Manipulating OH−‐Mediated Anode‐Cathode Cross‐Communication Toward Long‐Life Aqueous Zinc‐Vanadium Batteries

• Published in: Angewandte Chemie International Edition Vol. 62; no. 5; pp. e202215385 - n/a
• Main Authors: Liu, Dao‐Sheng, Zhang, Zhaoyu, Zhang, Yufei, Ye, Minghui, Huang, Song, You, Shunzhang, Du, Zijian, He, Jiangfeng, Wen, Zhipeng, Tang, Yongchao, Liu, Xiaoqing, Li, Cheng Chao
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 26.01.2023
• Edition: International ed. in English
• Subjects: Acidic Aqueous Electrolytes; Acidification; Al2(SO4)3 Additive; Aluminum sulfate; Anode-Cathode Interplay; Anodic dissolution; Cathodes; Dissolution; Life span; Phase transitions; Rechargeable batteries; Solid electrolytes; V Dissolution; Vanadium; Zinc; Anode-Cathode Interplay; Acidic Aqueous Electrolytes; Al2(SO4)3 Additive; V Dissolution
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202215385

The anode‐cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V‐based AZIBs, Al2(SO4)3 is proposed as decent electrolyte additive to manipulate OH−‐mediated cross‐communication between Zn anode and NaV3O8 ⋅ 1.5H2O (NVO) cathode. The hydrolysis of Al3+ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH− accumulation by Al3+ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH− toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH−‐mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates. An innovative concept of manipulating anode‐cathode interplay for cycling durability improvement is demonstrated by employing Al2(SO4)3 as electrolyte additive. The suppression of OH−‐mediated cross‐communication between Zn and NVO by Al2(SO4)3 simultaneously stabilize the two electrodes, even under ultra‐acidic environment (pH≈0.9). The as‐assembled Zn||NVO batteries exhibit satisfactory lifespan at both low and high scan rates.