Novel lithium- and sodium-ion battery materials capable of high charge-discharge rates and storing large quantities of energy are increasingly of interest to modern society for use in devices, transportation and grid-based energy storage. Probing the electronic and magnetic structures of these materials provides a handle on their ability to fulfill the aforementioned properties; doing so in a non-invasive, even operando, manner is particularly important to obtain an accurate picture of their structures and properties. We employ first principles and statistical mechanics methods to understand the electronic and magnetic structures of these materials.