Recently, attention has been given to the investigation of
glasses containing transition metal (TM) cations [1–6].
Several strategies have been used to design novel lithium
ion-conducting glasses. Lithium ion-conducting batteries
develop high-voltages and high-energy density due to their
lightweight and highly electropositive character of the
lithium metal [7]. Glasses with covalent networks often
tend to possess open structures and support high ionic
conductivities [8]. The investigation of the structure of such
materials is essential to obtain a better insight into the
structure–property relations. It is reported that lithium
borates form good glasses over a wide range of compositions
[9,10]. Some recent structural studies [11] show the
presence of BiO6 octahedra as the main structural unit in
the Bi2O3-based glasses containing Li+ions. Li+ions
occupy the interstices to compensate the excess negative
charge of BiO6 octahedra in low-alkali-content glasses,
whereas with high alkali content the replacement of some