The spinel Li[Mn2]O4 is a candidate cathode for a Li-ion battery, but its capacity fades over a charge/discharge cycle of Li1–x[Mn2]O4 (0 < x < 1) that is associated with a loss of Mn to the organic-liquid electrolyte. It is known that the disproportionation reaction 2Mn3+ = Mn2+ + Mn4+ occurs at the surface of a Mn spinel, and it is important to understand the atomic structure and composition of the surface of Li[Mn2]O4 in order to understand how Mn loss occurs. We report a study of the surface reconstruction of Li[Mn2]O4 by aberration-corrected scanning transmission electron microscopy. The atomic structure coupled with Mn-valence and the distribution of the atomic ratio of oxygen obtained by electron energy loss spectroscopy reveals a thin, stable surface layer of Mn3O4, a subsurface region of Li1+x[Mn2]O4 with retention of bulk Li[Mn2]O4. This observation is compatible with the disproportionation reaction coupled with oxygen deficiency and a displacement of surface Li+ from the Mn3O4 surface phase. These results provide a critical step toward understanding how Mn is lost from Li[Mn2]O4, once inside a battery.

Five membrane-electrode assemblies (MEAs) with different average sizes of platinum (Pt) nanoparticles (2.2, 3.5, 5.0, 6.7, and 11.3 nm) in the cathode were analyzed before and after potential cycling (0.6 to 1.0 V, 50 mV/s) by transmission electron microscopy. Cathodes loaded with 2.2 and 3.5 nm catalyst nanoparticles exhibit the following changes during electrochemical cycling: (i) substantial broadening of the size distribution relative to the initial size distribution, (ii) presence of coalesced particles within the electrode, and (iii) precipitation of submicron-sized particles with complex shapes within the membrane. In contrast, cathodes loaded with 5.0, 6.7, and 11.3 nm size catalyst nanoparticles are significantly less prone to the aforementioned effects. As a result, the electrochemically active surface area (ECA) of MEA cathodes loaded with 2.2 and 3.5 nm nanoparticle catalysts degrades dramatically within 1000 cycles of operation, while the electrochemically active surface area of MEA cathodes loaded with 5.0, 6.7, and 11.3 nm nanoparticle catalysts appears to be stable even after 10 000 cycles. The loss in MEA performance for cathodes loaded with 2.2 and 3.5 nm nanoparticle catalysts appears to be due to the loss in electrochemically active surface area concomitant with the observed morphological changes in these nanoparticle catalysts.

Lithium-rich layered Li[Li1/3−2x/3Mn2/3−x/3Nix]O2 (0 < x ≤ 1/2) oxide cathodes show promise as a potential candidate for Li-ion batteries due to their high capacity. However, the intricacies of the role of composition with increasing excess Li on the degree of oxygen loss during the first charge and the discharge capacity in subsequent cycles are not fully understood. With an aim to develop a better fundamental understanding, we present here an in-depth investigation of the Li[Li1/3−2x/3Mn2/3−x/3Nix]O2 (0 < x ≤ 1/2) series with a range of different excess lithium contents prepared by two different synthesis methods. The oxygen loss from the lattice during the first charge and the discharge capacity in subsequent cycles increase with increasing lithium content. In-depth analysis with a combination of X-ray diffraction, scanning electron microscopy (SEM), aberration-corrected scanning transmission electron microscopy (STEM), diffraction-STEM (D-STEM), and energy dispersive X-ray spectroscopy (EDS) reveals that the samples transition from an Rm structure to a C2/m structure with increasing lithium content and decreasing nickel to manganese ratio, for both the synthesis methods, indicating that the maximum oxygen loss and discharge capacity are achieved with a single C2/m phase. We further show that within a single particle, the cation layers of these materials can order on different {111} planes in the basic NaCl structure.

In this work, in situ transmission electron microscopy heating has been used to investigate the effects of a carbon capping layer on sintering of silver nanoparticles. For the first time, we make direct and real-time measurements of surface diffusivity of silver in nanoparticles coated with carbon. We observe that the carbon surface coatings may significantly inhibit sintering in silver nanoparticles.

Pt3Co nanoparticles are used to promote the oxygen reduction kinetics and increase the efficiency of proton exchange membrane (PEM) fuel cells. For the first time, aberration-corrected scanning transmission electron microscopy (STEM), STEM image simulations, and DFT calculations are combined to provide insight into the origin of enhanced catalysis of Pt3Co nanoparticles. Acid-leached nanoparticles exhibit a solid-solution structure but heterogeneous composition, while heat-treated nanoparticles exhibit an ordered structure, except for the first three surface layers where Pt enrichment is observed.Keywords: aberration-corrected STEM; nanoparticles; PEM fuel cells; platinum-alloyed catalysts;

In situ heating experiments were performed in a transmission electron microscope (TEM) to monitor the thermal stability of silver nanoparticles. The sublimation kinetics from isothermal experiments on individual nanoparticles was used to assess the actual temperatures of the nanoparticles by considering the localized heating from the electron beam. For isolated nanoparticles, beam heating under normal TEM operating conditions was found to increase the temperature by tens of degrees. For nominally isothermal experiments, the observed sublimation temperatures generally decreased with decreasing particle size, in agreement with the predictions from the Kelvin equation. However, sublimation of smaller nanoparticles was often observed to occur in discrete steps, which led to faceting of the nanoparticles. This discrete behavior differs from that predicted by conventional theory as well as from experimental observations in larger nanoparticles where sublimation was continuous. A hypothesis that explains the mechanism for this size-dependent behavior is proposed.Keywords: in situ transmission electron microscopy; kinetics; nanoparticles; silver; sublimation

The deformation behavior of nanoparticles continues to be an exciting area for materials research. Typically, nanoparticles show a conspicuous lack of dislocations, even after significant deformation. Therefore, it has been suggested that dislocations cannot exist or/do not play a role on the deformation of nanoparticles. In situ TEM nanoindentation is a critical tool for addressing this issue because it allows for the deformation to be monitored in real time. In this article, we discuss some of the experimental needs and challenges for performing in situ nanoindentation TEM experiments on nanoparticles. In addition, we show both diffraction contrast and phase contrast in situ TEM nanoindentation experiments on silver nanoparticles with diameters below 50 nm. Evidence of the presence of dislocations was observed during deformation, but upon unloading dislocations disappeared.Highlights► In situ TEM nanoindentation experiments were performed on silver nanoparticles ranging from 10 nm to 35 nm. ► In situ TEM nanoindentation experiments were carried out under diffraction-contrast and phase-contrast. ► Under diffraction-contrast conditions, contrast bands appear in the nanoparticle upon nanoindentation. However, whether these contrast bands are bend contours or dislocations remain unconfirmed. ► Under phase-contrast conditions, dislocations were observed to appear within the nanoparticle upon nanoindentation. ► Upon removal of the nanoindentation holder, dislocations disappear, which is due to the fact that they unstable in nanoparticles below a critical size.

Li[Li0.2Ni0.2Mn0.6]O2, which is a cathode material for Li-ion batteries with enhanced capacity, has been examined, for the first time, with a combination of aberration-corrected scanning transmission electron microscopy (STEM), STEM computer simulations, and diffraction scanning transmission electron microscopy (D-STEM). These techniques, in combination with X-ray diffraction (XRD) and conventional electron diffraction (ED), indicate that this material is composed of a solid solution with C2/m monoclinic symmetry and multiple planar defects. In addition, we show that XRD and ED alone can give misleading information and cannot resolve the structure of these materials without the additional use of the aforementioned techniques.Keywords: characterization tools; Li-ion batteries; nanostructures;

An ultra-fine-grained AISI 301LN austenitic stainless steel has been achieved by heavy cold rolling, to induce the formation of martensite, and subsequent annealing at 800 °C, 900 °C, and 1000 °C, from 1 to 100 seconds. The microstructural evolution was analyzed using transmission electron microscopy and the yield strength determined by tension testing. Ultra-fine austenite grains, as small as ∼0.54 μm, were obtained in samples annealed at 800 °C for 1 second. For these samples, tensile tests revealed a very high yield strength of ∼700 MPa, which is twice the typical yield strength of conventional fully annealed AISI 301LN stainless steels. An analysis of the relationship between yield strength and grain size in these submicron-grained stainless steels indicates a classical Hall–Petch behavior. Furthermore, when the yield dependence on annealing temperature is considered, the results show that the Hall–Petch relation is due to an interplay between fine-grained austenite, solid solution strengthening, precipitate hardening, and strain hardening.

The magnetically driven shape memory effect in Ni2MnGa body-centered tetragonal martensite is onset by the motion of 0.144 〈1 1 1〉 type twin dislocations on the {1 1 2} type planes. Calculations show that the application of a 400 kA/m magnetic field can induce a shear stress of approximately 2.8 MPa on these twin dislocations, a value exceeding the Peierls and the yield stress for Ni2MnGa.

•Dominant degradation mechanism of Pt3Co catalysts on realistic MEAs is revealed.•New mechanisms for the coalescence of the nanocatalysts are proposed and validated.•Particle dissolution rather than particle migration has a critical role in the coalescence.•Composition and morphology of the nanocatalysts throughout the cathode are analyzed.Pt3CoPt3Co catalyst nanoparticles of 4.9 nm size present on the cathode side of a PEMFC membrane-electrode assembly (MEA) were analyzed by transmission electron microscopy after 10 K voltage cycles under different operating conditions. The operating conditions include baseline (0.4–0.95 V, 80° C, 100% Relative Humidity (RH)), high potential (0.4–1.05 V, 80° C, 100% RH), high temperature (0.4–0.95 V, 90° C, 100% RH), and low humidity (0.4–0.95 V, 80° C, 30% RH). Particle growth and particle loss to the membrane is more severe in the high potential sample than in the high temperature and baseline MEAs, while no significant particle growth and particle precipitation in the membrane can be observed in the low humidity sample. Particles with different morphologies were seen in the cathode including: 1-Spherical individual particles resulting from modified electro-chemical Ostwald ripening and 2-aggregated and coalesced particles resulting from either necking of two or more particles or preferential deposition of Pt between particles with consequent bridging. The difference in the composition of these morphologies results in composition variations through the cathode from cathode/diffusion media (DM) to the cathode/membrane interface.

In this work, in situ transmission electron microscopy heating has been used to investigate the effects of a carbon capping layer on sintering of silver nanoparticles. For the first time, we make direct and real-time measurements of surface diffusivity of silver in nanoparticles coated with carbon. We observe that the carbon surface coatings may significantly inhibit sintering in silver nanoparticles.

Lithium-rich layered Li[Li1/3−2x/3Mn2/3−x/3Nix]O2 (0 < x ≤ 1/2) oxide cathodes show promise as a potential candidate for Li-ion batteries due to their high capacity. However, the intricacies of the role of composition with increasing excess Li on the degree of oxygen loss during the first charge and the discharge capacity in subsequent cycles are not fully understood. With an aim to develop a better fundamental understanding, we present here an in-depth investigation of the Li[Li1/3−2x/3Mn2/3−x/3Nix]O2 (0 < x ≤ 1/2) series with a range of different excess lithium contents prepared by two different synthesis methods. The oxygen loss from the lattice during the first charge and the discharge capacity in subsequent cycles increase with increasing lithium content. In-depth analysis with a combination of X-ray diffraction, scanning electron microscopy (SEM), aberration-corrected scanning transmission electron microscopy (STEM), diffraction-STEM (D-STEM), and energy dispersive X-ray spectroscopy (EDS) reveals that the samples transition from an Rm structure to a C2/m structure with increasing lithium content and decreasing nickel to manganese ratio, for both the synthesis methods, indicating that the maximum oxygen loss and discharge capacity are achieved with a single C2/m phase. We further show that within a single particle, the cation layers of these materials can order on different {111} planes in the basic NaCl structure.