Li-6 and Al-27 MAS NMR and EPR of low-spin Ni3+ were used to study the loca
l environment of aluminium and the electronic structure of LiNi1-yAlyO2 sol
id solutions. The citrate precursor method was used to obtain layered Li1-y
AlyO2 with reproducible compositions. It has been found that Al additives f
avour the stabilization of both Ni3+ and the two-dimensionality of the crys
tal lattice and perturb the transition from a layered to a monoclinic struc
ture during lithium extraction. EPR of low-spin Ni3+ shows a more covalent
Ni3+-O2- bonding when Ni3+ is replaced by Al3+ in the NiO2, layer. In order
to improve the resolution of MAS NMR spectra, acid delithiated Li1-xNi1-yA
lyO2 were studied. The local environment of Al was assessed by comparing th
e observed chemical shifts for Li1-xNi1-yAlyO2 with that for isostructural
diamagnetic LiCo1-yAlyO2. Al-27 MAS NMR spectra demonstrate that, depending
on the total Al content, Al ions occupy non-octahedral or octahedral posit
ions. The ability of Al to fill non-octahedral sites is more pronounced for
LiCo1-yAlyO2 solid solutions. The stabilisation of Al in non-octahedral po
sitions in the trigonal crystal structure of LiCo/Ni1-yAlyO2 is discussed.
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