Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines
Transition metal substitution is a key strategy to optimize the functional properties of advanced crystalline materials used as positive electrodes in secondary lithium batteries (LIBs). Here we investigate the structural alterations in the olivine lattice of Mn and Ni substituted LiCoPO<sub>4...
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doaj-c6c57fbd150448dd8a5c239b415ddb152020-11-25T01:42:38ZengMDPI AGMolecules1420-30492020-01-0125360110.3390/molecules25030601molecules25030601Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> OlivinesOriele Palumbo0Jessica Manzi1Daniele Meggiolaro2Francesco M. Vitucci3Francesco Trequattrini4Mariangela Curcio5Annalisa Paolone6Sergio Brutti7CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Rome, ItalyCNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Rome, ItalyComputational Laboratory for Hybrid/Organic Photovoltaics (CLHYO) Istituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta”(CNR-SCITEC), Via Elce di Sotto 8, 06123 Perugia, ItalyCNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Rome, ItalyCNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Rome, ItalyDepartment of Sciences, University of Basilicata, V.le dell’Ateneo Lucano 10, 85100 Potenza, ItalyCNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Rome, ItalyDepartment of Chemistry, University of Rome ‘‘La Sapienza’’, Piazzale Aldo Moro 5, 00185 Rome, ItalyTransition metal substitution is a key strategy to optimize the functional properties of advanced crystalline materials used as positive electrodes in secondary lithium batteries (LIBs). Here we investigate the structural alterations in the olivine lattice of Mn and Ni substituted LiCoPO<sub>4</sub> phase and the impact on performance in LIBs. X-ray diffraction (XRD) and extended X-ray absorption experiments have been carried out in order to highlight the structural alterations induced by partial substitution of cobalt by manganese and nickel. XRD analysis suggests that substitution induces an expansion of the lattices and an increase of the antisite disorder between lithium and transition metal ions in the structure. XAS data highlight negligible electronic disorder but a relevant modulation in the local coordination around the different metal ions. Moreover, galvanostatic tests showed poor reversibility of the redox reaction compared to the pure LCP sample, and this failure is discussed in detail in view of the observed remarkable structural changes.https://www.mdpi.com/1420-3049/25/3/601cathode materialsolivinex-ray diffractionx-ray absorption |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Oriele Palumbo Jessica Manzi Daniele Meggiolaro Francesco M. Vitucci Francesco Trequattrini Mariangela Curcio Annalisa Paolone Sergio Brutti |
spellingShingle |
Oriele Palumbo Jessica Manzi Daniele Meggiolaro Francesco M. Vitucci Francesco Trequattrini Mariangela Curcio Annalisa Paolone Sergio Brutti Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines Molecules cathode materials olivine x-ray diffraction x-ray absorption |
author_facet |
Oriele Palumbo Jessica Manzi Daniele Meggiolaro Francesco M. Vitucci Francesco Trequattrini Mariangela Curcio Annalisa Paolone Sergio Brutti |
author_sort |
Oriele Palumbo |
title |
Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines |
title_short |
Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines |
title_full |
Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines |
title_fullStr |
Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines |
title_full_unstemmed |
Effect of Transitional Metals (Mn and Ni) Substitution in LiCoPO<sub>4</sub> Olivines |
title_sort |
effect of transitional metals (mn and ni) substitution in licopo<sub>4</sub> olivines |
publisher |
MDPI AG |
series |
Molecules |
issn |
1420-3049 |
publishDate |
2020-01-01 |
description |
Transition metal substitution is a key strategy to optimize the functional properties of advanced crystalline materials used as positive electrodes in secondary lithium batteries (LIBs). Here we investigate the structural alterations in the olivine lattice of Mn and Ni substituted LiCoPO<sub>4</sub> phase and the impact on performance in LIBs. X-ray diffraction (XRD) and extended X-ray absorption experiments have been carried out in order to highlight the structural alterations induced by partial substitution of cobalt by manganese and nickel. XRD analysis suggests that substitution induces an expansion of the lattices and an increase of the antisite disorder between lithium and transition metal ions in the structure. XAS data highlight negligible electronic disorder but a relevant modulation in the local coordination around the different metal ions. Moreover, galvanostatic tests showed poor reversibility of the redox reaction compared to the pure LCP sample, and this failure is discussed in detail in view of the observed remarkable structural changes. |
topic |
cathode materials olivine x-ray diffraction x-ray absorption |
url |
https://www.mdpi.com/1420-3049/25/3/601 |
work_keys_str_mv |
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