Yuwei Su, Zhiwei Zhao, Erkang Wang, Zhangquan Peng
{"title":"Mechanistic Study on Oxygen Reduction Reaction in High-Concentrated Electrolytes for Aprotic Lithium–Oxygen Batteries","authors":"Yuwei Su, Zhiwei Zhao, Erkang Wang, Zhangquan Peng","doi":"10.1021/acs.jpclett.4c02455","DOIUrl":null,"url":null,"abstract":"Highly concentrated electrolytes (HCEs) have energized the development of high-energy-density lithium metal batteries by facilitating the formation of robust inorganic-derived solid electrolyte interfaces on the lithium anode. However, the oxygen reduction reaction (ORR) occurring on the cathode side remains ambiguous in HCE-based lithium–oxygen (Li–O<sub>2</sub>) batteries. Herein, we investigate the ORR mechanism in a highly concentrated LiTFSI-CH<sub>3</sub>CN electrolyte using ultra-microelectrode voltammetry coupled with in situ spectroscopies. It is found that, compared to the dilute electrolyte, the HCE prolongs the lifespan of superoxide intermediates and decelerates their migration rate to the bulk solution, resulting in a change in growth mode for the discharge product of Li<sub>2</sub>O<sub>2</sub> from traditional two-dimensional film growth to surface three-dimensional expansion growth. This alteration reduces the cathode passivation and thus delivers the enhanced discharge capacity. Additionally, the HCE also increases the reaction energy barrier between superoxide and solvent molecules, thereby minimizing parasitic reactions and improving the cycle performance of Li–O<sub>2</sub> batteries. Our study reveals the intricate interplay between electrolytes and oxygen intermediates and provides important insights into electrolyte chemistries for better Li–O<sub>2</sub> batteries.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpclett.4c02455","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Highly concentrated electrolytes (HCEs) have energized the development of high-energy-density lithium metal batteries by facilitating the formation of robust inorganic-derived solid electrolyte interfaces on the lithium anode. However, the oxygen reduction reaction (ORR) occurring on the cathode side remains ambiguous in HCE-based lithium–oxygen (Li–O2) batteries. Herein, we investigate the ORR mechanism in a highly concentrated LiTFSI-CH3CN electrolyte using ultra-microelectrode voltammetry coupled with in situ spectroscopies. It is found that, compared to the dilute electrolyte, the HCE prolongs the lifespan of superoxide intermediates and decelerates their migration rate to the bulk solution, resulting in a change in growth mode for the discharge product of Li2O2 from traditional two-dimensional film growth to surface three-dimensional expansion growth. This alteration reduces the cathode passivation and thus delivers the enhanced discharge capacity. Additionally, the HCE also increases the reaction energy barrier between superoxide and solvent molecules, thereby minimizing parasitic reactions and improving the cycle performance of Li–O2 batteries. Our study reveals the intricate interplay between electrolytes and oxygen intermediates and provides important insights into electrolyte chemistries for better Li–O2 batteries.
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.