A Solid-State Battery Cathode with a Polymer Composite Electrolyte and Low Tortuosity Microstructure by Directional Freezing and Polymerization

Solid‐state Li metal batteries (SSLMBs) combine improved safety and high specific energy that can surpass current Li ion batteries. However, the Li^{+} ion diffusivity in a composite cathode—a combination of active material and solid‐state electrolyte (SSE)—is at least an order of magnitude lower than that of the SSE alone because of the highly tortuous ion transport pathways in the cathode. This lowers the realizable capacity and mandates relatively thin (30–300 μm) cathodes, and hence low overall energy storage. Here, a thick (600 μm) hybrid cathode comprising vertically aligned LiNi_{0.8}Mn_{0.1}Co_{0.1}O_{2} (NMC811)‐rich channels filled with a [LiTFSI+PEGMA+MePrPyl TFSI] polymer composite electrolyte is fabricated by an innovative directional freezing and polymerization method. X‐ray micro‐computed tomography, ion mobility simulations, and DC depolarization show that the cathode structure improves Li^{+} ion diffusivity in the cathode from 4.4 × 10^{-9} to 1.4 × 10^{-7} cm^{2} s^{−1}. In a SSLMB full cell at 25 oC, the cathode provides gravimetric capacities of 199 and 120 mAh g^{−1}, and ultra‐high areal capacities of 16.7 and 10.1 mAh cm^{−2} at 0.05 and 1 C, respectively. The work demonstrates a scalable approach to realizing composite cathode structures with kinetically favorable ion transport characteristics in SSLMBs

Revealing hot tear formation dynamics in Al–Cu alloys with X-ray radiography

Hot tears can arise during the late part of alloy solidification because of the shrinkage of isolated liquid as it turns to solid and may have a catastrophic effect on cast tensile properties. Although there are correlations to suggest alloy hot tear sensitivity to casting conditions, they do not capture the influence of microstructure on tearing, such as second-phase particles or intermetallic compounds (IMCs) commonly present in engineering alloys. We use in situ X-ray radiography to quantify the formation and growth behaviour of hot tears in Al-5Cu and Al-5Cu-1Fe alloys during solidification. An automated hot tear detection, tracking and merging algorithm is developed and applied to reveal the role of Fe-rich IMC particles, typical of recycled alloys, on hot tear behaviour. These defects are termed hot tears here on the basis of their complex, extended inter-connected morphology, distinct from more rounded shrinkage porosity. We also visualise and quantify the velocity of interdendritic flow driven by solidification shrinkage, and estimate the pressure changes due to shrinkage. Hot tearing starts at lower solid fraction when IMCs are present due to reduced interdendritic flow, and hot tear formation is more spatially homogeneous, less clustered and more numerous. We show that the largest, most damaging hot tears form from many merging events, that is enhanced by the presence of IMCs

Active Metamaterials with Negative Static Electric Susceptibility

Although well‐established textbook arguments suggest that static electric susceptibility χ(0) must be positive in “all bodies,” it has been pointed out that materials that are not in thermodynamic equilibrium are not necessarily subject to this restriction. Media with inverted populations of atomic and molecular energy levels have been predicted theoretically to exhibit a χ(0) < 0 state, however the systems envisioned require reduced temperature, reduced pressure, and an external pump laser to maintain the population inversion. Further, the existence of χ(0) < 0 has never been confirmed experimentally. Here, a completely different approach is taken to the question of χ(0) < 0 and a design concept to achieve “true” χ(0) < 0 is proposed based on active metamaterials with internal power sources. Two active metamaterial structures are fabricated that, despite still having their power sources implemented externally for reasons of practical convenience, provide evidence in support of the general concept. Effective values are readily achieved at room temperature and pressure and are tunable throughout the range of stability −1 < χ(0) < 0, resulting in experimentally‐determined magnitudes that are over one thousand times greater than those predicted previously. Since χ(0) < 0 is the missing electric analog of diamagnetism, this work opens the door to new technological capabilities such as stable electrostatic levitation

3D Imaging of Lithium Protrusions in Solid‐State Lithium Batteries using X‐Ray Computed Tomography

Solid‐state lithium batteries will revolutionize the lithium‐ion battery and energy storage applications if certain key challenges can be resolved. The formation of lithium‐protrusions (dendrites) that can cause catastrophic short‐circuiting is one of the main obstacles, and progresses by a mechanism that is not yet fully understood. By utilizing X‐ray computed tomography with nanoscale resolution, the 3D morphology of lithium protrusions inside short‐circuited solid electrolytes has been obtained for the first time. Distinguishable from adjacent voids, lithium protrusions partially filled cracks that tended to propagate intergranularly through the solid electrolyte, forming a large waved plane in the shape of the grain boundaries. Occasionally, the lithium protrusions bifurcate into flat planes in a transgranular mode. Within the cracks themselves, lithium protrusions are preferentially located in regions of relatively low curvature. The crack volume filled with lithium in two samples is 82.0% and 83.1%, even though they have distinctly different relative densities. Pre‐existing pores in the solid electrolyte, as a consequence of fabrication, can also be part‐filled with lithium, but do not have a significant influence on the crack path. The crack/lithium‐protrusion behavior qualitatively supports a model of propagation combining electrochemical and mechanical effects

The Role of Grain Refiner in the Nucleation of AlFeSi Intermetallic Phases During Solidification of a 6xxx Aluminum Alloy

© 2019, The Author(s). Primary grain refinement using inoculant additions and intermetallic compound (IMC) phase selection are critical aspects in the solidification of commercial aluminum alloys, controlling the final mechanical properties in service. Although there have been studies which suggest there are explicit interactions between the two phenomena, they have yet to be fully elucidated. Here, through study of intermetallic phase particles extracted from an inoculated casting, key features relating to the nucleation of different intermetallic phases via eutectic reactions are recognized and explained. In particular, rake-like IMCs are identified as initiation points for the deleterious β-AlFeSi IMC phase in a model 6xxx series Al alloy. A mechanism is proposed for how TiB 2 inoculant particles, which are commonly used for primary phase refinement, play a role in enhancing the nucleation of intermetallic phases during eutectic reactions at the liquid/α-Al interface in the final stages of solidification. The implication of this mechanism is that, after the event of primary grain refinement, any unused TiB 2 inoculant particles could be contributing to IMC formation thereby affecting the overall type, size, and distribution of intermetallic phases in the solidified alloy.U.K. Engineering and Physical Sciences Research Counci

4D Bragg Edge Tomography of Directional Ice Templated Graphite Electrodes

Bragg edge tomography was carried out on novel, ultra-thick, directional ice templated graphite electrodes for Li-ion battery cells to visualise the distribution of graphite and stable lithiation phases, namely LiC12 and LiC6. The four-dimensional Bragg edge, wavelength-resolved neutron tomography technique allowed the investigation of the crystallographic lithiation states and comparison with the electrode state of charge. The tomographic imaging technique provided insight into the crystallographic changes during de-/lithiation over the electrode thickness by mapping the attenuation curves and Bragg edge parameters with a spatial resolution of approximately 300 µm. This feasibility study was performed on the IMAT beamline at the ISIS pulsed neutron spallation source, UK, and was the first time the 4D Bragg edge tomography method was applied to Li-ion battery electrodes. The utility of the technique was further enhanced by correlation with corresponding X-ray tomography data obtained at the Diamond Light Source, UK

Wandering behaviour prevents inter and intra oceanic speciation in a coastal pelagic fish

Small pelagic fishes have the ability to disperse over long distances and may present complex evolutionary histories. Here, Old World Anchovies (OWA) were used as a model system to understand genetic patterns and connectivity of fish between the Atlantic and Pacific basins. We surveyed 16 locations worldwide using mtDNA and 8 microsatellite loci for genetic parameters, and mtDNA (cyt b; 16S) and nuclear (RAG1; RAG2) regions for dating major lineage-splitting events within Engraulidae family. The OWA genetic divergences (0-0.4%) are compatible with intra-specific divergence, showing evidence of both ancient and contemporary admixture between the Pacific and Atlantic populations, enhanced by high asymmetrical migration from the Pacific to the Atlantic. The estimated divergence between Atlantic and Pacific anchovies (0.67 [0.53-0.80] Ma) matches a severe drop of sea temperature during the Gunz glacial stage of the Pleistocene. Our results support an alternative evolutionary scenario for the OWA, suggesting a coastal migration along south Asia, Middle East and eastern Africa continental platforms, followed by the colonization of the Atlantic via the Cape of the Good Hope.Portuguese Foundation for Science & Technology (FCT) [SFRH/BD/36600/2007]; FCT [UID/MAR/04292/2013, SFRH/BPD/65830/2009]; FCT strategic plan [UID/Multi/04326/2013]info:eu-repo/semantics/publishedVersio

Ultrasonic liquid metal processing: The essential role of cavitation bubbles in controlling acoustic streaming

The acoustic streaming behaviour below an ultrasonic sonotrode in water was predicted by numerical simulation and validated by experimental studies. The flow was calculated by solving the transient Reynolds-Averaged Navier-Stokes equations with a source term representing ultrasonic excitation implemented from the predictions of a nonlinear acoustic model. Comparisons with the measured flow field from Particle Image Velocimetry (PIV) water experiments revealed good agreement in both velocity magnitude and direction at two power settings, supporting the validity of the model for acoustic streaming in the presence of cavitating bubbles. Turbulent features measured by PIV were also recovered by the model. The model was then applied to the technologically important area of ultrasonic treatment of liquid aluminium, to achieve the prediction of acoustic streaming for the very first time that accounts for nonlinear pressure propagation in the presence of acoustic cavitation in the melt. Simulations show a strong dependence of the acoustic streaming flow direction on the cavitating bubble volume fraction, reflecting PIV observations. This has implications for the technological use of ultrasound in liquid metal processing

Till death (or an intruder) do us part: intrasexual-competition in a monogamous Primate

Polygynous animals are often highly dimorphic, and show large sex-differences in the degree of intra-sexual competition and aggression, which is associated with biased operational sex ratios (OSR). For socially monogamous, sexually monomorphic species, this relationship is less clear. Among mammals, pair-living has sometimes been assumed to imply equal OSR and low frequency, low intensity intra-sexual competition; even when high rates of intra-sexual competition and selection, in both sexes, have been theoretically predicted and described for various taxa. Owl monkeys are one of a few socially monogamous primates. Using long-term demographic and morphological data from 18 groups, we show that male and female owl monkeys experience intense intra-sexual competition and aggression from solitary floaters. Pair-mates are regularly replaced by intruding floaters (27 female and 23 male replacements in 149 group-years), with negative effects on the reproductive success of both partners. Individuals with only one partner during their life produced 25% more offspring per decade of tenure than those with two or more partners. The termination of the pair-bond is initiated by the floater, and sometimes has fatal consequences for the expelled adult. The existence of floaters and the sporadic, but intense aggression between them and residents suggest that it can be misleading to assume an equal OSR in socially monogamous species based solely on group composition. Instead, we suggest that sexual selection models must assume not equal, but flexible, context-specific, OSR in monogamous species.Wenner-Gren Foundation, L.S.B. Leakey Foundation, the National Geographic Society, National Science Foundation (BCS- 0621020), the University of Pennsylvania Research Foundation and the Zoological Society of San Diego, German Science Foundation (HU 1746-2/1