Thin film positive electrodes of lithium-rich manganese oxide spinels were prepared by radiofrequency magnetron sputtering from a LiMn2O4 ceramic target at a total pressure close to 2 Pa. Post-annealing treatments were necessary to get well-crystallized thin films displaying interesting electrochemical performances. Raman spectrum exhibiting several well-defined bands between 296 and 635 cm−1 is typical for the lithium-rich spinel. Based on ICP, RBS and XRD analyses, the thin films composition is close to Li1.2Mn1.8O4. The latter is also in accordance with a Mn3+/Mn4+ ratio close to 0.1 deduced from XPS measurements. Best electrochemical performance (capacity value, cycling life) between 2 V and 3.5 V vs Li+/Li was obtained for thin films annealed at 600 °C. A volumetric capacity of 52 μAh cm−2 μm−1 (close to about 90% of the theoretical value) was obtained at the first cycle at a C/100 regime. Contrary to most studies carried out on spinel thin films cycled in the 3 V range, no appreciable degradation of the discharge capacity was observed after few tens of cycles at room temperature, highlighting the beneficial effect of substituting 20% of Mn ions by Li ions and the presence of microvoids in thin films that limits the effect of strain generated from volume variation during the Li insertion/deinsertion process.
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | COTTE, Stéphane | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | PECQUENARD, Brigitte | |
| hal.structure.identifier | Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux [LITEN] | |
| dc.contributor.author | LE CRAS, Frédéric | |
| hal.structure.identifier | Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux [IPREM] | |
| dc.contributor.author | GRISSA, Rabeb | |
| hal.structure.identifier | Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux [IPREM] | |
| dc.contributor.author | MARTINEZ, Hervé | |
| hal.structure.identifier | Institut des Sciences Moléculaires [ISM] | |
| dc.contributor.author | BOURGEOIS, Lydie | |
| dc.date.issued | 2015 | |
| dc.identifier.issn | 0013-4686 | |
| dc.language.iso | en | |
| dc.publisher | Elsevier | |
| dc.title | Thin film positive electrodes of lithium-rich manganese oxide spinels were prepared by radiofrequency magnetron sputtering from a LiMn2O4 ceramic target at a total pressure close to 2 Pa. Post-annealing treatments were necessary to get well-crystallized thin films displaying interesting electrochemical performances. Raman spectrum exhibiting several well-defined bands between 296 and 635 cm−1 is typical for the lithium-rich spinel. Based on ICP, RBS and XRD analyses, the thin films composition is close to Li1.2Mn1.8O4. The latter is also in accordance with a Mn3+/Mn4+ ratio close to 0.1 deduced from XPS measurements. Best electrochemical performance (capacity value, cycling life) between 2 V and 3.5 V vs Li+/Li was obtained for thin films annealed at 600 °C. A volumetric capacity of 52 μAh cm−2 μm−1 (close to about 90% of the theoretical value) was obtained at the first cycle at a C/100 regime. Contrary to most studies carried out on spinel thin films cycled in the 3 V range, no appreciable degradation of the discharge capacity was observed after few tens of cycles at room temperature, highlighting the beneficial effect of substituting 20% of Mn ions by Li ions and the presence of microvoids in thin films that limits the effect of strain generated from volume variation during the Li insertion/deinsertion process. | |
| dc.title.en | Lithium-rich manganese oxide spinel thin films as 3V electrode for lithium batteries | |
| dc.type | Article de revue | |
| dc.identifier.doi | 10.1016/j.electacta.2015.08.145 | |
| dc.subject.hal | Chimie/Matériaux | |
| bordeaux.journal | Electrochimica Acta | |
| bordeaux.page | 528-534 | |
| bordeaux.volume | 180 | |
| bordeaux.peerReviewed | oui | |
| hal.identifier | hal-01195602 | |
| hal.version | 1 | |
| hal.popular | non | |
| hal.audience | Internationale | |
| hal.origin.link | https://hal.archives-ouvertes.fr//hal-01195602v1 | |
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