Since the advent of the transmission electron microscope (TEM), continuing efforts have been made to image material under native and reaction environments that typically involve liquids, gases, and external stimuli. With the advances of aberration-corrected TEM for improving the imaging resolution, steady progress has been made on developing methodologies that allow imaging under dynamic operating conditions, or in situ TEM imaging. The success of in situ TEM imaging is closely associated with advances in microfabrication techniques that enable manipulation of nanoscale objects around the objective lens of the TEM. This study summarizes and highlights recent progress involving in situ TEM studies of energy storage materials, especially rechargeable batteries. The study is organized to cover both the in situ TEM techniques and the scientific discoveries made possible by in situ TEM imaging.

X-ray and neutron diffraction are particularly useful for characterizing ferroelectric materials in situ, e.g., during application of temperature, pressure, electric field, and stress. In this review, we introduce many experimental approaches for such measurements and highlight important discoveries in ferroelectrics that utilized diffraction. We focus our examples on polycrystalline ferroelectrics, though many of the approaches and analysis methods can also be applied to thin films and single crystals. Methods discussed for characterization of structure include, phase identification, line profile analysis, whole pattern fitting, pair distribution functions, and the x-ray diffraction based three-dimensional microscopy. Further advancement of these and other techniques offers potential for continued important contributions to the fundamental understanding of ferroelectric materials.

Considerable interest in understanding interfacial phenomena occurring across nanostructured solid oxide fuel cell (SOFC) membrane electrode assemblies has increased demand for in situ characterization techniques with higher resolution. We briefly outline recent advancements in atomic force microscopy (AFM) instrumentation and subsystems in realizing real time imaging at high temperatures and ambient pressures, and the use of these in situ, multi-stimuli probes in collecting local information related to physical and fundamental processes. Here we demonstrate direct probing of local surface potential gradients related to the ionic conductivity of yttria-stabilized zirconia (YSZ) within symmetric SOFCs under intermediate operating temperatures (500–600 °C) via variable temperature scanning surface potential microscopy (VT-SSPM). The conductivity values obtained at different temperatures are then used to estimate the activation energy. These locally collected conductivity and activation energy values are subsequently compared to macroscopic electrochemical impedance results and bulk literature values, thus supporting the validity of the approach.

In this work, we report an experimental technique with nanometer resolution to reveal the microstructural mechanism for electric fatigue in ferroelectrics. The electric field in situ transmission electron microscopy (TEM) was used to directly visualize the domain evolution during the fatigue process in a 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 ceramic. The structure–property relationship was well demonstrated by combining the microscopic observations with corresponding dielectric, piezoelectric, and ferroelectric properties measured on bulk specimens. It was found that the domain switching capability was substantially suppressed after 103 cycles of bipolar fields, leading to an immobilized domain configuration thereafter. Correspondingly, a pronounced degradation of the functionality of the ceramic was manifested, accompanying with a coercive field bumping and polarization current density peak broadening. The reduction of the polarization, dielectric constant, and piezoelectric coefficient were found to follow a power-law relation. Seed inhibition mechanism was suggested to be responsible for the observed fatigue behaviors.

The dissimilar lattice-evolution of the isostructural layered Li(Ni,Co,Al)O2 (NCR) and Li(Ni,Co,Mn)O2 (CGR) cathodes in commercial lithium-ion batteries during overcharging/discharging was examined using operando neutron powder-diffraction. The stacking axis (c parameter) of both cathodes expands on initial lithiation and contracts on further lithiation. Although both the initial increase and later decrease are smaller for the CGR cathode, the overall change between battery charged and discharged states of the c parameter is larger for the CGR (1.29%) than for the NCR cathode (0.33%). We find these differences are correlated to the transition metal to oxygen bond (as measured through the oxygen positional-parameter) which is specific to the different cathode chemistries. Finally, we note the formation of and suggest a model for a LiCx intermediate between graphite and LiC12 in the anode of both batteries.

Designing materials for application as electrodes in sodium-ion batteries may require the use of unconventional materials to realize acceptable reversible sodium insertion/extraction capabilities. To design new materials simple electrochemical methods need to be coupled with other techniques such as in situ x-ray diffraction (XRD) to correlate the influence of electrochemical performance on a parameter that can be modified, e.g., the crystal structure of the material. Here we use in situ synchrotron XRD data on Gd2TiO5-containing cells to show the minor changes in reflection positions during discharge/charge that illustrates minimal volume expansion and contraction due to insertion/extraction reactions. These small changes correlate to the Gd2TiO5 anode material in both lithium- and sodium-ion batteries showing reversible capacities of ∼45 and ∼23 mA h/g after 20 cycles, respectively. Analysis of sodium location in the crystal structure shows a preference for sodium in the smaller channels along the c axis direction during the first discharge before moving to the larger channels at the charged state. Therefore, in this work, in situ studies highlight minimal structural changes with respect to volume expansion during electrochemical cycling and illustrate where sodium ions locate within the Gd2TiO5 structure.

Indentation-induced phase transformation processes were studied by in situ Raman imaging of the deformed contact region of silicon thin films, using a Raman spectroscopy-enhanced instrumented indentation technique (IIT). In situ Raman imaging was used to study the generation and evolution of the phase transformation of silicon while performing an IIT experiment analyzed to determine the average contact pressure and indentation strain. This is, to our knowledge, the first sequence of Raman images documenting the evolution of the strain fields and changes in the phase distributions of a material while conducting an indentation experiment. The reported in situ experiments provide insights into the transformation processes in silicon during indentation, confirming, and providing the experimental evidence for, some of the previous assumptions made on this subject. The developed Raman spectroscopy-enhanced IIT has shown its potential in advancing the understanding of deformation mechanisms and will provide a very useful tool in validating and refining contact models and related simulation studies.

Electrochemical reactions at both positive and negative electrodes in a nickel metal hydride (Ni-MH) battery during charge have been investigated by in situ neutron powder diffraction. Commercially available β-Ni(OH)2 and LaNi5-based powders were used in this experiment as positive and negative electrodes, respectively. Exchange of hydrogen by deuterium for the β-Ni(OH)2 electrode was achieved by ex situ cycling of the cell prior to in situ measurements. Neutron diffraction data collected in situ show that the largest amount of deuterium contained at the positive electrode is de-intercalated from the electrode with no phase transformation involved up to ∼100 mA h/g and, in addition, the 110 peak width for the positive electrode increases on charge. The negative electrode of composition MmNi3.6Al0.4Mn0.3Co0.7, where Mm = Mischmetal, exhibits a phase transformation to an intermediate hydride γ phase first and then to the β phase on charge. Unit cell dimensions and phase fractions have been investigated by Rietveld refinement of the crystal structure.

Operando energy-dispersive x-ray diffraction (EDXRD) was carried out on a newly formed 8 Ah lithium iron phosphate (LiFePO4) battery with the goal of elucidating the origin of asynchronous phase transformation commonly seen with in situ x-ray diffraction studies. The high-energy photons at the NSLS X17B1 beamline allow for penetration into a fully assembled battery and therefore negate any need for a specially designed in situ cell which often uses modified current collectors to minimize x-ray attenuation. Spatially-and-temporally resolved phase-mapping was conducted with a semiquantitative reference intensity ratio (RIR) analysis to estimate the relative abundance of the delithiated phase. The data show an asynchronous response in the stoichiometry versus the electrochemical profile and suggest limited diffusion in the electrode toward the end of discharge. Our results confirm that the asynchronous electrode response is not just limited to specially designed cells but occurs in fully assembled cells alike. We attribute this behavior to be a consequence of performing a local measurement over a wide-area heterogeneous reaction.

For understanding the atomic processes involved, in situ observation at near-atomic spatial resolution is needed in the studies of lithium ion battery materials. We show that the Li transport and the lithiation of carbon atoms may be triggered by the electron beam in an electron microscope, together with simultaneous real-time monitoring of electron energy-loss spectroscopy to reveal the chemical state of the species. The local electric field induced in an electrolyte particle by an electron beam acts on Li ions, resulting in Li transport and reaction with carbons. This process closely mimics the charging process of an electrochemical battery charge cycle, without an external power supply. We find that the lithium transport occurs in the form of Li+.

Microelectromechanical systems (MEMS) are increasingly at our fingertips. To understand and thereby improve their performance, especially given their ever-decreasing sizes, it is crucial to measure their functionality in situ. Atomic force microscopy (AFM) is well suited for such studies, allowing nanoscale lateral and vertical resolution of static displacements, as well as mapping of the dynamic response of these physically actuating microsystems. In this work, the vibration of a tuning fork based viscosity sensor is mapped and compared to model experiments in air, liquid, and a curing collagen gel. The switching response of a MEMS switch with nanosecond time-scale activation is also monitored – including mapping resonances of the driving microcantilever and the displacement of an overhanging contact structure in response to periodic pulsing. Such nanoscale in situ AFM investigations of MEMS can be crucial for enhancing modeling, design, and the ultimate performance of these increasingly important and sophisticated devices.

Many solar fuel generator designs involve illumination of a photoabsorber stack coated with a catalyst for the oxygen evolution reaction (OER). In this design, impinging light must pass through the catalyst layer before reaching the photoabsorber(s), and thus optical transmission is an important function of the OER catalyst layer. Many oxide catalysts, such as those containing elements Ni and Co, form oxide or oxyhydroxide phases in alkaline solution at operational potentials that differ from the phases observed in ambient conditions. To characterize the transparency of such catalysts during OER operation, 1031 unique compositions containing the elements Ni, Co, Ce, La, and Fe were prepared by a high throughput inkjet printing technique. The catalytic current of each composition was recorded at an OER overpotential of 0.33 V with simultaneous measurement of the spectral transmission. By combining the optical and catalytic properties, the combined catalyst efficiency was calculated to identify the optimal catalysts for solar fuel applications within the material library. The measurements required development of a new high throughput instrument with integrated electrochemistry and spectroscopy measurements, which enables various spectroelectrochemistry experiments.