{"title":"Design principles of novel Zn fluorocarboxylate protection layer toward durable dendrite-free Zn metal anodes","authors":"","doi":"10.1016/j.jechem.2024.10.004","DOIUrl":null,"url":null,"abstract":"<div><div>Aqueous Zn ion batteries (ZIBs) have received extensive attention due to their intrinsic safety, high abundance, and low cost. However, uncontrolled dendrite growth and water-induced side reactions at electrode/electrolyte interfaces hinder the advancement of ZIBs. Herein, density functional theory (DFT) calculation indicates that Zn heptafluorobutyrate can facilitate uniform Zn<sup>2+</sup> deposition by leveraging the abundant zincophilic groups (e.g., –COO<sup>−</sup> and –CF) and inhibit water-induced side reactions due to the presence of hydrophobic carbon chains. A Zn heptafluorobutyrate protective layer (denoted as ZFA) is constructed on the metallic Zn surface in situ by acid etching process to control Zn<sup>2+</sup> desolvation and nucleation behaviors, ensuring enhanced reversibility and stability of Zn anodes. Consequently, the Zn@ZFA anode demonstrates stable operation for more than 2200 h at 1 mA cm<sup>−2</sup> and over 7300 cycles at 40 mA cm<sup>−2</sup>, with high Coulombic efficiency of 99.8% over 1900 cycles at 5 mA cm<sup>−2</sup>. Impressively, Zn@ZFA||VO<sub>2</sub> full cell achieves exceptional cycle life (204 mA h g<sup>−1</sup> after 750 cycles at 3 A g<sup>−1</sup>) and remarkable rate performance (236 mA g<sup>−1</sup> at 10 A g<sup>−1</sup>). This work provides an insightful guidance for constructing a protection layer of dendrite-free Zn anodes for high-performance ZIBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Energy Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2095495624006971","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Energy","Score":null,"Total":0}
引用次数: 0
Abstract
Aqueous Zn ion batteries (ZIBs) have received extensive attention due to their intrinsic safety, high abundance, and low cost. However, uncontrolled dendrite growth and water-induced side reactions at electrode/electrolyte interfaces hinder the advancement of ZIBs. Herein, density functional theory (DFT) calculation indicates that Zn heptafluorobutyrate can facilitate uniform Zn2+ deposition by leveraging the abundant zincophilic groups (e.g., –COO− and –CF) and inhibit water-induced side reactions due to the presence of hydrophobic carbon chains. A Zn heptafluorobutyrate protective layer (denoted as ZFA) is constructed on the metallic Zn surface in situ by acid etching process to control Zn2+ desolvation and nucleation behaviors, ensuring enhanced reversibility and stability of Zn anodes. Consequently, the Zn@ZFA anode demonstrates stable operation for more than 2200 h at 1 mA cm−2 and over 7300 cycles at 40 mA cm−2, with high Coulombic efficiency of 99.8% over 1900 cycles at 5 mA cm−2. Impressively, Zn@ZFA||VO2 full cell achieves exceptional cycle life (204 mA h g−1 after 750 cycles at 3 A g−1) and remarkable rate performance (236 mA g−1 at 10 A g−1). This work provides an insightful guidance for constructing a protection layer of dendrite-free Zn anodes for high-performance ZIBs.
期刊介绍:
The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies.
This journal focuses on original research papers covering various topics within energy chemistry worldwide, including:
Optimized utilization of fossil energy
Hydrogen energy
Conversion and storage of electrochemical energy
Capture, storage, and chemical conversion of carbon dioxide
Materials and nanotechnologies for energy conversion and storage
Chemistry in biomass conversion
Chemistry in the utilization of solar energy