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dc.contributor.authorLin, Chia-Ching
dc.contributor.authorHsu, Chi-Ting
dc.contributor.authorLiu, Wenjing
dc.contributor.authorHuang, Shao-Chu
dc.contributor.authorLin, Ming-Hsien
dc.contributor.authorKortz, Ulrich
dc.contributor.authorMougharbel, Ali S
dc.contributor.authorChen, Tsan-Yao
dc.contributor.authorHu, Chih-Wei
dc.contributor.authorLee, Jyh-Fu
dc.contributor.authorWang, Chun-Chieh
dc.contributor.authorLiao, Yen-Fa
dc.contributor.authorLi, Lain-Jong
dc.contributor.authorLi, Linlin
dc.contributor.authorPeng, Shengjie
dc.contributor.authorStimming, Ulrich
dc.contributor.authorChen, H.-Y.
dc.identifier.citationLin, C.-C., Hsu, C.-T., Liu, W., Huang, S.-C., Lin, M.-H., Kortz, U., … Chen, H.-Y. (2020). In Operando X-ray Studies of High-Performance Lithium-Ion Storage in Keplerate-Type Polyoxometalate Anodes. ACS Applied Materials & Interfaces. doi:10.1021/acsami.0c09344
dc.description.abstractPolyoxometalates (POMs) have emerged as potential anode materials for lithium-ion batteries (LIBs) owing to their ability to transfer multiple electrons. Although POM anode materials exhibit notable results in LIBs, their energy-storage mechanisms have not been well-investigated. Here, we utilize various in operando and ex situ techniques to verify the charge-storage mechanisms of a Keplerate-type POM Na2K23{[(MoVI)MoVI5O21(H2O)3(KSO4)]12 [(VIVO)30(H2O)20(SO4)0.5]}·ca200H2O ({Mo72V30}) anode in LIBs. The {Mo72V30} anode provides a high reversible capacity of up to ∼1300 mA h g-1 without capacity fading for up to 100 cycles. The lithium-ion storage mechanism was studied systematically through in operando synchrotron X-ray absorption near-edge structure, ex situ X-ray diffraction, ex situ extended X-ray absorption fine structure, ex situ transmission electron microscopy, in operando synchrotron transmission X-ray microscopy, and in operando Raman spectroscopy. Based on the abovementioned results, we propose that the open hollow-ball structure of the {Mo72V30} molecular cluster serves as an electron/ion sponge that can store a large number of lithium ions and electrons reversibly via multiple and reversible redox reactions (Mo6+ ↔ Mo1+ and V5+/V4+↔ V1+) with fast lithium diffusion kinetics (DLi+: 10-9-10-10 cm2 s-1). No obvious volumetric expansion of the microsized {Mo72V30} particle is observed during the lithiation/delithiation process, which leads to high cycling stability. This study provides comprehensive analytical methods for understanding the lithium-ion storage mechanism of such complicated POMs, which is important for further studies of POM electrodes in energy-storage applications.
dc.description.sponsorshipThe authors thank the Instrumentation Center at National Tsing Hua University for providing assistance in electron spectroscopy for chemical analysis, XRD measurement for structural analysis, and TEM for morphological and microstructural analyses. The authors also thank Dr. Chih-Wen Pao and Dr. Jeng-Lung Chen for their help on the in operando synchrotron XAS (beamline TPS 44A1) in National Synchrotron Radiation Research Center (NSRRC), Hsinchu, Taiwan.
dc.publisherAmerican Chemical Society (ACS)
dc.rightsThis is an open access article.
dc.titleInOperando X-ray Studies of High-Performance Lithium-Ion Storage in Keplerate-Type Polyoxometalate Anodes.
dc.contributor.departmentMaterial Science and Engineering Program
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalACS applied materials & interfaces
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionDepartment of Materials Science and Engineering, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan
dc.contributor.institutionDepartment of Life Sciences and Chemistry, Jacobs University, Campus Ring 1, 28759 Bremen, Germany
dc.contributor.institutionKey Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, P. R. China
dc.contributor.institutionDepartment of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, Taoyuan 334, Taiwan
dc.contributor.institutionDepartment of Engineering and System Science, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan
dc.contributor.institutionNational Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu 30013, Taiwan
dc.contributor.institutionJiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
dc.contributor.institutionChemistry–School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, U.K.
kaust.personLi, Lain-Jong

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