Wang Yao, Zhang Zhanrui, Wang Liwen, Wang Jingxuan, Meng Weijia, Sun Jie, Li Qi, He Xuexia, Liu Zonghuai, Lei Zhibin
Key Laboratory of Applied Surface and Colloid Chemistry, MOE, Shaanxi Engineering Lab for Advanced Energy Technology, Shaanxi Key Laboratory for Advanced Energy Devices, School of Materials Science and Engineering, Shaanxi Normal University, 620 West Chang'an Street, Xi'an, Shaanxi 710119, China.
Shaanxi Key Laboratory of New Transportation Energy and Automotive Energy Saving, School of Energy and Electrical Engineering, Chang'an University, Xi'an 710061, China.
ACS Appl Mater Interfaces. 2024 Aug 14;16(32):43026-43037. doi: 10.1021/acsami.4c09699. Epub 2024 Aug 2.
The aqueous zinc-ion batteries (ZIBs) have gained increasing attention because of their high specific capacity, low cost, and good safety. However, side reactions, hydrogen evolution reaction, and uncontrolled zinc dendrites accompanying the Zn metal anodes have impeded the applications of ZIBs in grid-scale energy storage. Herein, the poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires as an interfacial layer on the Zn anode (Zn-PEDOT) are reported to address the above issues. Our experimental results and density functional theory simulation reveal that the interactions between the Zn and S atoms in thiophene rings of PEDOT not only facilitate the desolvation of hydrated Zn but also can regulate the diffusion of Zn along the thiophene molecular chains and induce the dendrite-free deposition of Zn along the (002) surface. Consequently, the Zn||Cu-PEDOT half-cell exhibits highly reversible plating/stripping behavior with an average Coulombic efficiency of 99.7% over 2500 cycles at 1 mA cm and a capacity of 0.5 mAh cm. A symmetric Zn-PEDOT cell can steadily operate over 1100 h at 1 mA cm (1 mAh cm) and 470 h at 10 mA cm (2 mAh cm), outperforming the counterpart bare Zn anodes. Besides, a Zn-PEDOT||VO full cell could deliver a specific capacity of 280 mAh g at 1 A g and exhibits a decent cycling stability, which are much superior to the bare Zn||VO cell. Our results demonstrate that PEDOT nanowires are one of the promising interfacial layers for dendrite-free aqueous ZIBs.
水系锌离子电池（ZIBs）因其高比容量、低成本和良好的安全性而受到越来越多的关注。然而，伴随锌金属负极出现的副反应、析氢反应和不受控制的锌枝晶阻碍了ZIBs在电网规模储能中的应用。在此，报道了聚（3,4-亚乙基二氧噻吩）（PEDOT）纳米线作为锌负极（Zn-PEDOT）上的界面层来解决上述问题。我们的实验结果和密度泛函理论模拟表明，PEDOT噻吩环中锌原子与硫原子之间的相互作用不仅有助于水合锌的去溶剂化，还能调节锌沿噻吩分子链的扩散，并诱导锌沿（002）面无枝晶沉积。因此，Zn||Cu-PEDOT半电池在1 mA cm和0.5 mAh cm的容量下，在2500次循环中表现出高度可逆的镀覆/剥离行为，平均库仑效率为99.7%。对称的Zn-PEDOT电池在1 mA cm（1 mAh cm）下可稳定运行超过1100小时，在10 mA cm（2 mAh cm）下可稳定运行470小时，优于对应的裸锌负极。此外，Zn-PEDOT||VO全电池在1 A g时可提供280 mAh g的比容量，并表现出良好的循环稳定性，这远优于裸Zn||VO电池。我们的结果表明，PEDOT纳米线是无枝晶水系ZIBs有前景的界面层之一。
