title: Insights into the Distinct Lithiation/Sodiation of Porous Cobalt Oxide by in Operando Synchrotron X-ray Techniques and Ab Initio Molecular Dynamics Simulations.
abstract: Sodium-ion batteries (SIBs) have been considered as one of the promising power source candidates for the stationary storage industries owing to the much lower cost of sodium than lithium. It is well-known that the electrode materials largely determine the energy density of the battery systems. However, recent discoveries on the electrode materials showed that most of them present distinct lithium and sodium storage performance, which is not yet well understood. In this work, we performed a comparative understanding on the structural changes of porous cobalt oxide during its electrochemical lithiation and sodiation process by in operando synchrotron small angel X-ray scattering, X-ray diffraction, and X-ray absorption spectroscopy. It was found that compared to the lithiation process, the porous cobalt oxide undergoes less pore structure changes, oxidation state, and local structure changes as well as crystal structure evolution during its sodiation process, which is attributed to the intrinsic low sodiation activity of cobalt oxide as evidenced by ab initio molecular dynamics simulations. Moreover, it was indicated that the sodiation activity of metal sulfides is higher than that of metal oxides, indicating a better candidate for SIBs. Such understanding is crucial for future design and improvement of high-performance electrode materials for SIBs.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Gui-Liang
authors.initials: GL
authors.lastname: Xu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University , Xiamen, 361005, China.
authors.forename: Tian
authors.initials: T
authors.lastname: Sheng
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Lina
authors.initials: L
authors.lastname: Chong
authors.affiliation: Materials Science Program, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Tianyuan
authors.initials: T
authors.lastname: Ma
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Cheng-Jun
authors.initials: CJ
authors.lastname: Sun
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Xiaobing
authors.initials: X
authors.lastname: Zuo
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Di-Jia
authors.initials: DJ
authors.lastname: Liu
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Yang
authors.initials: Y
authors.lastname: Ren
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Xiaoyi
authors.initials: X
authors.lastname: Zhang
authors.affiliation: Nanoscience and Technology Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Yuzi
authors.initials: Y
authors.lastname: Liu
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Steve M
authors.initials: SM
authors.lastname: Heald
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University , Xiamen, 361005, China.
authors.forename: Shi-Gang
authors.initials: SG
authors.lastname: Sun
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Zonghai
authors.identifier: 0000-0001-5371-9463
authors.initials: Z
authors.lastname: Chen
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Khalil
authors.identifier: 0000-0001-9206-3719
authors.initials: K
authors.lastname: Amine
keywords: Lithiation; ab initio molecular dynamic simulation; batteries; cobalt oxide; in operando X-ray; sodiation