Structural analysis of lanthanum-containing battery materials using 139La solid-state NMR

2011 ◽  
Vol 89 (9) ◽  
pp. 1105-1117 ◽  
Author(s):  
Leigh Spencer ◽  
Eric Coomes ◽  
Eric Ye ◽  
Victor Terskikh ◽  
Adam Ramzy ◽  
...  
Keyword(s):  
Solid State ◽  
Structural Analysis ◽  
Lithium Ion Battery ◽  
Solid State Nmr ◽  
Nmr Spectra ◽  
Lithium Ion ◽  
Atomic Level ◽  
Coupling Constants ◽  
Battery Materials ◽  
Quadrupolar Coupling

139La solid-state NMR spectra, acquired at 21.1 and 11.7 T, have been used to evaluate the structural properties of the lithium ion battery materials, La32Li16Fe6.4O67 and Li3xLa2/3–xTiO3. In particular, atomic-level disorder in the second coordination sphere environment of lanthanum in these materials has been indicated by the observation of a distribution in the asymmetry parameters and the quadrupolar coupling constants derived from experimental NMR spectra, and supported by theoretical calculations. For comparison, 139La NMR has been obtained for the two model compounds La2O3 and LaNbO4, in which there is no atomic-level disorder. Quadrupolar coupling constants in the range of 17 to 59 MHz have been measured, and these values are supported by previous work as well as theoretical predictions performed in CASTEP. It has been shown that 139La NMR is a useful tool for the structural analysis of lithium ion battery materials, and when combined with 7Li MAS NMR and powder X-ray diffraction, can be used to determine the structure of complex solid-state electrolyte and electrode materials.

scholarly journals Revealing Defects in Crystalline Lithium-Ion Battery Electrodes by Solid-State NMR: Applications to LiVPO4F

2015 ◽  
Vol 27 (15) ◽  
pp. 5212-5221 ◽  
Author(s):  
Robert J. Messinger ◽  
Michel Ménétrier ◽  
Elodie Salager ◽  
Adrien Boulineau ◽  
Mathieu Duttine ◽  
...  
Keyword(s):  
Solid State ◽  
Lithium Ion Battery ◽  
Solid State Nmr ◽  
Lithium Ion

Investigation of thin film all-solid-state lithium ion battery materials

Ionics ◽  
2003 ◽  
Vol 9 (5-6) ◽  
pp. 348-356 ◽  
Author(s):  
J. Schwenzel ◽  
V. Thangadurai ◽  
W. Weppner
Keyword(s):  
Thin Film ◽  
Solid State ◽  
Lithium Ion Battery ◽  
Lithium Ion ◽  
Battery Materials

A solid state NMR and molecular orbital study of hydroxylammonium chloride

1999 ◽  
Vol 77 (11) ◽  
pp. 1813-1820 ◽  
Author(s):  
Glenn H Penner ◽  
YC Phillis Chang ◽  
H Michelle Grandin
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Chemical Shift ◽  
Molecular Orbital ◽  
Solid State Nmr ◽  
Coupling Constants ◽  
Basis Sets ◽  
Exponential Factor ◽  
Line Shapes ◽  
Quadrupolar Coupling

Deuterium and nitrogen-15 NMR spectroscopy has been used to measure the 2H quadrupolar coupling and 15N chemical shift tensors in solid hydroxylammonium chloride, NH3OH+Cl-, (HAC). In addition, the NH3 and OH dynamics have been investigated by variable temperature 2H line shapes and T1 measurements. The Arrhenius activation energy for NH3 rotation is 22.5 ± 1.8 kJ/mol with a pre-exponential factor of 8 ± 3 × 1012 s-1 from line shapes and 21.3 ± 2 kJ/mol with an infinite temperature correlation time, τinf,, of 5.0 ± 0.4 × 10-14 s from the T1 analysis. The latter value corresponds to a pre-exponential factor of 6.7 ± 0.5 × 1012 s-1, if a three-site exchange is assumed. There was no evidence for OH reorientation up to 405 K, indicating a rather strong OH···Cl hydrogen bond. Previously reported inconsistencies between crystal structure and molecular orbital derived N-O bond lengths are cleared up by performing geometry optimizations with large basis sets and taking electron correlation into account. The internal rotational potential for the isolated HA cation is calculated to be 5.8 kJ/mol at the MP2/6-31G** level, with the trans geometry preferred. Calculations that employ the neutron diffraction geometry and include the Cl- anions that surround the HA+ cation yield an upper limit for the activation energy for NH3 group rotation of 62 kJ/mol. Analysis of the deuterium spectrum and T1 data yield nuclear quadrupolar coupling constants of 160 ± 5 kHz and 194 ± 5 kHz (η = 0.50 ± 0.05) for the ND3 and OD deuterons, respectively. Density functional calculations of the deuterium and nitrogen-14 nuclear quadrupolar coupling constants at the B3LYP level show that it is necessary to include the influence of the surrounding chloride anions. We have also shown that it is possible to obtain accurate proton chemical shifts from the deuterium MAS spectrum of solid HAC-d4.Key words: solid state NMR, molecular dynamics, nitrogen 15 chemical shift anisotropy.

Cobalt-59 chemical shift and quadrupolar tensors of simple octahedral cobalt(III) complexes

2001 ◽  
Vol 79 (3) ◽  
pp. 296-303
Author(s):  
Christopher W Kirby ◽  
William P Power
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
Principal Components ◽  
Solid State Nmr ◽  
Nmr Spectra ◽  
Line Shapes ◽  
Quadrupolar Coupling ◽  
Molecular Frame ◽  
Specific Ligand

Analysis of the solid-state powder 59Co NMR spectra of ten simple inorganic cobalt(III) complexes at 11.75, and in most cases, 4.7 T have permitted the assignment of specific ligand planes to ranges of values of the observed chemical shift principal components. The relevant chemical shift components were determined from the simulations of the powder line shapes. These simulations also provided the relative orientations of the chemical shift (CS) and electric field gradient (efg) tensors, as well as magnitude and asymmetry of the 59Co quadrupolar coupling. Using symmetry arguments and ab initio calculations, as appropriate or necessary, the orientations of the efg tensors in the molecular frame were deduced. This allowed the determination of the CS tensors in the molecular frame and thus assignment of the ligand planes responsible for the observed values of chemical shifts.Key words: cobalt, chemical shift, quadrupolar coupling, solid state NMR.

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