Correlation between Structural Features and Ionic Transport in Lithium-Ion Conducting Glass–Ceramics from the Li_1+<i>x</i>Cr<i>_x</i>GeTi_1–<i>x</i>(PO₄)₃ System

NASICON-structured glass–ceramics based on the Li1+xCrxGeTi1–x (PO4)3 (0 ≤ x 1) system are synthesized by melt-quenching method followed glass crystallization. Since Ti4+ and Cr3+ have approximately same crystal radius in octahedral coordination, this aliovalent substitution should avoid considerable changes cell volume, thus allowing us to evaluate true contribution of a tetravalent cation trivalent one other structural factors. The structure these is investigated X-ray high-resolution neutron diffraction while electrical properties accessed impedance spectroscopy. Fourier differences bond valence energy landscape analyses used determine additional Li position occupancies caused Cr3+. most important change features increase lithium content chemical formula occupation 36f partial depopulation 6b sites. Furthermore, grain-related ionic conductivity activation for conduction notably dependent substitution. correlations between two main findings discussed herein.