GITT Analysis of Lithium Insertion Cathodes for Determining the Lithium Diffusion Coefficient at Low Temperature: Challenges and Pitfalls

Understanding thermodynamic and kinetic properties of electrode materials for Li-ion batteries is of great importance for their optimization and development of novel materials and cell designs. The galvanostatic intermittent titration technique (GITT) is widely applied in battery research to study the state-of-charge (SOC) dependent kinetics of Li ion insertion. Low temperature diffusion and rate coefficients are hardly reported in the literature and can vary by orders of magnitude for identical active materials. Herein, we demonstrate and discuss challenges and pitfalls during the application and evaluation of GITT measurements for determining kinetic coefficients of Li-insertion electrodes, which becomming important at low temperatures. Including theoretical considerations and experimental analysis of the cathode material LiNi0.5Co0.2Mn0.3O2 (NCM523) in the temperature range of -40 to 40 °C. We show how the choice of experimental conditions for the GITT measurements and of the subsequent mathematical evaluation procedure to determine the lithium diffusion coefficient significantly influence the derived value of the diffusion coefficient. Simple calculation methods appear to be less suited the lower the temperature is. We outline that the proper estimation of the apparent Li ion chemical diffusion coefficient from GITT data requires an additional impedance analysis and a detailed knowledge of the cathode microstructure.