Electrochemical Techniques for Intercalation Electrode Materials in Rechargeable Batteries.

Understanding of the thermodynamic and kinetic properties of electrode materials is of great importance to develop new materials for high performance rechargeable batteries. Compared with computational understanding of physical and chemical properties of electrode materials, experimental methods provide direct and convenient evaluation of these properties. Often, the information gained from experimental work can not only offer feedback for the computational methods but also provide useful insights for improving the performance of materials. However, accurate experimental quantification of some properties can still be challenging. Among them, chemical diffusion coefficient is one representative example. It is one of the most crucial parameters determining the kinetics of intercalation compounds, which are by far the dominant electrode type used in rechargeable batteries. Therefore, it is of significance to quantitatively evaluate this parameter. For this purpose, various electrochemical techniques have been invented, for example, galvanostatic intermittent titration technique (GITT), potentiostatic intermittent titration technique (PITT), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). One salient advantage of these electrochemical techniques over other characterization techniques is that some implicit thermodynamic and kinetic quantities can be linked with the readily measurable electrical signals, current, and voltage, with very high precision. Nevertheless, proper application of these techniques requires not just an understanding of the structure and chemistry of the studied materials but sufficient knowledge of the physical model for ion transport within solid host materials and the analysis method to solve for chemical diffusion coefficient. Our group has been focusing on using various electrochemical techniques to investigate battery materials, as well as developing models for studying some emerging materials. In this Account, the principles of the aforementioned four electrochemical techniques and the corresponding analytical equations for calculating the chemical diffusion coefficients are first briefly summarized, followed by a discussion of the hidden assumptions for deriving these analytical equations and the resulting limitations in their implementation. To address these limitations, various corrections have been made in the literature. Nevertheless, the phase transition behavior, which is the typical feature for many intercalation materials, is barely considered. Here we retrospect our previous work on developing a two-phase model for describing the phase transition behavior of some intercalation compounds and discuss how to obtain the chemical diffusion coefficients based on the model, using LiFePO as an example material. After that, we have a discussion on the methodology for using electrochemical techniques to investigate new material features. It is our hope that this Account can serve as a call for more endeavors into the development of novel electrochemical tools for battery research.