Optical analysis has widely been used to capture macroscopic changes in the electrode and phase transitions can also be analyzed when color changes occur as shown in the graphite electrode [4]. Here we report phase transition behavior of LiFePO4 electrodes analyzed by color confocal optical system. Reaction distribution in the cross-section of the electrode was observed in operando. We also detected a metastable intermediate "LxFP", which is stabilized at low temperatures [5].
A layer of the LiFePO4 composite electrode, separator and lithium foil was cut and the cross-section was observed by color confocal optical system (ECCS B320, Lasertec Corporation) after the electrolyte was immersed. The reflective images of the electrode were recorded as a color video and the time changes of the whole (averaged) or local RGB brightness were compared with charge-discharge data. The blue brightness change (centered at 436 nm) can reasonably be correlated to the state of charge, with FePO4 having higher reflection intensity as shown in Fig. 1(a). At 0.1C at room temperature, the change occurred faster than the linear correlation, probably because the observed surface was filled with electrolyte and thus the reaction proceeded fast in the observed area under ion-transfer limitation conditions.
The inhomogeneity in the cross-sectional direction of the electrode was clearly observed in operando using the optical system. As shown in Fig. 1(b), the separator side reacted faster than the current collector side, in good agreement with the result analyzed by XAFS [3].
At a low temperature (-10 deg.), the sample in the fully charged state (FePO4) was able to be discharged only ca. 75%, which implies the slow kinetics of “LxFP” to form LiFePO4 [5]. The reflection intensity of “LxFP” was much lower than that at room temperature. When the temperature was increased to room temperature, the intensity was recovered to the originally observed value, suggesting the disproportionation of metastable “LxFP” to LiFePO4 and FePO4 [5]. These results clearly indicate that “LxFP” is optically captured as well as LiFePO4 and FePO4.
References
[1] K. Padhi et al., J. Electrochem. Soc., 144, 1188 (1997).
[2] H. Tanida et al., J. Phys. Chem. C, 120, 4739 (2016).
[3] Y. Orikasa et al., Sci. Rep., 6, 26382 (2016).
[4] P. Maire et al., J. Electrochem. Soc., 155, A862 (2008).