Abstract
The lithiated spinels LiyMg(Yb2)X4, X=S or Se and y approximately=0.8, have been compared with the parent spinels via the following physical measurements: electron paramagnetic resonance. AC and DC electrical conductivity, high-pressure electrical conductivity and magnetic susceptibility. The lithiated compounds are shown to be of mixed valence with a partially occupied Yb3+/2+:4f13/14 redox couple located well below the bottom of the Yb 5d conduction band. In contrast to intermediate-valence compounds, these mixed-valence compounds behave magnetically as their non lithiated analogues Mg(Yb2)X4, but with a dilution of the magnetic Yb3+:4f13 ion due to transfer of one electron per lithium ion to the host to create diamagnetic Yb2+:4f14 ions. The small-polaron motional enthalpy is Delta Hm<or=0.23 eV in LiyMg(Yb2)S4 and Delta Hm<or=0.14 eV in LiyMg(Yb2)Se.
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