R. Stoyanova et al., NI3-NI2+ SEGREGATION IN LIXNI2-XO2 SOLID-SOLUTIONS (0.6-LESS-THAN-OR-EQUAL-TO-X-LESS-THAN-1)(), Solid state ionics, 73(1-2), 1994, pp. 1-7
EPR of low-spin Ni3+ ions is used to refine Ni3+-Ni2+ segregation in L
ixNi2-xO2 oxides with 0.6 less-than-or-equal-to x < 1 where a transfor
mation from cubic to layered structure occurs. It is shown that, above
the temperature of magnetic ordering, the spin-lattice relaxation com
prising phonon modulation of antiferromagnetic interplane Ni3+-O-Ni2and ferromagnetic intraplane Ni3+-O-Ni3+ interactions governs the line
ar temperature dependence of the EPR line width (DELTAH(pp)). The dDEL
TAH(pp)/dT coefficient can be used as a parametersensitive to the Ni2-Ni3+ segregation in neighbouring cubic (111) planes. For LixNi2-xO2 (
0.6 < x < 0.7), where Li+, Ni3+ and Ni2+ are approximately in the same
amounts, clustering of the Li+, Ni3+ and Ni2+ ions takes place in the
alternative (111) planes. For x > 0.7, Li+ and Ni3+ segregation evolv
e two discrete LiO2- and NiO2-layers, but a small part of Li+ and Ni3 fall into the ''alien'' layer. In addition, Ni2+ segregate into both
layers, their amount being almost equal when x > 0.7.