State-of-charge of individual active material particles in lithium ion batteries: a perspective of analytical techniques and their capabilities

The state-of-charge (SOC) is an essential parameter for battery management systems to reflect and monitor the remaining capacity of individual battery cells. In addition to its application at the cell level, the SOC also plays an important role in the investigation of redox processes of cathode active materials (CAMs) in lithium ion batteries (LIBs) during electrochemical cycling. These processes can be influenced by a large variety of factors such as active material properties, inhomogeneities of the electrode, degradation phenomena and the charge/discharge protocol during cycling. Consequently, non-uniform redox reactions can occur, resulting in charge heterogeneities of the active material. This heterogeneity can translate into accelerated aging of the CAM and a reduction in reversible capacity of the battery cell, since the active material is not fully utilized. To understand and monitor the SOC heterogeneity at the mesoscale, a wide range of techniques have been implemented in the past. In this perspective an overview of current state-of-the-art techniques to evaluate charge heterogeneities of CAMs in LIBs is presented. Therefore, techniques which utilize synchrotron radiation like X-ray absorption near-edge structure (XANES) and transmission X-ray spectroscopy (TXM) are presented as well as Raman spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Next to these established techniques, classification single particle inductively coupled plasma optical emission spectroscopy (CL-SP-ICP-OES) as a new approach is also discussed in this perspective. For these techniques, the areas of application, advantages as well as drawbacks are highlighted and discussed. Schematic visualization of charge state heterogeneities within an electrode and their potential effects on the battery cell.