zinc Anode Using a Bifunctional Citrulline Additive
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DOI：
10.1002/adfm.202313925
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发表时间：
2024-02
影响因子：
19
通讯作者：
Jingzhu Chen;Ning Liu;W. Dong;Yang Xu;Yuge Cao;Shicong Zhang;Jingshan Hou;Hui Bi;Tianquan Lin;Fuqiang Huang
中科院分区：
文献类型：
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作者：
Jingzhu Chen;Ning Liu;W. Dong;Yang Xu;Yuge Cao;Shicong Zhang;Jingshan Hou;Hui Bi;Tianquan Lin;Fuqiang Huang
水性锌离子电池是大规模储能的有前途的候选者。尽管如此，Zn阳极在水性电解质中的稳定性受到树枝状生长和不期望的副反应的损害。在这篇文章中，瓜氨酸（Cit），生物相容性化合物，作为电解质添加剂，以实现上级稳定性的锌阳极进行了研究。实验结果和理论计算表明，Cit作为一种双功能添加剂，具有丰富的高极性基团（─ NH 2和─COOH），有利于与Zn 2+和Zn金属的强相互作用。在阳极/电解质界面处的Zn 2+溶剂化壳层和双电层的这种双重调节有效地减轻了枝晶生长并抑制了界面副反应，导致Zn阳极的异常稳定性。因此，Zn||采用Cit添加剂的锌对称电池在1.0 mA cm−2和1.0 mAh cm−2下可稳定运行超过1600 h，即使在10.0 mA cm−2和10.0 mAh cm−2的苛刻条件下也可保持稳定循环650 h，相当于3.25 Ah cm−2的超高累积电镀容量。此外，Zn||铜不对称电池在1.0 mA cm−2和0.5 mAh cm−2时实现了99.6%的显着库仑效率。这些进步还扩展到组装的全电池的性能改进。
Aqueous zinc ion batteries are promising candidates for large‐scale energy storage. Nonetheless, the stability of Zn anodes in aqueous electrolytes is compromised by dendritic growth and undesirable side reactions. In this article, citrulline (Cit), a biocompatible compound, is investigated as an electrolyte additive to achieve superior stability of Zn anodes. Experimental results and theoretical calculations demonstrate that the Cit, serving as a bifunctional additive, possesses abundant highly polar groups (─NH2 and ─COOH) that facilitate strong interactions with Zn2+ and Zn metal. This dual regulation of the Zn2+ solvation shell and the electrical double layer at the anode/electrolyte interface effectively mitigates dendrite growth and suppresses interface side reactions, resulting in exceptional stability of Zn anode. Consequently, Zn||Zn symmetric batteries incorporating the Cit additive exhibit stable operation for over 1600 h at 1.0 mA cm−2 and 1.0 mAh cm−2, and maintain stable cycling for 650 h even under demanding conditions of 10.0 mA cm−2 and 10.0 mAh cm−2, corresponding to an ultra‐high cumulative plated capacity of 3.25 Ah cm−2. Furthermore, Zn||Cu asymmetric batteries achieve a remarkable Coulombic efficiency of 99.6% at 1.0 mA cm−2 and 0.5 mAh cm−2. These advancements also extend to the improved performance of assembled full batteries.