State-of-Health Diagnosis of Lithium-Ion Batteries Using Nonlinear Frequency Response Analysis

Estimation of the State-of-Health (SOH) of Lithium-ion Batteries (LIBs) is commonly conducted using in-situ measurement methods, such as Incremental Capacity Analysis (ICA) and Differential Voltage Analysis (DVA) as well as impedance based techniques. In this study, we present an alternative method for SOH estimation: The nonlinear dynamic measurement method Nonlinear Frequency Response Analysis (NFRA) is shown to be able to estimate capacity fade of LIBs due to loss of active material. Capacity loss correlates with the quotient of the root mean square of the second and the third harmonic response for different excitation amplitudes in the frequency range sensitive to electrochemical reactions at approximately 1 Hz. The results of the experimental cycle-aging study are validated and further analyzed by using a reaction model containing Butler-Volmer kinetics with a dynamic charge balance of the electrode. Simulations show that the NFR quotient and capacity fade due to loss of specific surface area correlate exactly. We identify the NFR quotient as a reliable, easily measurable parameter for the diagnosis of the SOH of LIBs. Therefore, this study reveals a novel approach for SOH estimation of LIBs based on dynamic analysis with NFRA.