The desire for scalable energy storage technologies with higher specific energy densities has been intensified. Along with this, exploring and advancing new chemistries could provide alternatives to cobalt-based cathodes in sourcing and cost. Glass electrodes can have a capacity of 500 mAh/g and can be produced in facile melt quench procedures. In particular, many vanadate glasses have shown the improved performance compared to their crystalline counterparts. For examples, vanadate glass-based electrodes have exhibited increased capacity, better cycling stability and higher rate capability when compared to those of crystalline counterparts, V2O5 based cathodes. The improved performance in the glass system is primarily linked to the lack of irreversible loss that occurs from a crystalline phase changes which do not occur in amorphous materials. Many vanadate-modified glass systems have been investigated. However, a more detailed analysis of the effect of lithium borates and how they alter the glass system has not been carried out. Here we report our systematic studies on the effects of altering the content of lithium borate ratios on the modification of the boron coordination, and thus the formation of boron superstructures and non-bridging oxygen (NBO) sites. While the LiBO2-V2O5 system is reported as a promising high-performance cathode material, this glass system shows inconsistent glass formability in literature at high vanadium content, which is the electroactive species. An analysis of the effect of LiBO2 and Al2O3 on the vanadate glass system has been performed. X-ray photoelectron spectroscopy (V) and nuclear magnetic resonance (B-11) data show that alumina stabilizes and increases the BO3 coordinated species and decreases V4+ concentration which promotes VO4 chains to form with BO3 units, which is a stable glass structure according to literature. This is likely due to the [AlO4]- species, which requires charge compensation and reduces the amount of [BO4]- units that need to form. The lithium being attracted to the alumina structures likely limits how much lithium can then depolymerize the borovanadate glass network. The boron coordination changes and NBO sites that can be seen can also be related back to the rate capability, stability and performance of these glasses in electrochemical cells. More NBO sites means better ionic conduction and thus better rate capability and utilization of the active material. This extension of the borovanadate glass forming region, confirmed by various structural analysis, could improve the energy density of lithium batteries as well as offer viable alternatives to cobalt-based cathodes. Glass electrodes are a very promising alternative to traditional intercalation chemistries and warrant more exploration.