Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS.

The continuous demand for improved performance in energy storage is driving the evolution of Li-ion battery technology toward emerging battery architectures such as 3D all-solid-state microbatteries (ASB). Being based on solid-state ionic processes in thin films, these new energy storage devices require adequate materials analysis techniques to study ionic and electronic phenomena. This is key to facilitate their commercial introduction. For example, in the case of cathode materials, structural, electrical and chemical information must be probed at the nanoscale and in the same area, to identify the ionic processes occurring inside each individual layer and understand the impact on the entire battery cell. In this work, we pursue this objective by using two well established nanoscale analysis techniques namely conductive atomic force microscopy (C-AFM) and secondary ion mass spectrometry (SIMS). We present a platform to study Li-ion composites with nanometer resolution that allows one to sense a multitude of key characteristics including structural, electrical and chemical information. First, we demonstrate the capability of a biased AFM tip to perform field-induced ionic migration in thin (cathode) films and its diagnosis through the observation of the local resistance change. The latter is ascribed to the internal rearrangement of Li-ions under the effect of a strong and localized electric field. Second, the combination of C-AFM and SIMS is used to correlate electrical conductivity and local chemistry in different cathodes for application in ASB. Finally, a promising starting point towards quantitative electrochemical information starting from C-AFM is indicated.