The changes in K + for the 1 st full CV, starting from PW, are shown in Figure . Deintercalation of K + , as evidenced by the decrease in the step edge, clearly occurs in two stages and at the same potentials of 0.22V and 0.88V as seen from the current responses in the voltammogram. When observing the evolution of individual K + species, the stages that occur are the deintercalation of K + from within PW due to its oxidation to PB, and then further deintercalation from oxidation to BG. The evolution of specific K + environments associated with these framework structures can be directly correlated to redox features within a CV. Each deintercalation event is followed by further small and gradual losses in K + signal (i.e., poorly defined plateaus of K + concentration), which occur within the voltage windows of 0.4-0.8 V and 1.0 V charging cycle to 1.0 V discharge cycle. Analysis of the individual XANES components shows that this gradual loss of K + concentration between oxidation events is due to deintercalation of kinetically hindered K + from within PW and PB environments respectively. Furthermore, the sluggish deintercalation of K + from residual PB sites within the cathode is particularly apparent from the LCF of the normalized spectra (Figure ). Zampardi et al. noted that the deintercalation of K + from PB to BG can be sluggish in composite electrodes, corresponding to the slow K + evolution seen in the XANES. Interestingly, this kinetically hindered K + was hypothesized not to be an intrinsic property of PB but of the assembled electrode and associated electrostatic effects, as supported by the resent multiscale measurements by Unwin and co-workers using scanning electrochemical microscopy on LiMn 2 O 4 . The corresponding two step intercalation of K + during reduction of BG to PB, and then to PW, can also be directly observed from the increases in K + concentration and the evolution of K + environment. In contrast to oxidation, a clear plateau in K + concentration, and PB speciation, is observed between the two reduction events. The result suggests that the reduction process is more facile, with no residual intercalation being observed. Given that the total edge step intensity does not return to its initial value the apparent improvement in kinetics could be the consequence of poorly conductive intercalation sites seen during reduction not participating in the subsequent oxidation. Evidently, throughout the entire redox process of PB, K + acts as the predominant charge-balancing species through intercalation processes, with no clear discrepancies seen between this process and the recorded current response during cycling. It is important to note that the apparent loss of solvated K + associated with electrolyte when the sample is fully reduced to PW is likely an artifact of the analysis, as the PW standard XANES spectrum used in LCF analysis itself contained an electrolyte component.