A new insight into the LiFePO4 delithiation process |
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| Institution: | 1. Departamento de Física, Universidade Federal do Ceará, Centro de Ciências, Caixa Postal 6030, Campus do Pici, 60455-970 Fortaleza, Ceará, Brazil;2. Departamento de Química, FFCLRP, Universidade de São Paulo, 14040-901 Ribeirão Preto, SP, Brazil;1. College of Materials Science and Engineering, Hunan University, Changsha, 410082, China;2. Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha, Hunan, 410082, China;1. School of Science and Technology, University of Camerino, I-62032 Camerino, Italy;2. Department für Geo- und Umweltwissenschaften, Sektion Mineralogie, Petrologie und Geochemie, Universität München, Theresienstr 41, 80333, München, Germany;1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991 Leninsky Pr. 31, Moscow, Russia;2. Lomonosov Moscow State University, 119991 Leninsky Gory 1, Moscow, Russia;3. A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119991 Leninsky Pr. 31, Moscow, Russia;1. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China;2. Key Laboratory of Nonferrous Metals Vacuum Metallurgy of Yunnan Province, Kunming University of Science and Technology, Kunming 650093, China;3. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China |
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| Abstract: | Raman and Fourier transform infrared measurements for LixM0.03Fe0.97PO4, M = Cr, Cu, Al, Ti were performed. The spectra for delithiated samples to a low content of lithium extraction are practically the same as those of LiFePO4. For a high content of lithium extraction, the spectra repeat that of FePO4. In the case of the Li0.11FePO4 oxide the spectra cannot be reproduced just by the superposition of the end member profiles. An additional broad band contribution is found in both Raman and infrared spectra probably due to a disordered structure present in the mixture. This suggests that the well accepted two-phase model for the delithiation process in LiFePO4 is incorrect. The model should be revised to include the new phase as detected here for a particular level of lithium extraction close to that of complete oxidation of the Fe2+ ions to Fe3+. |
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