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Advancements in energy storage technologies such as Li-based batteries depend on a deep understanding of the chemical and structural aspects of critical interfaces. Among these, the solid electrolyte interphase (SEI) governs how batteries operate yet remains one of the most elusive to characterize due to its rapid degradation under an electron beam and sensitivity to ambient conditions. In recent years, cryogenic electron microscopy (cryo-EM) has emerged as a promising technique to provide atomic-resolution imaging of beam-sensitive battery materials. Distinct SEIs have been discovered with unique chemical compositions and structural features. In this perspective, the role of cryo-EM in uncovering the physicochemical properties of three classes of SEIs (i.e., compact, extended, and indirect SEI) will be defined and discussed. Furthermore, an in-depth analysis of new cryo-EM imaging modalities will be provided to highlight directions for the future development of cryo-EM.

Surface properties of electrode materials play a critical role in the function of batteries. Therefore, surface modifications, such as coatings, have been widely used to improve battery performance. Understanding how these coatings function to improve battery performance is crucial for both scientific research and applications. In this study the electrochemical performance of coated and uncoated LiNi0.5Mn1.5O4 (LNMO) electrodes is correlated with ensemble-averaged soft X-ray absorption spectroscopy (XAS) and spatially resolved scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) to illustrate the mechanism of how ultrathin layer Al2O3 coatings improve the cycle life of LiNi0.5Mn1.5O4. Mn2+ evolution on the surface is clearly observed in the uncoated sample, which results from the reaction between the electrolytic solution and the surfaces of LiNi0.5Mn1.5O4 particles, and also possibly atomic structure reconstructions and oxygen loss from the surface region in LiNi0.5Mn1.5O4. The coating effectively suppresses Mn2+ evolution and improves the battery performance by decelerating the impedance buildup from the surface passivation. This study demonstrates the importance of combining ensemble-averaged techniques (e.g., XAS) with localized techniques (e.g., STEM-EELS), as the latter may yield unrepresentative information due to the limited number of studied particles, and sheds light on the design of future coating processes and materials.

We report a microscopic study of p-GaAs/TiO2 heterojunctions using cross-sectional high resolution transmission electron microscopy (HRTEM). The photocatalytic performance for both H2 evolution and CO2 reduction of these heterostructures shows a very strong dependence on the thickness of the TiO2 over the range of 0-15 nm. Thinner films (1-10 nm) are amorphous and show enhanced catalytic performance with respect to bare GaAs. HRTEM images and electron energy loss spectroscopy (EELS) maps show that the native oxide of GaAs is removed by the TiCl4 atomic layer deposition (ALD) precursor, which is corrosive. Ti3+ defect states (i.e., O vacancies) in the TiO2 film provide catalytically active sites, which improve the photocatalytic efficiency. Density functional theory (DFT) calculations show that water molecules and CO2 molecules bind stably to these Ti3+ states. Thicker TiO2 films (15 nm) are crystalline and have poor charge transfer due to their insulating nature, while thinner amorphous TiO2 films are conducting.

Heterostructure devices with specific and extraordinary properties can be fabricated by stacking two-dimensional crystals. Cleanliness at the inter-crystal interfaces within a heterostructure is crucial for maximizing device performance. However, because these interfaces are buried, characterizing their impact on device function is challenging. Here, we show that electron-beam induced current (EBIC) mapping can be used to image interfacial contamination and to characterize the quality of buried heterostructure interfaces with nanometer-scale spatial resolution. We applied EBIC and photocurrent imaging to map photo-sensitive graphene-MoS2 heterostructures. The EBIC maps, together with concurrently acquired scanning transmission electron microscopy images, reveal how a device's photocurrent collection efficiency is adversely affected by nanoscale debris invisible to optical-resolution photocurrent mapping.