Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Bin Li; Pengchao Ruan; Xieyu Xu; Zhangxing He; Xinyan Zhu; Liang Pan; Ziyu Peng; Yangyang Liu; Peng Zhou; Bingan Lu; Lei Dai; Jiang Zhou

doi:10.1007/s40820-023-01278-0

Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Nanomicro Lett. 2024 Jan 4;16(1):76. doi: 10.1007/s40820-023-01278-0.

Authors

Bin Li¹, Pengchao Ruan², Xieyu Xu³, Zhangxing He⁴, Xinyan Zhu¹, Liang Pan¹, Ziyu Peng¹, Yangyang Liu⁵, Peng Zhou⁶, Bingan Lu⁷, Lei Dai¹, Jiang Zhou⁸

Affiliations

¹ School of Chemical Engineering, North China University of Science and Technology, Tangshan, 063009, People's Republic of China.
² School of Materials Science and Engineering, Central South University, Changsha, 410083, People's Republic of China.
³ State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an, 710049, People's Republic of China.
⁴ School of Chemical Engineering, North China University of Science and Technology, Tangshan, 063009, People's Republic of China. zxhe@ncst.edu.cn.
⁵ State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an, 710049, People's Republic of China. liuyy0510@hotmail.com.
⁶ Hunan Provincial Key Defense Laboratory of High Temperature Wear-Resisting Materials and Preparation Technology, Hunan University of Science and Technology, Xiangtan, 411201, People's Republic of China.
⁷ School of Physics and Electronics, Hunan University, Changsha, 410082, People's Republic of China.
⁸ School of Materials Science and Engineering, Central South University, Changsha, 410083, People's Republic of China. zhou_jiang@csu.edu.cn.

Abstract

Achieving a highly robust zinc (Zn) metal anode is extremely important for improving the performance of aqueous Zn-ion batteries (AZIBs) for advancing "carbon neutrality" society, which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction, corrosion, and passivation, etc. Herein, an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups (COF-S-F) is developed on Zn metal (Zn@COF-S-F) as the artificial solid electrolyte interface (SEI). Sulfonic acid group (- SO₃H) in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions, and the three-dimensional channel with fluoride group (-F) can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects, endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions. Consequently, Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage (50.5 mV) at the current density of 1.5 mA cm^-2. Zn@COF-S-F|MnO₂ cell delivers the discharge specific capacity of 206.8 mAh g^-1 at the current density of 1.2 A g^-1 after 800 cycles with high-capacity retention (87.9%). Enlightening, building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

Keywords: Aqueous Zn ion batteries; Covalent organic framework; Desolvation effect; Interfacial modification; Zn ion flux regulation.