Deciphering the Oxygen Absorption Pre-edge: A Caveat on its Application for Probing Oxygen Redox Reactions in Batteries

作     者：Subhayan Roychoudhury Ruimin Qiao Zengqing Zhuo Qinghao Li Yingchun Lyu Jung-Hyun Kim Jun Liu Eungje Lee Bryant J.Polzin Jinghua Guo Shishen Yan Yongsheng Hu Hong Li David Prendergast Wanli Yang Subhayan Roychoudhury;Ruimin Qiao;Zengqing Zhuo;Qinghao Li;Yingchun Lyu;Jung-Hyun Kim;Jun Liu;Eungje Lee;Bryant J.Polzin;Jinghua Guo;Shishen Yan;Yongsheng Hu;Hong Li;David Prendergast;Wanli Yang

作者机构：Advanced Light SourceLawrence Berkeley National Laboratory1 Cyclotron RoadBerkeley CA 94720USA School of Advanced MaterialsShenzhen Graduate SchoolPeking UniversityShenzhen 518055China School of PhysicsNational Key Laboratory of Crystal MaterialsShandong UniversityJinan 250100China Beijing National Laboratory for Condensed Matter PhysicsInstitute of PhysicsChinese Academy of SciencesBeijing 100190China Mechanical and Aerospace EngineeringThe Ohio State UniversityColumbus OH 43210USA R&D department2M LLC193 Thompson DrHockessin DE 19707USA Chemical Science and Engineering Division Argonne National LaboratoryArgonne IL 60439 USA The Molecular FoundryLawrence Berkeley National Laboratory1 Cyclotron Road Berkeley CA 94720 USA 

出 版 物：《Energy & Environmental Materials》 (能源与环境材料（英文）)

年 卷 期：2021年第4卷第2期

页      面：246-254页

核心收录：

学科分类：0710[理学-生物学] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 0808[工学-电气工程] 08[工学] 0807[工学-动力工程及工程热物理] 0815[工学-水利工程] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0706[理学-大气科学] 0702[理学-物理学] 

基　　金：supported by the LDRD program at the LBNL and facilitated by a User Program at The Molecular Foundry(TMF) provided by the TMF clusters(managed by the High Performance Computing Services Group,at LBNL) by the National Energy Research Scientific Computing Center(NERSC) supported by the Office of Science of the US DOE under Contract No.DE-AC02-05CH11231 support from EERE VTO under the Applied Battery Materials Program of the US DOE with Contract No.DE-AC02-05CH11231 supported by the DOE VTO at Argonne National Laboratory 

主　　题：battery oxygen redox x-ray absorption spectroscopy cathode material redox reaction 

摘      要：The pre-edges of oxygen-K X-ray absorption spectra have been ubiquitous in transition metal(TM)oxide studies in various fields,especially on the fervent topic of oxygen redox states in battery ***,critical debates remain on the use of the O-K pre-edge variations upon electrochemical cycling as evidences of oxygen redox reactions,which has been a popular practice in the battery *** study presents an investigation of the O-K pre-edge of 55 oxides covering all 3d TMs with different elements,structures,and electrochemical states through combined experimental and theoretical *** is shown unambiguously that the O-K pre-edge variation in battery cathodes is dominated by changing TM-d ***,the pre-edge enables a unique opportunity to project the lowest unoccupied TM-d states onto one common energy window,leading to a summary map of the relative energy positions of the low-lying TM states,with higher TM oxidation states at lower energies,corresponding to higher electrochemical *** results naturally clarify some unusual redox reactions,such as Cr^(3+/6+).This work provides a critical clarification on O-K pre-edge interpretation and more importantly a benchmark database of O-K pre-edge for characterizing redox reactions in batteries and other energy materials.