Abstract: As the demand for higher-performance batteries has increased, so has the body of research on theoretical high-capacity anode materials. However, the research has been hindered because the high-capacity anode material properties and interactions are not well understood, largely due to the difficulty of observing cycling in situ. Using electrochemical scanning transmission electron microscopy (ec-STEM), we report the real-time observation and electrochemical analysis of pristine tin (Sn) and titanium dioxide-coated Sn (TiO2@Sn) electrodes during lithiation/delithiation. As expected, we observed a volume expansion of the pristine Sn electrodes during lithiation, but we further observed that the expansion was followed by Sn detachment from the current collector. Remarkably, although the TiO2@Sn electrodes also exhibited similar volume expansion during lithiation, they showed no evidence of Sn detachment. We found that the TiO2 surface layer acted as an electrochemically activated artificial solid-electrolyte interphase that serves to conduct Li ions. As a physical coating, it mechanically prevented Sn detachment following volume changes during cycling, providing significant degradation resistance and 80% Coulombic efficiency for a complete lithiation/delithiation cycle. Interestingly, upon delithiation, TiO2@Sn electrode displayed a self-healing mechanism of small pore formation in the Sn particle followed by agglomeration into several larger pores as delithiation continued. Graphical abstract: [Figure not available: see fulltext.]
Lithium metal is considered the “holy grail” material to replace typical Li-ion anodes due to the absence of a host structure coupled with a high theoretical capacity. The absence of a host structure results in large volumetric changes when lithium is electrodeposited/dissolved, making the lithium prone to stranding and parasitic reactions with the electrolyte. Lithium research is focused on enabling highly reversible lithium electrodeposition/dissolution, which is important to achieving long cycle life. Understanding the various mechanisms of self-discharge is also critical for realizing practical lithium metal batteries but is often overlooked. In contrast to previous work, it is shown here that self-discharge via galvanic corrosion is negligible, particularly when lithium is cycled to relevant capacities. Rather, the continued electrochemical cycling of lithium metal results in self-discharge when periodic rest is applied during cycling. The extent of self-discharge can be controlled by increasing the capacity of plated lithium, tuning electrolyte chemistry, incorporating regular rest, or introducing lithiophilic materials. Finally, the Coulombic losses that occur during periodic rest are largely reversible, suggesting that the dominant self-discharge mechanism in this work is not an irreversible chemical process but rather a morphological process.
Lithium-metal anodes can theoretically enable 10x higher gravimetric capacity than conventional graphite anodes. However, Li-metal anode cycling has proven difficult due to porous and dendritic morphologies, extensive parasitic solid electrolyte interphase reactions, and formation of dead Li. We systematically investigate the effects of applied interfacial pressure on Li-metal anode cycling performance and morphology in the recently developed and highly efficient 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane electrolyte. We present cycling, morphology, and impedance data at a current density of 0.5 mA/cm2 and a capacity of 2 mAh/cm2 at applied interfacial pressures of 0, 0.01, 0.1, 1, and 10 MPa. Cryo-focused ion beam milling and cryo-scanning electron microscopy imaging in cross section reveal that increasing the applied pressure during Li deposition from 0 to 10 MPa leads to greater than a fivefold reduction in thickness (and therefore volume) of the deposited Li. This suggests that pressure during cycling can have a profound impact on the practical volumetric energy density for Li-metal anodes. A “goldilocks zone” of cell performance is observed at intermediate pressures of 0.1–1 MPa. Increasing pressure from 0 to 1 MPa generally improves cell-to-cell reproducibility, cycling stability, and Coulombic efficiency. However, the highest pressure (10 MPa) results in high cell overpotential and evidence of soft short circuits, which likely result from transport limitations associated with increased pressure causing local pore closure in the separator. All cells exhibit at least some signs of cycling instability after 50 cycles when cycled to 2 mAh/cm2 with thin 50 μm Li counter electrodes, though instability decreases with increasing pressure. In contrast, cells cycled to only 1 mAh/cm2 perform well for 50 cycles, indicating that capacity plays an important role in cycling stability.
The dramatic 50% improvement in energy density that Li-metal anodes offer in comparison to graphite anodes in conventional lithium (Li)-ion batteries cannot be realized with current cell designs because of cell failure after a few cycles. Often, failure is caused by Li dendrites that grow through the separator, leading to short circuits. Here, we used a new characterization technique, cryogenic femtosecond laser cross sectioning and subsequent scanning electron microscopy, to observe the electroplated Li-metal morphology and the accompanying solid electrolyte interphase (SEI) into and through the intact coin cell battery's separator, gradually opening pathways for soft-short circuits that cause failure. We found that separator penetration by the SEI guided the growth of Li dendrites through the cell. A short-circuit mechanism via SEI growth at high current density within the separator is provided. These results will inform future efforts for separator and electrolyte design for Li-metal anodes.
Abstract: 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: [Figure not available: see fulltext.].
The development of solid-state batteries has encountered a number of problems due to the complex interfacial contact conditions between lithium (Li) metal and solid electrolytes (SEs). Recent experiments have shown that applying stack pressure can ameliorate these problems. Here, we report a multi-scale three-dimensional time-dependent contact model for describing the Li-SE interface evolution under stack pressure. Our simulation considers the surface roughness of the Li and SEs, Li elastoplasticity, Li creep, and the Li metal plating/stripping process. Consistency between the very recent experiments from two different research groups indicates effective yield strength of the Li used in those experiments of 16 ± 2 MPa. We suggest that the preferred stack pressure be at least 20 MPa to maintain a relatively small interface resistance while reducing void volume.
Zachman, Michael Z.; de Jonge, Niels d.; Fischer, Robert F.; Perea, Daniel P.; Jungjohann, Katherine L.
We report new cryogenic characterization techniques for exploring the nanoscale structure and chemistry of intact solid–liquid interfaces have recently been developed. These techniques provide high-resolution information about buried interfaces from large samples or devices that cannot be obtained by other means. These advancements were enabled by the development of instrumentation for cryogenic focused ion beam liftout, which allows intact solid–liquid interfaces to be extracted from large samples and thinned to electron-transparent thicknesses for characterization by cryogenic scanning transmission electron microscopy or atom probe tomography. Future implementation of these techniques will complement current strides in imaging of materials in fluid environments by in situ liquid-phase electron microscopy, providing a more complete understanding of the morphology, surface chemistry, and dynamic processes that occur at solid–liquid interfaces.
Mitigating corrosion remains a daunting challenge due to localized, nanoscale corrosion events that are poorly understood but are known to cause unpredictable variations in material longevity. Here, the most recent advances in liquid-cell transmission electron microscopy were employed to capture the advent of localized aqueous corrosion in carbon steel at the nanoscale and in real time. Localized corrosion initiated at a triple junction formed by a solitary cementite grain and two ferrite grains and then continued at the electrochemically-active boundary between these two phases. With this analysis, we identified facetted pitting at the phase boundary, uniform corrosion rates from the steel surface, and data that suggest that a re-initiating galvanic corrosion mechanism is possible in this environment. These observations represent an important step toward atomically defining nanoscale corrosion mechanisms, enabling the informed development of next-generation inhibition technologies and the improvement of corrosion predictive models.
Under the direction of the James W. Todd, Assistant Manager for Engineering within the National Nuclear Security Administration Sandia Field Office, the team listed above has performed the attached study to evaluate the vibration sensitivity of the Center for Integrated Nanotechnolog ies and propose possible mitigation strategies .
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.
Sukrittanon, Supanee; Liu, Ren; Breeden, Michael C.; Pan, Janet L.; Jungjohann, Katherine L.; Tu, Charles W.; Dayeh, Shadi A.
We report the demonstration of dilute nitride heterostructure core/shell microwire solar cells utilizing the combination of top-down reactive-ion etching to create the cores (GaP) and molecular beam epitaxy to create the shells (GaNP). Systematic studies of cell performance over a series of microwire lengths, array periods, and microwire sidewall morphologies examined by transmission electron microscopy were conducted to shed light on performance-limiting factors and to optimize the cell efficiency. We show by microscopy and correlated external quantum efficiency characterization that the open circuit voltage is degraded primarily due to the presence of defects at the GaP/GaNP interface and in the GaNP shells, and is not limited by surface recombination. Compared to thin film solar cells in the same growth run, the microwire solar cells exhibit greater short circuit current but poorer open circuit voltage due to greater light absorption and number of defects in the microwire structure, respectively. The comprehensive understanding presented in this work suggests that performance benefits of dilute nitride microwire solar cells can be achieved by further tuning of the epitaxial quality of the underlying materials.
Epitaxy-enabled bottom-up synthesis of self-assembled planar nanowires via the vapor-liquid-solid mechanism is an emerging and promising approach toward large-scale direct integration of nanowire-based devices without postgrowth alignment. Here, by examining large assemblies of indium tin oxide nanowires on yttria-stabilized zirconia substrate, we demonstrate for the first time that the growth dynamics of planar nanowires follows a modified version of the Gibbs-Thomson mechanism, which has been known for the past decades to govern the correlations between thermodynamic supersaturation, growth speed, and nanowire morphology. Furthermore, the substrate orientation strongly influences the growth characteristics of epitaxial planar nanowires as opposed to impact at only the initial nucleation stage in the growth of vertical nanowires. The rich nanowire morphology can be described by a surface-energy-dependent growth model within the Gibbs-Thomson framework, which is further modulated by the tin doping concentration. Our experiments also reveal that the cutoff nanowire diameter depends on the substrate orientation and decreases with increasing tin doping concentration. These results enable a deeper understanding and control over the growth of planar nanowires, and the insights will help advance the fabrication of self-assembled nanowire devices.
Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. Here, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge-discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Our results show that electrochemically induced solid-solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.
Advanced semiconductor devices often utilize structural and geometrical effects to tailor their characteristics and improve their performance. We report here detailed understanding of such geometrical effects in the epitaxial selective area growth of GaN on sapphire substrates and utilize them to enhance light extraction from GaN light emitting diodes. Systematic size and spacing effects were performed side-by-side on a single 2" sapphire substrate to minimize experimental sampling errors for a set of 144 pattern arrays with circular mask opening windows in SiO2. We show that the mask opening diameter leads to as much as 4 times increase in the thickness of the grown layers for 20 μm spacings and that spacing effects can lead to as much as 3 times increase in thickness for a 350 μm dot diameter. We observed that the facet evolution in comparison with extracted Ga adatom diffusion lengths directly influences the vertical and lateral overgrowth rates and can be controlled with pattern geometry. Such control over the facet development led to 2.5 times stronger electroluminescence characteristics from well-faceted GaN/InGaN multiple quantum well LEDs compared to non-faceted structures.
In this work, we demonstrate ∼2.05eV dilute nitride GaNP solar cells on GaP substrates for potential use as the top junction in dual-junction integrated cells on Si. By adding a small amount of N into indirect-bandgap GaP, GaNP has several extremely important attributes: a direct-bandgap that is also tunable, and easily attained lattice-match with Si. Our best GaNP solar cell ([N]∼1.8%, Eg∼2.05eV) achieves an efficiency of 7.9%, even in the absence of a window layer. This GaNP solar cell's efficiency is 3× higher than the most efficient GaP solar cell to date and higher than other solar cells with similar direct bandgap (InGaP, GaAsP). Through a systematic study of the structural, electrical, and optical properties of the device, efficient broadband optical absorption and enhanced solar cell performance are demonstrated.
Optical fluorescence-based DNA assays are commonly used for pathogen detection and consist of an optical substrate containing DNA capture molecules, binding of target RNA or DNA sequences, followed by detection of the hybridization event with a fluorescent probe. Though fluorescence detection can offer exquisite signal-to-background ratios, with high specificity, vast opportunities exist to improve current optical-based genomic sensing approaches. For these reasons, there is a clear need to explore alternative optical sensing paradigms to alleviate these restrictions. Bio-templated nanomaterial synthesis has become a powerful concept for developing new platforms for bio-sensing, as the biomolecule of interest can act as part of the sensing transducer mechanism. We explored the use of DNA origami structures to immobilize gold nanoparticles in very precise localized arrangements producing unique optical absorption properties with implications in novel DNA sensing schemes. We also explored the use of in-situ TEM as a novel characterization method for DNA-nanoparticle assemblies.
Janish, Matthew T.; Mackay, David T.; Liu, Yang; Jungjohann, Katherine L.; Carter, C.B.; Norton, M.G.
Materials such as tin (Sn) and silicon that alloy with lithium (Li) have attracted renewed interest as anode materials in Li-ion batteries. Although their superior capacity to graphite and other intercalation materials has been known for decades, their mechanical instability due to extreme volume changes during cycling has traditionally limited their commercial viability. This limitation is changing as processes emerge that produce nanostructured electrodes. The nanostructures can accommodate the repeated expansion and contraction as Li is inserted and removed without failing mechanically. Recently, one such nano-manufacturing process, which is capable of depositing coatings of Sn “nanoneedles” at low temperature with no template and at industrial scales, has been described. The present work is concerned with observations of the lithiation and delithiation behavior of these Sn nanoneedles during in situ experiments in the transmission electron microscope, along with a brief review of how in situ TEM experiments have been used to study the lithiation of Li-alloying materials. Individual needles are successfully lithiated and delithiated in solid-state half-cells against a Li-metal counter-electrode. The microstructural evolution of the needles is discussed, including the transformation of one needle from single-crystal Sn to polycrystalline Sn–Li and back to single-crystal Sn.
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.
Three-dimensional (3D) network structure has been envisioned as a superior architecture for lithium ion battery (LIB) electrodes, which enhances both ion and electron transport to significantly improve battery performance. Herein, a 3D carbon nano-network is fabricated through chemical vapor deposition of carbon on a scalably manufactured 3D porous anodic alumina (PAA) template. As a demonstration on the applicability of 3D carbon nano-network for LIB electrodes, the low conductivity active material, TiO2, is then uniformly coated on the 3D carbon nano-network using atomic layer deposition. High power performance is demonstrated in the 3D C/TiO2 electrodes, where the parallel tubes and gaps in the 3D carbon nano-network facilitates fast Li ion transport. A large areal capacity of ~0.37mAh·cm-2 is achieved due to the large TiO2 mass loading in the 60μm-thick 3D C/TiO2 electrodes. At a test rate of C/5, the 3D C/TiO2 electrode with 18nm-thick TiO2 delivers a high gravimetric capacity of ~240mAhg-1, calculated with the mass of the whole electrode. A long cycle life of over 1000 cycles with a capacity retention of 91% is demonstrated at 1C. The effects of the electrical conductivity of carbon nano-network, ion diffusion, and the electrolyte permeability on the rate performance of these 3D C/TiO2 electrodes are systematically studied.
This report documents work that was performed under the Laboratory Directed Research and Development project, Science of Battery Degradation. The focus of this work was on the creation of new experimental and theoretical approaches to understand atomistic mechanisms of degradation in battery electrodes that result in loss of electrical energy storage capacity. Several unique approaches were developed during the course of the project, including the invention of a technique based on ultramicrotoming to cross-section commercial scale battery electrodes, the demonstration of scanning transmission x-ray microscopy (STXM) to probe lithium transport mechanisms within Li-ion battery electrodes, the creation of in-situ liquid cells to observe electrochemical reactions in real-time using both transmission electron microscopy (TEM) and STXM, the creation of an in-situ optical cell utilizing Raman spectroscopy and the application of the cell for analyzing redox flow batteries, the invention of an approach for performing ab initio simulation of electrochemical reactions under potential control and its application for the study of electrolyte degradation, and the development of an electrochemical entropy technique combined with x-ray based structural measurements for understanding origins of battery degradation. These approaches led to a number of scientific discoveries. Using STXM we learned that lithium iron phosphate battery cathodes display unexpected behavior during lithiation wherein lithium transport is controlled by nucleation of a lithiated phase, leading to high heterogeneity in lithium content at each particle and a surprising invariance of local current density with the overall electrode charging current. We discovered using in-situ transmission electron microscopy that there is a size limit to lithiation of silicon anode particles above which particle fracture controls electrode degradation. From electrochemical entropy measurements, we discovered that entropy changes little with degradation but the origin of degradation in cathodes is kinetic in nature, i.e. lower rate cycling recovers lost capacity. Finally, our modeling of electrode-electrolyte interfaces revealed that electrolyte degradation may occur by either a single or double electron transfer process depending on thickness of the solid-electrolyte-interphase layer, and this cross-over can be modeled and predicted.
Wan, Jiayu W.; Bao, Wenzhong B.; Liu, Yang L.; Dai, Jiaqi D.; Shen, Fei S.; Zhou, Lihui Z.; Cai, Xinghan C.; Urban, Dan U.; Li, Yuanyuan L.; Jungjohann, Katherine L.; Fuhrer, Michael S.; Hu, Lianghing H.
For this study, a planar microbattery that enables various in situ measurements of lithiation of 2D materials on the individual-flake scale is developed. A large conductivity increase of thick MoS2 crystallite lithiation due to the formation of a percolative Mo nanoparticle network embedded in a Li2S matrix is observed. The nanoscale study leads to the development of a novel charging strategy for batteries that largely improves the capacity and cycling performance confirmed in bulk MoS2/Li coin cells.