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  4. Spin-Transfer Pathways in Paramagnetic Lithium Transition-Metal Phosphates from Combined Broadband Isotropic Solid-State MAS NMR Spectroscopy and DFT Calculations
 
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research article

Spin-Transfer Pathways in Paramagnetic Lithium Transition-Metal Phosphates from Combined Broadband Isotropic Solid-State MAS NMR Spectroscopy and DFT Calculations

Clement, Raphaele J.
•
Pell, Andrew J.
•
Middlemiss, Derek S.
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2012
Journal of the American Chemical Society

Substituted lithium transition-metal (TM) phosphate LiFexMn1-xPO4, materials with olivine-type structures are among the most promising next generation lithium ion battery cathodes. However, a complete atomic-level description of the structure of such phases is not yet available. Here, a combined experimental and theoretical approach to the detailed assignment of the P-31 NMR spectra of the LiFexMn1-xPO4 (x = 0, 0.25, 0.5, 0.75, 1) pure and mixed TM phosphates is developed and applied. Key to the present work is the development of a new NMR experiment enabling the characterization of complex paramagnetic materials via the complete separation of the individual isotropic chemical shifts, along with solid-state hybrid DFT calculations providing the separate hyperfine contributions of all distinct Mn-O-P and Fe-O-P bond pathways. The NMR experiment, referred to as aMAT, makes use of short high-powered adiabatic pulses (SHAPs), which can achieve 100% inversion over a range of isotropic shifts on the order of 1 MHz and with anisotropies greater than 100 kHz. In addition to complete spectral assignments of the mixed phases, the present study provides a detailed insight into the differences in electronic structure driving the variations in hyperfine parameters across the range of materials. A simple model delimiting the effects of distortions due to Mn/Fe substitution is also proposed and applied. The combined approach has clear future applications to TM-bearing battery cathode phases in particular and for the understanding of complex paramagnetic phases in general.

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Type
research article
DOI
10.1021/ja306876u
Web of Science ID

WOS:000309854700044

Author(s)
Clement, Raphaele J.
•
Pell, Andrew J.
•
Middlemiss, Derek S.
•
Strobridge, Fiona C.
•
Miller, Joel K.
•
Whittingham, M. Stanley
•
Emsley, Lyndon  
•
Grey, Clare P.
•
Pintacuda, Guido
Date Issued

2012

Publisher

AMER CHEMICAL SOC

Published in
Journal of the American Chemical Society
Volume

134

Issue

41

Start page

17178

End page

17185

Peer reviewed

REVIEWED

Written at

OTHER

EPFL units
LRM  
Available on Infoscience
January 8, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/109983
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