Stabilization of Oxygen‐Dependent Fe3+/4+ Redox in Li‐Excess DRX Cathode Exhibiting Anionic Redox via Transition Metal Combination

Author:

Lee Hayeon1,Kim Minji1,Park Hyunyoung1,Yoo Yiseul2,Na Sangmun1,Lim Hee‐Dae3,Kim Jongsoon14,Yoon Won‐Sub14ORCID

Affiliation:

1. Department of Energy Science Sungkyunkwan University Suwon 16419 Republic of Korea

2. Energy Storage Research Center Korea Institute of Science and Technology (KIST) Seoul 02792 Republic of Korea

3. Department of Chemical Engineering Hanyang University Seoul 04763 Republic of Korea

4. SKKU Institute of Energy Science and Technology (SIEST) Sungkyunkwan University Suwon 16419 Republic of Korea

Abstract

AbstractDeveloping sustainable Li‐ion batteries requires high‐energy cathodes based on low‐cost, earth‐abundant elements, moving away from low‐reserve nickel and cobalt. Fe‐based oxide cathodes with Fe3+/4+ and O2−/n− redox couples offer potential but face low initial Coulombic efficiency and significant voltage hysteresis. This study investigates Li‐excess Fe‐based disordered rock‐salt (DRX) oxyfluorides (Li2Fe0.5M0.5O2F; M = Fe, Ti, Mn) using combined electrochemical/spectroscopic characterization and first‐principles calculation. Oxygen‐dependent Fe3+/4+ redox, related to Fe 3d–O 2p hybrid state, can be stabilized when combined with Mn3+/4+ redox in DRX structure owing to the unusual decrease in its redox potential. The moderately high charge transfer gap stabilizes Fe4+ against ligand‐to‐metal charge transfer (LMCT) on charge, reduces the amount of oxygen oxidation, thereby increasing Coulombic efficiency. On discharge, it allows metal‐to‐ligand charge transfer (MLCT) without substantial overpotential, reducing hysteresis in oxygen redox. The resulting composition exhibits high capacity (309 mAh g−1) and energy density (998 Wh kg−1), providing insights for next‐generation Ni‐ and Co‐free cathode materials.

Funder

National Research Foundation of Korea

Publisher

Wiley

Subject

Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials

Cited by 1 articles. 订阅此论文施引文献 订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3