LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) undergoes crystallographic and electronic changes when charging and discharging, which drive the cathode material close to or even beyond its stability window. To unravel the charge compensation mechanism of NCM622, spatially resolved atomic force microscopy (AFM) measurements in electrochemical strain microscopy (ESM) and conductive AFM (C-AFM) modes are obtained, and the spectroscopic information and crystallographic information are compared. All experiments are performed with two sets of samples: state-of-the-art samples that are composed of a binder, a conductive additive, and an active material and polished samples for single-particle analysis. Near-edge X-ray absorption fine structure spectroscopy shows that ionic Ni²⁺ reacts to give Ni³⁺ when charging and forms covalent bonds with its oxygen neighbors. A Ni²⁺/Ni³⁺ gradient across the particles balances out with the increasing state of charge, as verified by ESM. Therefore, the results also provide an important view that improves the mechanistic understanding of ESM in electrode materials. Finally, the interplay between the electronic and ionic conductivities and the crystallinities of NCM622 cathodes is elaborated and discussed.

Functional separators, which have additional functions apart from the ionic conduction and electronic insulation of conventional separators, are highly in demand to realize the development of advanced lithium ion secondary batteries with high safety, high power density, and so on. Their fabrication is simply performed by additional deposition of diverse functional materials on conventional separators. However, the hydrophobic wetting nature of conventional separators induces the polarity-dependent wetting feature of slurries. Thus, an eco-friendly coating process of water-based slurry that is highly polar is hard to realize, which restricts the use of various functional materials dispersible in the polar solvent. This paper presents a surface modification of conventional separators that uses a solution-based coating of graphene oxide with a hydrophilic group. The simple method enables the large-scale tuning of surface wetting properties by altering the morphology and the surface polarity of conventional separators, without significant degradation of lithium ion transport. On the surface modified separator, superior wetting properties are realized and a functional separator, applicable to lithium metal secondary batteries, is demonstrated as an example. We believe that this simple surface modification using graphene oxide contributes to successful fabrication of various functional separators that are suitable for advanced secondary batteries.