Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO4 over Multiple Lithium Intercalation
| Autor: | Kamila M. Wiaderek, Fredrick Omenya, Shawn Sallis, M. Stanley Whittingham, Bohua Wen, Natasha A. Chernova, Nicholas F. Quackenbush, Yuh-Chieh Lin, Louis F. J. Piper, Hao Liu, Karena W. Chapman, Shyue Ping Ong, Saul H. Lapidus, Olaf J. Borkiewicz, Peter J. Chupas, Khim Karki |
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| Rok vydání: | 2016 |
| Předmět: |
Work (thermodynamics)
Extended X-ray absorption fine structure Chemistry General Chemical Engineering Kinetics Intercalation (chemistry) Pair distribution function Thermodynamics 02 engineering and technology General Chemistry Electrolyte 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences XANES 0104 chemical sciences Materials Chemistry Density functional theory 0210 nano-technology |
| Zdroj: | Chemistry of Materials. 28:1794-1805 |
| ISSN: | 1520-5002 0897-4756 |
| Popis: | In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized e-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of e-LixVOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFS techniques show a reversible hysteretic change in the short ( 2.4 A) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the ∼2.4 A V—O bond and its irreversible extension. Finally, we show tha... |
| Databáze: | OpenAIRE |
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