To estimate the solid state diffusion coefficient of lithium in lithium intercalated carbon electrodes, a new model based upon the galvanostatic intermittent titration technique method was developed after a careful consideration of the models and methods used in the literature. The concept of constant phase element which was often used in the interpretation of ac impedance spectroscopy was introduced to account for the roughness of the electrode, leading to a model closer to the powder pellet electrode often used in lithium batteries. Diffusion coefficient of lithium in three kinds of carbon, i.e. pyrolytic poly(furfural alcohol), coke and mesophase carbon (1000C) were calculated by fitting the voltage response due to a constant low current perturbation with the new proposed model. The results were compared with those obtained according to an old model, which involved an ideal planar electrode. Introduction of the constant phase element led to an increase of two orders of magnitude in the D values. The D∼x (x in LixC6) and diffusion activation energy Ea ∼ x relationships were also obtained and were interpreted in terms of the structures of the carbons.

Diffusion of Lithium in Carbon. Liu, P., Wu, H.: Solid State Ionics, 1996, 92[1-2], 91-7