Unlocking Zn Storage Performance of Ammonium Vanadate Nanoflowers as High-Capacity Cathodes for Aqueous Zinc-ion Batteries via Potassium Ion and Ethylene Glycol Co-Intercalation Engineering
{"title":"Unlocking Zn Storage Performance of Ammonium Vanadate Nanoflowers as High-Capacity Cathodes for Aqueous Zinc-ion Batteries via Potassium Ion and Ethylene Glycol Co-Intercalation Engineering","authors":"Ji Chen, Xiaoyue Zhang, Yangjie Li, Xiaoying Li, Xiaoqin Zhang, Yuxiang Chen, Qiaoji Zheng, Xingqiao Wu, Heng Zhang, Xin Tan, Dunmin Lin","doi":"10.1039/d4ta04112g","DOIUrl":null,"url":null,"abstract":"Ammonium vanadate (NH4V4O10) is a highly promising cathode for aqueous zinc ion batteries (AZIBs) due to its tunable layered structure and high specific capacity; however, limited active sites, poor kinetics and irreversible structural collapse during cycling suppress its wide application. Herein, the engineering of the co-intercalation of K+ and ethylene glycol molecules is proposed to unlock Zn storage performance of the NH4V4O10. It is found that the co-intercalation of K+ and ethylene glycol enlarges the interlayer spacing to 11.5 Å, induces a high level of oxygen vacancies and enhances the strength of ionic bonding in the NH4V4O10, ensuring large Zn2+ diffusion channels, efficient redox reactivity and strong layered-structure stability. Meanwhile, K+ ions and ethylene glycol also weaken the crystallinity of NH4V4O10 and induce the transformation of microscopic morphology from strips to nanoflowers self-assembled from ultrathin nanosheets, promoting the transfer of electrons and ions and complete penetration of the electrolyte during electrochemical reactions. In addition, the band gap is significantly reduced by 0.2 eV after the co-intercalation of K+ and ethylene glycol, improving the electronic conductivity and decreasing the diffusion barrier of Zn2+. As expected, K+ and ethylene glycol co-intercalated NH4V4O10 exhibit excellent Zn storage properties, delivering an ultrahigh capacity of 614.1 mAh g-1 at 0.5 A g-1, and presenting an outstanding rate performance of 472.9 mAh g-1 and a high retention of 89% after 2000 cycles at 10 A g-1. This work provides a useful reference for unlocking the Zn storage performance of layered V-based cathodes for AZIBs by synergistically modulating interlayer spacing, oxygen defects and microscopic morphology of the materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":10.7000,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ta04112g","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Ammonium vanadate (NH4V4O10) is a highly promising cathode for aqueous zinc ion batteries (AZIBs) due to its tunable layered structure and high specific capacity; however, limited active sites, poor kinetics and irreversible structural collapse during cycling suppress its wide application. Herein, the engineering of the co-intercalation of K+ and ethylene glycol molecules is proposed to unlock Zn storage performance of the NH4V4O10. It is found that the co-intercalation of K+ and ethylene glycol enlarges the interlayer spacing to 11.5 Å, induces a high level of oxygen vacancies and enhances the strength of ionic bonding in the NH4V4O10, ensuring large Zn2+ diffusion channels, efficient redox reactivity and strong layered-structure stability. Meanwhile, K+ ions and ethylene glycol also weaken the crystallinity of NH4V4O10 and induce the transformation of microscopic morphology from strips to nanoflowers self-assembled from ultrathin nanosheets, promoting the transfer of electrons and ions and complete penetration of the electrolyte during electrochemical reactions. In addition, the band gap is significantly reduced by 0.2 eV after the co-intercalation of K+ and ethylene glycol, improving the electronic conductivity and decreasing the diffusion barrier of Zn2+. As expected, K+ and ethylene glycol co-intercalated NH4V4O10 exhibit excellent Zn storage properties, delivering an ultrahigh capacity of 614.1 mAh g-1 at 0.5 A g-1, and presenting an outstanding rate performance of 472.9 mAh g-1 and a high retention of 89% after 2000 cycles at 10 A g-1. This work provides a useful reference for unlocking the Zn storage performance of layered V-based cathodes for AZIBs by synergistically modulating interlayer spacing, oxygen defects and microscopic morphology of the materials.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.