Characterizing aging effects of lithium ion batteries by impedance spectroscopy

Impedance spectroscopy is one of the most promising methods for characterizing aging effects of portable secondary batteries online because it provides information about different aging mechanisms. However, application of impedance spectroscopy 'in the field' has some higher requirements than for laboratory experiments. It requires a fast impedance measurement process, an accurate model applicable with several batteries and a robust method for model parameter estimation. In this paper, we present a method measuring impedance at different frequencies simultaneously. We propose to use a composite electrode model, capable to describe porous composite electrode materials. A hybrid method for parameter estimation based on a combination of evolution strategy and Levenberg-Marquardt method allowed a robust and fast parameter calculation. Based on this approach, an experimental investigation of aging effects of a lithium ion battery was carried out. After 230 discharge/charge cycles, the battery showed a 14% decreased capacity. Modeling results show that series resistance, charge transfer resistance and Warburg coefficient changed thereby their values by approximately 60%. A single frequency impedance measurement, usually carried out at 1 kHz, delivers only information about series resistance. Impedance spectroscopy allows additionally the estimation of charge transfer resistance and Warburg coefficient. This fact and the high sensitivity of model parameters to capacity change prove that impedance spectroscopy together with an accurate modeling deliver information that significantly improve characterization of aging effects