Challenging Prevalent Solid Electrolyte Interphase (SEI) Models: An Atom Probe Tomography Study on a Commercial Graphite Electrode.

Lithium-ion batteries (LIBs) are the dominating energy storage technology for electric vehicles and portable electronic devices. Since the resources of raw materials for LIBs are limited and recycling technologies for LIBs are still under development, improvements in the long-term stability of LIBs are of paramount importance and, in addition, would lead to a reduction in the levelized cost of storage (LCOS). A crucial limiting factor is the aging of the solid electrolyte interphase (SEI) on the active material particles in the anode. Here, we demonstrate the potential of atom probe tomography for elucidating the complex mosaic-type structure of the SEI in a graphite composite anode. Our 3D reconstruction shows unseen details and reveals the existence of an apolar organic microphase pervading the SEI over its entire thickness. This finding is in stark contrast to the prevalent two-layer SEI model, in which organic compounds are the dominating species only in the outer SEI layer being in contact with the liquid electrolyte. The observed spatial arrangement of the apolar organic microphase promises a better understanding of the passivation capability of the SEI, which is necessary to expand the battery lifetime.

Characterization of Vegard strain related to exceptionally fast Cu-chemical diffusion in Cu[Formula: see text]Mo[Formula: see text]S[Formula: see text] by an advanced electrochemical strain microscopy method.

Electrochemical strain microscopy (ESM) has been developed with the aim of measuring Vegard strains in mixed ionic-electronic conductors (MIECs), such as electrode materials for Li-ion batteries, caused by local changes in the chemical composition. In this technique, a voltage-biased AFM tip is used in contact resonance mode. However, extracting quantitative strain information from ESM experiments is highly challenging due to the complexity of the signal generation process. In particular, electrostatic interactions between tip and sample contribute significantly to the measured ESM signals, and the separation of Vegard strain-induced signal contributions from electrostatically induced signal contributions is by no means a trivial task. Recently, we have published a compensation method for eliminating frequency-independent electrostatic contributions in ESM measurements. Here, we demonstrate the potential of this method for detecting Vegard strain in MIECs by choosing Cu[Formula: see text]Mo[Formula: see text]S[Formula: see text] as a model-type MIEC with an exceptionally high Cu chemical diffusion coefficient. Even for this material, Vegard strains are only measurable around and above room-temperature and with proper elimination of electrostatics. The analyis of the measured Vegards strains gives strong indication that due to a high charge transfer resistance at the tip/interface, the local Cu concentration variations are much smaller than predicted by the local Nernst equation. This suggests that charge transfer resistances have to be analyzed in more detail in future ESM studies.