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A lithium battery includes a cathode, a composite lithium metal anode, and an electrolyte in contact with the cathode and the composite lithium metal anode. The composite lithium metal anode includes a porous matrix and lithium metal disposed within the porous matrix.
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Paper submitted to ICONS '25
Gravity-driven convection induced in the liquid by density gradients of temperature or composition disrupts uniform dendritic growth during controlled directional solidification and promotes severe macrosegregation. The solute-rich region about the dendrite tip appears to play a pivotal role in channel initiation. Allen and Hunt referred to this region as an "initial transient" or dynamic region constituting steep concentration gradients. Experimental investigation also point to the role the tip region plays in developing microstructure. Hellawell and co-workers showed that flow-through dendritic channels could be effectively disrupted, and segregation minimized, during the gradient freezing of bulk castings by rotating the melt through a slight angle with respect to Earth's gravity vector. Adapting this principle to controlled directional solidification, it has been shown" that segregation in dendritic alloys can be minimized, and properties improved, by processing the sample near horizontal in conjunction with a slow axial rotation of the crucible. It is postulated that the observed microstructural uniformity arises by maintaining the developing solute field about the dendrite tip. Solute rejected during vertical directional solidification will rise or sink parallel to the primary dendrite arms during axial rotation setting the stage for accumulation, instabilities, and segregation. In contrast, during horizontal growth, the rejected solute will sink or rise perpendicular to the primary dendrite. Now, in the presence of a slight axial rotation, solute that was initially sinking (or rising) will find itself above (or below) its parent dendrite, i.e., still about the tip region. The following is intended to experimentally demonstrate the viability of this concept in coordination with a model that gives predictive insight regarding solute distribution about growing dendrites. Alloys based on the lead-tin eutectic system were used in this study. The system is well characterized, the constituent metals are available in a very pure form, and the thermophysical properties are well known. During solidification of hypoeutectic alloys, e.g., 55 wt pct Pb, the primary dendrites reject the less dense tin, and for the hypereutectic alloys, e.g., 75 wt pct Sn, the primary dendrites reject denser lead. Alloys were prepared by melting appropriate amounts of lead and tin in a glass crucible after which the homogeneous liquid was sucked directly into 5-mm i.d. glass tubes. The sample tube, containing approximately 30 cm of alloy, was then mechanically driven into the directional solidification furnace assembly and positioned such that approx. 20 cm of the sample was remelted. Subsequently, directional solidification was initiated by withdrawing the sample through a water-cooled jacket at a constant growth velocity of 2 ,microns/s. After 5 to 6 cm of growth, the sample was quickly removed from the furnace and quenched in a water bath to preserve the solid-liquid interface. Samples were directionally solidified vertically upward, nearly horizontally, and some in conjunction with an applied axial rotation of the crucible. Temperature gradients at the solid-liquid interface were measured with an in-siru K-type thermocouple. Solidified samples were cut perpendicular and parallel to the growth direction and conventionally prepared for microscopic examination.
Modeling solidification microstructures has become an area of intense study in recent years. The properties of large scale cast products, ranging from automobile engine blocks to aircraft components and other industrial applications, are strongly dependent on the physics that occur at the mesoscopic and microscopic length scales during solidification. The predominant morphology found in solidification microstructures is the dendrite, a tree-like pattern of solid around which solidification proceeds. The microscopic properties of cast products are determined by the length scales of these dendrites, and their associated segregation profiles. For this reason understanding the mechanisms for pattern selection in dendritic growth has attracted a great deal of interest from the experimental and theoretical communities. In particular, a great deal of research has been undertaken to understand such issues as dendrite morphology, shape and growth speed. Experiments on dendrite evolution in pure materials by Glicksman and coworkers on succinonitrile (SCN), and more recently pivalic acid (PVA), as well as other transparent analogs of metals, have provided tests of theories for dendritic growth, and have stimulated considerable theoretical progress. These experiments have clearly demonstrated that in certain parameter ranges the physics of the dendrite tip can be characterized by a steady value for the dendrite tip velocity, radius of curvature and shape. Away from the tip, the time-dependent dendrite exhibits a characteristic sidebranching as it propagates, which is not yet well understood. These experiments are performed by observing individual dendrites growing into an undercooled melt. The experiments are characterized by the dimensionless undercooling. Most experiments are performed at low undercooling.
Projections of the entorhinal cortex to the hippocampus are well known from the classical studies of Cajal (Ramon y Cajal, 1904) and Lorente de No (1933). Projections from the entorhinal cortex to neocortical areas are less well understood. Such connectivity is likely to underlie the consolidation of long-term declarative memory in neocortical sites. In the present study, a projection arising in layer V of the entorhinal cortex and terminating in a polymodal association area of the superior temporal gyrus has been identified with the use of retrograde tracing. The dendritic arbors of neurons giving rise to this projection were further investigated by cell filling and confocal microscopy with computer reconstruction. This analysis demonstrated that the dendritic arbor of identified projection neurons was largely confined to layer V, with the exception of a solitary, simple apical dendrite occasionally ascending to superficial laminae but often confined to the lamina dissecans (layer IV). Finally, immunoreactivity for glutamate-receptor subunit proteins GluR 5/6/7 of the dendritic arbor of identified entorhinal projection neurons was examined. The solitary apical dendrite of identified entorhinal projection neurons was prominently immunolabeled for GluR 5/6/7, as was the dendritic arbor of basilar dendrites of these neurons. The restriction of the large bulk of the dendritic arbor of identified entorhinal projection neurons to layer V implies that these neurons are likely to be heavily influenced by hippocampal output arriving in the deep layers of the entorhinal cortex. Immunoreactivity for GluR 5/6/7 throughout the dendritic arbor of such neurons indicates that this class of glutamate receptor is in a position to play a prominent role in mediating excitatory neurotransmission within hippocampal-entorhinal circuits.
Since significantly different solidification structures of a given alloy can be obtained by varying experimental growth rates, it is desirable to understand the basic factors which control the formation and stability of these microstructures when conditions are altered. Directional solidification experiments are described and the results obtained in metallic and transparent organic systems are presented. Emphasis is on the characteristics of dendritic structures obtained under different solidification conditions. Specifically, the effect of the growth rate on the primary dendritic spacing, the secondary dendrite spacing, and the dendrite tip radius is discussed. It is shown that significant changes in the primary spacing are observed when a dendrite to cellular transition takes place at lower velocities. It is found that the primary cellular spacing is much smaller than the primary dendrite spacing so that a maximum in the primary spacing occurs as a function of velocity at the dendrite-cellular transition. A theoretical model is also described which quantitatively explains various microstructural features of dendritic and cellular structures.
Four high-pressure gas tanks, the basis of this study, were especially made by a private contractor and tested before being delivered to NASA Kennedy Space Center. In order to insure 100% reliability of each individual tank the staff at KSC decided to again submit the four tanks under more rigorous tests. These tests were conducted during a period from April 10 through May 8 at KSC. This application further validates the predictive safety model for accident prevention and system failure in the testing of four high-pressure gas tanks at Kennedy Space Center, called Continuous Hazard Tracking and Failure Prediction Methodology (CHTFPM). It is apparent from the variety of barriers available for a hazard control that some barriers will be more successful than others in providing protection. In order to complete the Barrier Analysis of the system, a Task Analysis and a Biomechanical Study were performed to establish the relationship between the degree of biomechanical non-conformities and the anomalies found within the system on particular joints of the body. This relationship was possible to obtain by conducting a Regression Analysis to the previously generated data. From the information derived the body segment with the lowest percentage of non-conformities was the neck flexion with 46.7%. Intense analysis of the system was conducted including Preliminary Hazard Analysis (PHA), Failure Mode and Effect Analysis (FMEA), and Barrier Analysis. These analyses resulted in the identification of occurrences of conditions, which may be becoming hazardous in the given system. These conditions, known as dendritics, may become hazards and could result in an accident, system malfunction, or unacceptable risk conditions. A total of 56 possible dendritics were identified. Work sampling was performed to observe the occurrence each dendritic. The out of control points generated from a Weighted c control chart along with a Pareto analysis indicate that the dendritics "Personnel not Wearing Proper Protective and Hose/tubing located in high-traffic area" which account for 59.18% of total dendritic frequency need to be addressed to reduce the chance of a hazard from occurring. However, the occurrences of some dendritics are more important than others. As a result immediate, from a Weighted c perspective, corrective action should be taken to ameliorate the cause of the Class A dendritic "Personnel located under suspended or moving loads" rather than just the most commonly occurring dendritics. In any case the vast majority of data obtained indicates that testing operations possess a relatively high degree of safety.
Artificial neural networks comprising spiking neurons of a novel type have been conceived as improved pattern-analysis and pattern-recognition computational systems. These neurons are represented by a mathematical model denoted the state-variable model (SVM), which among other things, exploits a computational parallelism inherent in spiking-neuron geometry. Networks of SVM neurons offer advantages of speed and computational efficiency, relative to traditional artificial neural networks. The SVM also overcomes some of the limitations of prior spiking-neuron models. There are numerous potential pattern-recognition, tracking, and data-reduction (data preprocessing) applications for these SVM neural networks on Earth and in exploration of remote planets. Spiking neurons imitate biological neurons more closely than do the neurons of traditional artificial neural networks. A spiking neuron includes a central cell body (soma) surrounded by a tree-like interconnection network (dendrites). Spiking neurons are so named because they generate trains of output pulses (spikes) in response to inputs received from sensors or from other neurons. They gain their speed advantage over traditional neural networks by using the timing of individual spikes for computation, whereas traditional artificial neurons use averages of activity levels over time. Moreover, spiking neurons use the delays inherent in dendritic processing in order to efficiently encode the information content of incoming signals. Because traditional artificial neurons fail to capture this encoding, they have less processing capability, and so it is necessary to use more gates when implementing traditional artificial neurons in electronic circuitry. Such higher-order functions as dynamic tasking are effected by use of pools (collections) of spiking neurons interconnected by spike-transmitting fibers. The SVM includes adaptive thresholds and submodels of transport of ions (in imitation of such transport in biological neurons). These features enable the neurons to adapt their responses to high-rate inputs from sensors, and to adapt their firing thresholds to mitigate noise or effects of potential sensor failure. The mathematical derivation of the SVM starts from a prior model, known in the art as the point soma model, which captures all of the salient properties of neuronal response while keeping the computational cost low. The point-soma latency time is modified to be an exponentially decaying function of the strength of the applied potential. Choosing computational efficiency over biological fidelity, the dendrites surrounding a neuron are represented by simplified compartmental submodels and there are no dendritic spines. Updates to the dendritic potential, calcium-ion concentrations and conductances, and potassium-ion conductances are done by use of equations similar to those of the point soma. Diffusion processes in dendrites are modeled by averaging among nearest-neighbor compartments. Inputs to each of the dendritic compartments come from sensors. Alternatively or in addition, when an affected neuron is part of a pool, inputs can come from other spiking neurons. At present, SVM neural networks are implemented by computational simulation, using algorithms that encode the SVM and its submodels. However, it should be possible to implement these neural networks in hardware: The differential equations for the dendritic and cellular processes in the SVM model of spiking neurons map to equivalent circuits that can be implemented directly in analog very-large-scale integrated (VLSI) circuits.
The solidification mechanism and segregation behavior of laser-melted Mn 35 Fe 5 Co 20 Ni 20 Cu 20 was firstly investigated via in situ synchrotron x-ray diffraction at millisecond temporal resolution. The transient composition evolution of the random solid solution during sequential solidification of dendritic and interdendritic regions complicates the analysis of synchrotron diffraction data via any single conventional tool, such as Rietveld refinement. Therefore, a novel approach combining a hard-sphere approximation model, thermodynamic simulation, thermal expansion measurement and microstructural characterization was developed to assist in a fundamental understanding of the evolution of local composition, lattice parameter, and dendrite volume fraction corresponding to the diffraction data. This methodology yields self-consistent results across different methods. Via this approach, four distinct stages were identified, including: (I) FCC dendrite solidification, (II) solidification of FCC interdendritic region, (III) solid-state interdiffusion and (IV) final cooling with marginal diffusion. It was found out that in Stage I, Cu and Mn were rejected into liquid as Mn 35 Fe 5 Co 20 Ni 20 Cu 20 solidified dendritically. During Stage II, the lattice parameter disparity between dendrite and interdendritic region escalated as Cu and Mn continued segregating into the interdendritic region. After complete solidification, during Stage III, the lattice parameter disparity gradually decreases, demonstrating a degree of composition homogenization. The volume fraction of dendrites slightly grew from 58.3 to 65.5%, based on the evolving composition profile across a dendrite/interdendritic interface in diffusion calculations. Postmortem metallography further confirmed that dendrites have a volume fraction of 64.7 ± 5.3% in the final microstructure.
Abstract The drop freezing process is described by a phase-field model. Two cases are considered: when the freezing is triggered by central nucleation and when nucleation occurs on the drop surface. Depending on the environmental temperature and drop size, different morphological structures develop. Detailed dendritic growth was simulated at the first stage of drop freezing. Independent of the nucleation location, a decrease in temperature within the range from ~−5° to −25°C led to an increase in the number of dendrites and a decrease in their width and the interdendritic space. At temperatures lower than about −25°C, a planar front developed following surface nucleation, while dendrites formed a granular-like structure with small interdendritic distances following bulk nucleation. An ice shell grew in at the same time (but slower) as dendrites following surface nucleation, while it started forming once the dendrites have reached the drop surface in the case of central nucleation. The formed ice morphology at the first freezing stage predefined the splintering probability. We assume that stresses needed to break the ice shell arose from freezing of the water in the interdendritic spaces. Under this assumption, the number of possible splinters/fragments was proportional to the number of dendrites, and the maximum rate of splintering/fragmentation occurred within a temperature range of about −10° to −20°C, is in agreement with available laboratory and in situ measurements. At temperatures < −25°C, freezing did not lead to the formation of significant stresses, making splintering unlikely. The number of dendrites increased with drop size, causing a corresponding increase in the number of splinters. Examples of morphology that favors drop cracking are presented, and the duration of the freezing stages is evaluated. Sensitivity of the freezing process to the surface fluxes is discussed.
The dependence of microsegregation behavior on growth rate and thermal gradient has been examined in a Pb-8.4 at. pct Au alloy material partially directionally solidified and quenched. The composition of the quenched 'liquid' at the dendrite tip (Ct), that of the eutectic-like solid phase freezing from the interdendritic liquid at the base of dendrite (Cse), the volume fraction of this eutectic-like region (fe), and solute profiles in the interdendritic quenched liquid and ahead of the dendrite have been measured. Two dendritic growth models for solidification of a binary alloy melt in a positive thermal gradient at the liquid-solid interface, one for dendrites with 'minimum undercooled dendrite tip' and the other for an Ivantsov type of dendrite with 'marginally stable tip', have been examined for a quantitative comparison with measured values of Ct, Cse, and fe. Convection in the melt, possibly due to horizontal density gradients, is found to be a serious limitation for theoretical understanding of the observed experimental behavior and meaningful comparison of theories.
Liquid-solid interface distortion in the region of primary dendrite tips has been investigated in directionally solidified Pb-8 wt pct Au alloy. The distortions are caused by thermosolutal convection despite choice of growth conditions which should have been thermally and solutally stabilizing. The convection produces clustering of primary dendrites on a plane perpendicular to the growth direction. It produces a mushy zone, where the primary dendrites do not protrude with a uniform length, across the specimen cross section, resulting in large macrosegregation in the transverse direction. However, little macrosegregation is observed along the growth direction. The mushy zone, with uneven dendrite lengths, forms in the beginning of directional solidification. Its shape and dendrite distribution do not show much change during subsequent solidification. Tip morphologies of primary dendrites, within the dendrite clusters, appear to follow the morphological stability relationship.
This article reports research that has been carried out under the aegis of NASA as part of a collaboration between ESA and NASA for solidification experiments on the International Space Station (ISS). The focus has been on the effect of convection on the microstructural evolution and macrosegregation in hypoeutectic Al-Si alloys during directional solidification (DS). Terrestrial DS-experiments have been carried out at Cleveland State University (CSU) and under microgravity on the International Space Station (ISS). The thermal processing-history of the experiments is well defined for both the terrestrially processed samples and the ISS-processed samples. As of this writing, two dendritic metrics was measured: primary dendrite arm spacings and primary dendrite trunk diameters. We have observed that these dendrite-metrics of two samples grown in the microgravity environment show good agreements with models based on diffusion controlled growth and diffusion controlled ripening, respectively. The gravity-driven convection (i.e., thermosolutal convection) in terrestrially grown samples has the effect of decreasing the primary dendrite arm spacings and causes macrosegregation. Dendrite trunk diameters also show differences between the earth- and space-grown samples. In order to process DS-samples aboard the ISS, the dendritic seed crystals were partially remelted in a stationary thermal gradient before the DS was carried out. Microstructural changes and macrosegregation effects during this period are described and have modeled.
Primary dendrite spacings, secondary dendrite spacings, and microsegregation have been examined in PWA-1480 single crystal specimens which were directionally solidified during parabolic maneuvers on the KC-135 aircraft. Experimentally observed growth rate and thermal gradient dependence of primary dendrite spacings are in good agreement with predictions from dendrite growth models for binary alloys. Secondary dendrite coarsening kinetics show a reasonable fit with the predictions from an analytical model proposed by Kirkwood for a binary alloy. The partition coefficients of tantalum, titanium, and aluminum are observed to be less than unity, while that for tungsten and cobalt are greater than unity. This is qualitatively similar to the nickel base binaries. Microsegregation profiles experimentally observed for PWA-1480 superalloy show a good fit with Bower, Brody, and Flemings model developed for binary alloys. Transitions in gravity levels do not appear to affect primary dendrite spacings. A trend of decreased secondary arm spacings with transition from high gravity to the low gravity period was observed at a growth speed of 0.023 cm s(exp -1). However, definite conclusions can only be drawn by experiments at lower growth speeds which make it possible to examine the side-branch coarsening kinetics over a longer duration. Such experiments, not possible due to the insufficient low-gravity time of the KC-135, may be carried out in the low-gravity environment of space.
Reactive carbide precursor-based synthesis of NASICON-type NZSP (Na 1+x Zr 2 Si x P 3-x O 12 ) solid-state electrolyte (SSE) is demonstrated, in contrast to the established oxide-based approach. Exothermic decomposition of ZrC and SiC in air homogenizes microstructure, yielding 98% compact density after conventional sintering at 1200 °C. Quantitative stereology demonstrates that significant microstructural differences are present. Compacts of carbide-derived Carb-NZSP are 98% dense with a secondary zirconium oxide (ZrO 2 ) volume fraction of 0.2% ± 0.3%, versus 93% dense and 3% ± 1% for oxide-derived baseline. For Carb-NZSP, the secondary glassy phosphate phase is agglomerated, while for baseline, it is dispersed and percolated. Electrochemical testing combined with post-mortem analysis demonstrates how microstructural control of secondary phases is critical for dendrite suppression: Carb-NZSP critical current density (CCD) is 3.1 ± 0.8 mA cm −2 at 0.1 mAh cm −2 , versus 1.0 ± 0.7 mA cm −2 at 0.1 mAh cm −2 . Cryogenic focused ion beam (cryo-FIB) analysis demonstrates that in both materials, the porous 2D sheet-like sodium metal dendrites propagate around and subsume NZSP grains, likely following a path enriched with glassy phase and with porosity. Dendrites also flow around isolated zirconia particles. Phase field simulation reveals deflection of dendrites by mechanically tough zirconia, while brittle glassy phase accelerates dendrite growth, especially when finely distributed.
An in-situ electrochemical optical diagnosis is the key to the investigation of electrode interface during a redox reaction. Because the morphology changes particularly, dendrite formation, dendrite shapes, solid electrolyte interface formation and gas generation can be revealed visually. The challenge of ensuring uniform current density on a flat Li anode in a liquid electrolyte was addressed and uniform Li plating was demonstrated. The dendrite shape change under different reduction current density was discussed. Here the Li dendrite shape change and the performance of Li anodes with a surface lamination of graphite and red phosphate were used as examples to demonstrate the capability of the in-situ optical cell. An in-situ electrochemical optical cell used in the investigation of the increasingly popular solid-state Li batteries has its own challenges. Due to the untransparent nature of a solid-state electrolyte, an optical investigation on a solid-state electrolyte Li battery needs to be done by exposing the cross-section of the cell. In addition, it is very difficult to assemble an optical cell with a brittle and fragile solid-state electrolyte in a glove box. A set of formation and transfer dies, and an optical cell were introduced. The Li dendrite growth at the interface can be observed in a solid-state Li cell.