The combination of techniques provides an overall picture a relatively stable HC-cathode with a small but notable loss of long-range order over cycling, and a LC-PB cathode that undergoes rapid degradation through loss of PB short-range order and formation of non-conductive ferrihydrite. The analysis provides an understanding of differences in framework electrochemical properties and associated bulk structural changes, though further work is necessary to provide information on the K + charge carrier speciation and evolution during charge/discharge cycling.