Linking Local Environments and Hypertine Shifts: A Combined Experimental and Theoretical P and Li Solid-State NMR Study of Paramagnetic Fe(III) Phosphates.
Iron phosphates (FePO) are among the most promising candidate materials for advanced Li-ion battery cathodes. This work reports upon a combined nuclear magnetic resonance (NMR) experimental and periodic density functional theory (DFT) computational study of the environments and electronic structures...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 47; pp. 16825 - 16841 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
12/1/2010
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=55732466&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 55732466 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/1/2010 vid: 132 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 55732466 10.1021/ja102678r ppf: 16825 ppct: 16 formats: tig: atl: Linking Local Environments and Hypertine Shifts: A Combined Experimental and Theoretical P and Li Solid-State NMR Study of Paramagnetic Fe(III) Phosphates. aug: au: Jongsik Kim Middlemiss, Derek S. Chernova, Natasha A. Zhu, Ben Y. X. Masquelier, Christian Grey, Clare P. affil: Department of Chemistry, Stony Brook University, Stony Brook New York 11794-3400, United States Institute for Materials Research, SUNY Binghamton, Binghamton, New York 13902-6000, United States Laboratoire de Réactivité et Chimie des Solides, UMR CNPS 6007, Université de Picardie Jules Verne, 80039 Amiens, France Department of Chemistry, University of Cambridge, Lensfield Road Cambridge, United Kingdom CB2 1EW su: Iron Phosphates Nuclear magnetic resonance Density functionals Cathode rays Electronic structure sug: subj: Iron Phosphates Nuclear magnetic resonance Density functionals Cathode rays Electronic structure ab: Iron phosphates (FePO) are among the most promising candidate materials for advanced Li-ion battery cathodes. This work reports upon a combined nuclear magnetic resonance (NMR) experimental and periodic density functional theory (DFT) computational study of the environments and electronic structures occurring in a range of paramagnetic Fe(III) phosphates comprising FePO (heterosite), monoclinic LiFe(PO) (anti-NASICON A type), rhombohedral LiFe(PO) (NASICON B type), LiFePO, orthorhombic FePO∙2HO (strengite), monoclinic FePO∙2HO (phosphosiderite), and the dehydrated forms of the latter two phases. Many of these materials serve as model compounds relevant to battery chemistry. The P spin-echo mapping and Li magic angle spinning NMR techniques yield the hyperfine shifts of the species of interest, complemented by periodic hybrid functional DFT calculations of the respective hyperfine and quadrupolar tensors. A Curie-Weiss-based magnetic model scaling the DFT-calculated hyperfine parameters from the ferromagnetic into the experimentally relevant paramagnetic state is derived and applied, providing quantitative finite temperature values for each phase. The sensitivity of the hyperfine parameters to the composition of the DFT exchange functional is characterized by the application of hybrid Hamiltonians containing admixtures 0%, 20%, and 35% of Fock exchange. Good agreement between experimental and calculated values is obtained, provided that the residual magnetic couplings persisting in the paramagnetic state are included. The potential applications of a similar combined experimental and theoretical NMR approach to a wider range of cathode materials are discussed. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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