Qiu Jikai, Liu Zhipeng, Yuan Tao, Bai Shuai, Zhang Xiangxin, Chen Junting, Zhang Yining
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian 350007, PR China; Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, PR China; Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian 350002, PR China.
J Colloid Interface Sci. 2025 Apr;683(Pt 2):310-323. doi: 10.1016/j.jcis.2024.12.189. Epub 2024 Dec 25.
The reversibility and stability of aqueous zinc-ion batteries (AZIBs) are largely limited by free-water-induced side reactions (e.g., hydrogen evolution and zinc corrosion) and negative zinc dendrite growth. To address these issues, we introduced triethyl 2-phosphonopropionate (Tp), a novel high-dipole-moment electrolyte additive. Tp effectively replaces free water in the electrolyte through strong ion-dipole interactions, altering the solvation structure and suppressing hydrogen evolution and zinc corrosion at the zinc anode. Additionally, the high binding energy between Tp and zinc foil ensures that Tp adheres firmly to the zinc anode surface, while the hydrophobic alkyl chains repel free water, modifying the interfacial structure of the zinc anode, promoting reversible zinc deposition, and effectively suppressing zinc dendrite growth. With these excellent properties, the optimal concentration of Tp enables a cycle time of over 770 h for 1 mA cm and 1 mAh cm symmetric cells, which is 7.7 times longer than that of pure electrolyte. Furthermore, the cycle number of Zn//NaVO full cells increased from 600 to 4000 cycles compared to pure electrolyte, with capacity retention improved from 70 % to 92 %. These results highlight the significance of high-dipole moment electrolyte additives, provide new insights into electrolyte modification strategies, and are expected to accelerate the commercialization of AZIBs for practical applications.
水系锌离子电池（AZIBs）的可逆性和稳定性在很大程度上受到自由水引发的副反应（如析氢和锌腐蚀）以及负极锌枝晶生长的限制。为了解决这些问题，我们引入了一种新型的高偶极矩电解质添加剂——2-膦酰基丙酸三乙酯（Tp）。Tp通过强大的离子-偶极相互作用有效地取代了电解质中的自由水，改变了溶剂化结构，抑制了锌负极的析氢和锌腐蚀。此外，Tp与锌箔之间的高结合能确保Tp牢固地附着在锌负极表面，而疏水烷基链排斥自由水，改变了锌负极的界面结构，促进了锌的可逆沉积，并有效抑制了锌枝晶的生长。凭借这些优异的性能，Tp的最佳浓度使1 mA cm和1 mAh cm对称电池的循环时间超过770小时，比纯电解质长7.7倍。此外，与纯电解质相比，Zn//NaVO全电池的循环次数从600次增加到4000次，容量保持率从70%提高到92%。这些结果突出了高偶极矩电解质添加剂的重要性，为电解质改性策略提供了新的见解，并有望加速AZIBs在实际应用中的商业化。
