Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the ...Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. We discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.
Multimodal in-situ experiments are the wave of the future, as this approach will permit multispectral data collection and analysis during real-time nanoscale observation. In contrast, the evolution ...of technique development in the electron microscopy field has generally trended toward specialization and subsequent bifurcation into more and more niche instruments, creating a challenge for reintegration and backward compatibility for in-situ experiments on state-of-the-art microscopes. We do not believe this to be a requirement in the field; therefore, we propose an adaptive instrument that is designed to allow nearly simultaneous collection of data from aberration-corrected transmission electron microscopy (TEM), probe-corrected scanning transmission electron microscopy, ultrafast TEM, and dynamic TEM with a flexible in-situ testing chamber, where the entire instrument can be modified as future technologies are developed. The value would be to obtain a holistic understanding of the underlying physics and chemistry of the process-structure–property relationships in materials exposed to controlled extreme environments. Such a tool would permit the ability to explore, in-situ, the active reaction mechanisms in a controlled manner emulating those of real-world applications with nanometer and nanosecond resolution. If such a powerful tool is developed, it has the potential to revolutionize our materials understanding of nanoscale mechanisms and transients.
Graphical Abstract
Effective passivation of lithium metal surfaces, and prevention of battery-shorting lithium dendrite growth, are critical for implementing lithium metal anodes for batteries with increased power ...densities. Nanoscale surface heterogeneities can be “hot spots” where anode passivation breaks down. Motivated by the observation of lithium dendrites in pores and grain boundaries in all-solid batteries, we examine lithium metal surfaces covered with Li2O and/or LiF thin films with grain boundaries in them. Electronic structure calculations show that at >0.25 V computed equilibrium overpotential Li2O grain boundaries with sufficiently large pores can accommodate Li0 atoms which aid e– leakage and passivation breakdown. Strain often accompanies Li insertion; applying an ∼1.7% strain already lowers the computed overpotential to 0.1 V. Lithium metal nanostructures as thin as 12 Å are thermodynamically favored inside cracks in Li2O films, becoming “incipient lithium filaments”. LiF films are more resistant to lithium metal growth. The models used herein should in turn inform passivating strategies in all-solid-state batteries.
Carbonaceous materials have great potential for applications as anodes of alkali-metal ion batteries, such as Na-ion batteries and K-ion batteries (NIB and KIBs). We conduct an in situ study of the ...electrochemically driven sodiation and potassiation of individual carbon nanofibers (CNFs) by transmission electron microscopy (TEM). The CNFs are hollow and consist of a bilayer wall with an outer layer of disordered-carbon (d-C) enclosing an inner layer of crystalline-carbon (c-C). The d-C exhibits about three times volume expansion of the c-C after full sodiation or potassiation, thus suggesting a much higher storage capacity of Na or K ions in d-C than c-C. For the bilayer CNF-based electrode, a steady sodium capacity of 245 mAh/g is measured with a Coulombic efficiency approaching 98% after a few initial cycles. The in situ TEM experiments also reveal the mechanical degradation of CNFs through formation of longitudinal cracks near the c-C/d-C interface during sodiation and potassiation. Geometrical changes of the tube are explained by a chemomechanical model using the anisotropic sodiation/potassiation strains in c-C and d-C. Our results provide mechanistic insights into the electrochemical reaction, microstructure evolution and mechanical degradation of carbon-based anodes during sodiation and potassiation, shedding light onto the development of carbon-based electrodes for NIBs and KIBs.
Direct visualization of lead sulfide nanoparticle growth is demonstrated by selectively decomposing a chemical precursor from a multicomponent solution using in situ liquid transmission electron ...microscopy. We demonstrate reproducible control over growth mechanisms that dictate the final morphology of nanostructures while observing growth in real-time with subnanometer spatial resolution. Furthermore, while an intense electron beam can initiate nanoparticle growth, it is also shown that a laser can trigger the reaction independently of the imaging electrons.
Vacuum micro/nano-electronics can greatly benefit from the improved emission current density and temporal stability of the electron beam due to the morphological control and direct contact of cold ...field-emitters on a conducting substrate. In this work, high-performance vertically aligned carbon nanotube (VACNT) pillar-based field-emitter arrays (VACNT-P-FEAs) were synthesized directly on stainless-steel (SS) via plasma-enhanced chemical vapor deposition. Nanosphere lithography was employed to limit the growth sites of VACNTs and form VACNT-P-FEAs of different sizes on the SS substrate. The field emission (FE) properties of the VACNT-P-FEAs were dependent on the size of the pillar emitters. Remarkable FE properties, such as low turn-on electric field (ETo = 1.57 V/μm), low threshold electric field (ETh = 2.94 V/μm), high field enhancement factor (β = 4977), and high emission current density (∼33 mA/cm2 at a field of 4 V/μm) were observed from the VACNT-P-FEAs grown using polystyrene microspheres (450 nm diameter) for lithography. The excellent FE performance can be ascribed to the inherent properties of the sample, such as the high conductivity of the SS substrate, low contact resistance between the SS substrate and VACNTs, the suitable number of active VACNT pillar field-emitters, and the reduced screening effect between the VACNT pillars.
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We report a new hybrid integration scheme that offers for the first time a nanowire-on-lead approach, which enables independent electrical addressability, is scalable, and has superior spatial ...resolution in vertical nanowire arrays. The fabrication of these nanowire arrays is demonstrated to be scalable down to submicrometer site-to-site spacing and can be combined with standard integrated circuit fabrication technologies. We utilize these arrays to perform electrophysiological recordings from mouse and rat primary neurons and human induced pluripotent stem cell (hiPSC)-derived neurons, which revealed high signal-to-noise ratios and sensitivity to subthreshold postsynaptic potentials (PSPs). We measured electrical activity from rodent neurons from 8 days in vitro (DIV) to 14 DIV and from hiPSC-derived neurons at 6 weeks in vitro post culture with signal amplitudes up to 99 mV. Overall, our platform paves the way for longitudinal electrophysiological experiments on synaptic activity in human iPSC based disease models of neuronal networks, critical for understanding the mechanisms of neurological diseases and for developing drugs to treat them.
Vertically aligned carbon nanotube (VACNT) emitters were synthesized directly on stainless steel substrate using DC plasma-enhanced chemical vapor deposition. Remarkable field emission (FE) ...properties, such as low turn-on electric field (
E
TO
= 1.40 V/μm) and low threshold electric field (
E
TH
= 2.31 V/μm), were observed from VACNT arrays with long length and moderate density. The FE performance was significantly enhanced by a uniquely bundled structure of VACNTs formed through a simple water treatment process. The FE properties of VACNTs were further improved by coating the exterior of CNTs with a uniform layer of crystalline SnO
2
nanoparticles; the
E
TO
and
E
TH
were reduced to 1.18 and 2.01 V/μm, respectively. The enhancement of FE properties by SnO
2
coating can be attributed to the morphological change of VACNTs caused by the solution phase coating process. The coated samples also exhibited an improved FE stability which is attributed to the enhancement of the mechanical strength and chemical stability of the VACNTs after the SnO
2
coating. The VACNT emitters with characteristic features such as a conductive substrate, low contact resistance between the VACNTs and the substrate, uniform coating, and bundled morphology can be ideal candidates for FE devices.
We employed an in situ electrochemical cell in the transmission electron microscope (TEM) together with ex situ time-of-flight, secondary-ion mass spectrometry (TOF-SIMS) depth profiling, and ...FIB–helium ion scanning microscope (HIM) imaging to detail the structural and compositional changes associated with Na/Na+ charging/discharging of 50 and 100 nm thin films of Sb. TOF-SIMS on a partially sodiated 100 nm Sb film gives a Na signal that progressively decreases toward the current collector, indicating that sodiation does not proceed uniformly. This heterogeneity will lead to local volumetric expansion gradients that would in turn serve as a major source of intrinsic stress in the microstructure. In situ TEM shows time-dependent buckling and localized separation of the sodiated films from their TiN-Ge nanowire support, which is a mechanism of stress-relaxation. Localized horizontal fracture does not occur directly at the interface, but rather at a short distance away within the bulk of the Sb. HIM images of FIB cross sections taken from sodiated half-cells, electrically disconnected, and aged at room temperature, demonstrate nonuniform film swelling and the onset of analogous through-bulk separation. TOF-SIMS highlights time-dependent segregation of Na within the structure, both to the film-current collector interface and to the film surface where a solid electrolyte interphase (SEI) exists, agreeing with the electrochemical impedance results that show time-dependent increase of the films’ charge transfer resistance. We propose that Na segregation serves as a secondary source of stress relief, which occurs over somewhat longer time scales.