Quantitative and space-resolved in situ 1D EPR imaging for the detection of metallic lithium deposits

The ability to monitor lithium deposition on the anodes in real time is becoming progressively more important due to the development of advanced anode technology. Given the fact that the detrimental Li deposits are always on the micron scale, electron paramagnetic resonance (EPR) happens to be a very effective and selective detection technology due to the skin effect. Here, quantitative in situ 1D EPR imaging is carried out with a magnetic field gradient to achieve a one-dimensional spatial resolution along the Li growth direction in a capillary cell. The quantification of Li deposits is carefully calibrated using a 1,1-diphenyl-2-picrylhydrazyl standard, and a processing method is presented to correct the double integration of the Dysonian line from the metallic Li. The Li deposition processes are compared in two different electrolytes. For the electrolyte containing fluoroethylene carbonate (FEC) additive, the fitting results of Dysonian lines suggest that the plated Li has a larger dimension of the microstructure and the stripping proceeds more uniformly. It thus accounts for the higher Coulombic efficiency in the electrolyte with FEC. In situ EPR imaging also suggests that the Sand's capacity varies with the electrolytes. The forced growth of dendritic Li is carried out at a very large current density using a derivative operando EPR method to monitor the growth locus of the Li dendrites, indicating a tip-growing mechanism. This work can be instructive for those who are engaged in the study of electro-deposited lithium using in situ EPR imaging technology.