Voltage relaxation and impedance spectroscopy as in-operando methods for the detection of lithium plating on graphitic anodes in commercial lithium-ion cells
By Stefan Schindler and Marius Bauer and Mathias Petzl and Michael A. Danzer
Published in Journal of Power Sources
2016
Abstract
In this study, voltage relaxation and impedance spectroscopy are introduced as in-operando methods for detecting lithium plating in commercial lithium-ion cells with graphitic anodes. Voltage relaxation is monitored subsequent to defined charge steps of variable amplitudes, charge throughputs, termination criteria and at different ambient temperatures yielding dependencies over a wide experimental parameter range. An adapted differential voltage analysis is presented to resolve the characteristic mixed potential evolving in case of plating. Impedance spectroscopy is applied in parallel to the relaxation phase to trace a possible alteration of the cell's impedance due to the concurrent depletion of reversibly deposited lithium. The introduced voltage differentials are shown to resolve the mixed potential with restrictions only for little charge throughputs. The comparison of voltage relaxation and already established stripping discharge reveals similarities of the underlying physicochemical processes and allows an estimate of the amount of deposited lithium in case of relaxation. In the evolution of the cell's impedance, a reversible shrinkage of the high frequency intersection resistance and the arc representing the anodic charge transfer process are identified as indicators towards plating. The presented methods solely rely on non-destructive measurement quantities and thus are fully suitable for the application in battery management systems.