A battery management system (BMS) plays a pivotal role in providing optimal performance of lithium-ion batteries (LIBs). However, the eventual malfunction of the BMS may lead to safety hazards or reduce the remaining useful life of LIBs. Manganese hexacyanoferrate (MnHCF) was employed as the positive electrode material in a Li-ion half-cell and subjected to five cycles at high current densities (10 A g$_{MnHCF}$$^{−1}$) and to discharge at 0.1 A g$_{MnHCF}$$^{−1}$, instead of classical charge/discharge cycling with initial positive polarization at 0.01 A g$_{MnHCF}$$^{−1}$, to simulate a current sensor malfunctioning and to evaluate the electrochemical and structural effects on MnHCF. The operando set of spectra at the Mn and Fe K-edges was further analyzed through multivariate curve resolution analysis with an alternating least squares algorithm (MCR–ALS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate the structural modifications arising during cycling after the applied electrochemical protocol. The coulombic efficiency in the first cycle was dramatically affected; however, the local structural environment around each photo absorber recovered during charging. The identification of an additional spectral contribution in the electrochemical process was achieved through MCR-ALS analysis, and the Mn-local asymmetry was thoroughly explored via EXAFS analysis.