Multiscale dynamics of charging and plating in graphite electrodes coupling operando microscopy and phase-field modelling.

The phase separation dynamics in graphitic anodes significantly affects lithium plating propensity, which is the major degradation mechanism that impairs the safety and fast charge capabilities of automotive lithium-ion batteries. In this study, we present comprehensive investigation employing operando high-resolution optical microscopy combined with non-equilibrium thermodynamics implemented in a multi-dimensional (1D+1D to 3D) phase-field modeling framework to reveal the rate-dependent spatial dynamics of phase separation and plating in graphite electrodes. Here we visualize and provide mechanistic understanding of the multistage phase separation, plating, inter/intra-particle lithium exchange and plated lithium back-intercalation phenomena. A strong dependence of intra-particle lithiation heterogeneity on the particle size, shape, orientation, surface condition and C-rate at the particle level is observed, which leads to early onset of plating spatially resolved by a 3D image-based phase-field model. Moreover, we highlight the distinct relaxation processes at different state-of-charges (SOCs), wherein thermodynamically unstable graphite particles undergo a drastic intra-particle lithium redistribution and inter-particle lithium exchange at intermediate SOCs, whereas the electrode equilibrates much slower at low and high SOCs. These physics-based insights into the distinct SOC-dependent relaxation efficiency provide new perspective towards developing advanced fast charge protocols to suppress plating and shorten the constant voltage regime.

Computer-Vision-Based Approach to Classify and Quantify Flaws in Li-Ion Electrodes.

X-ray computed tomography (X-ray CT) is a non-destructive characterization technique that in recent years has been adopted to study the microstructure of battery electrodes. However, the often manual and laborious data analysis process hinders the extraction of useful metrics that can ultimately inform the mechanisms behind cycle life degradation. This work presents a novel approach that combines two convolutional neural networks to first locate and segment each particle in a nano-CT LiNiMnCoO2 (NMC) electrode dataset, and successively classifies each particle according to the presence of flaws or cracks within its internal structure. Metrics extracted from the computer vision segmentation are validated with respect to traditional threshold-based segmentation, confirming that flawed particles are correctly identified as single entities. Successively, slices from each particle are analyzed by a pre-trained classifier to detect the presence of flaws or cracks. The models are used to quantify microstructural evolution in uncycled and cycled NMC811 electrodes, as well as the number of flawed particles in a NMC622 electrode. As a proof-of-concept, a 3-phase segmentation is also presented, whereby each individual flaw is segmented as a separate pixel label. It is anticipated that this analysis pipeline will be widely used in the field of battery research and beyond.

Stable Sodium-Metal Batteries in Carbonate Electrolytes Achieved by Bifunctional, Sustainable Separators with Tailored Alignment.

Sodium (Na) is the most appealing alternative to lithium as an anode material for cost-effective, high-energy-density energy-storage systems by virtue of its high theoretical capacity and abundance as a resource. However, the uncontrolled growth of Na dendrites and the limited cell cycle life impede the large-scale practical implementation of Na-metal batteries (SMBs) in commonly used and low-cost carbonate electrolytes. Herein, the employment of a novel bifunctional electrospun nanofibrous separator comprising well-ordered, uniaxially aligned arrays, and abundant sodiophilic functional groups is presented for SMBs. By tailoring the alignment degree, this unique separator integrates with the merits of serving as highly aligned ion-redistributors to self-orientate/homogenize the flux of Na-ions from a chemical molecule level and physically suppressing Na dendrite puncture at a mechanical structure level. Remarkably, unprecedented long-term cycling performances at high current densities (≥1000 h at 1 and 3 mA cm-2 , ≥700 h at 5 mA cm-2 ) of symmetric cells are achieved in additive-free carbonate electrolytes. Moreover, the corresponding sodium-organic battery demonstrates a high energy density and prolonged cyclability over 1000 cycles. This work opens up a new and facile avenue for the development of stable, low-cost, and safe-credible SMBs, which could be readily extended to other alkali-metal batteries.

Porous 3D graphene aerogel co-doped with nitrogen and sulfur for high-performance supercapacitors.

Heteroatom-doped carbon materials with a high specific area, a well-defined porous structure is important to high-performance supercapacitors (SCs). Here, S and N co-doped three-dimensional porous graphene aerogel (NS-3DPGHs) have been synthesized in a facile and efficient self-assembly process with thiourea acting as the reducing and doping agent solution. Operating as a SC electrode, fabricated co-doping graphene, i.e. the sample of NS-3DPGH-150 exhibits the highest specific capacitance of 412.9 F g-1 under 0.5 A g-1 and prominent cycle stabilization with 96.4% capacitance retention in the back of 10 000 cycles. Furthermore, based on NS-3DPGH-150, the symmetrical supercapacitor as-prepared in 6 M KOH displays a superior energy density of 12.9 Wh kg-1 under the power density of 249 W kg-1. Hence, NS-3DPGHs could be considered as an excellent candidate for SCs.

3D microstructure design of lithium-ion battery electrodes assisted by X-ray nano-computed tomography and modelling.

Driving range and fast charge capability of electric vehicles are heavily dependent on the 3D microstructure of lithium-ion batteries (LiBs) and substantial fundamental research is required to optimise electrode design for specific operating conditions. Here we have developed a full microstructure-resolved 3D model using a novel X-ray nano-computed tomography (CT) dual-scan superimposition technique that captures features of the carbon-binder domain. This elucidates how LiB performance is markedly affected by microstructural heterogeneities, particularly under high rate conditions. The elongated shape and wide size distribution of the active particles not only affect the lithium-ion transport but also lead to a heterogeneous current distribution and non-uniform lithiation between particles and along the through-thickness direction. Building on these insights, we propose and compare potential graded-microstructure designs for next-generation battery electrodes. To guide manufacturing of electrode architectures, in-situ X-ray CT is shown to reliably reveal the porosity and tortuosity changes with incremental calendering steps.

Tracking the evolution of a single composite particle during redox cycling for application in H2 production.

Composite materials consisting of metal and metal oxide phases are being researched intensively for various energy conversion applications where they are often expected to operate under redox conditions at elevated temperature. Understanding of the dynamics of composite evolution during redox cycling is still very limited, yet critical to maximising performance and increasing durability. Here we track the microstructural evolution of a single composite particle over 200 redox cycles for hydrogen production by chemical looping, using multi-length scale X-ray computed tomography. We show that redox cycling triggers a centrifugal redispersion of the metal phase and a centripetal clustering of porosity, both seemingly driven by the asymmetric nature of oxygen exchange in composites. Initially, the particle develops a large amount of internal porosity which boosts activity, but on the long term this facilitates structural and compositional reorganisation and eventually degradation. These results provide valuable insight into redox-driven microstructural changes and also for the design of new composite materials with enhanced durability.

The Imaging Resolution and Knudsen Effect on the Mass Transport of Shale Gas Assisted by Multi-length Scale X-Ray Computed Tomography.

The spatial resolution of 3D imaging techniques is often balanced by the achievable field of view. Since pore size in shales spans more than two orders of magnitude, a compromise between representativeness and accuracy of the 3D reconstructed shale microstructure is needed. In this study, we characterise the effect of imaging resolution on the microstructural and mass transport characteristics of shales using micro and nano-computed tomography. 3D mass transport simulation using continuum and numerical physics respectively is also compared to highlight the significance of the Knudsen effect on the reconstructed solid surface. The result shows that porosity measured by micro-CT is 25% lower than nano-CT, resulting in an overestimated pore size distribution and underestimated pore connectivity. This leads to a higher simulated intrinsic permeability. An overestimated diffusive flux and underestimated permeability are obtained from the continuum mass transport simulation compared to the numerical ones when the molecular-wall collision is accounted, evidenced by the large deviation of the measured Knudsen tortuosity factor and permeability correction factor. This study is believed to provide new knowledge in understanding the importance of imaging resolution and gas flow physics on mass transport in porous media.

Anisotropic crack propagation and deformation in dentin observed by four-dimensional X-ray nano-computed tomography.

Understanding the cracking behaviour of biological composite materials is of practical importance. This paper presents the first study to track the interplay between crack initiation, microfracture and plastic deformation in three dimensions (3D) as a function of tubule and collagen fibril arrangement in elephant dentin using in situ X-ray nano-computed tomography (nano-CT). A nano-indenter with a conical tip has been used to incrementally indent three test-pieces oriented at 0°, 45° and 70° to the long axis of the tubules (i.e. radial to the tusk). For the 0° sample two significant cracks formed, one of which linked up with microcracks in the axial-radial plane of the tusk originating from the tubules and the other one occurred as a consequence of shear deformation at the tubules. The 70° test-piece was able to bear the greatest loads despite many small cracks forming around the indenter. These were diverted by the microstructure and did not propagate significantly. The 45° test-piece showed intermediate behaviour. In all cases strains obtained by digital volume correlation were well in excess of the yield strain (0.9%), indeed some plastic deformation could even be seen through bending of the tubules. The hoop strains around the conical indenter were anisotropic with the smallest strains correlating with the primary collagen orientation (axial to the tusk) and the largest strains aligned with the hoop direction of the tusk. STATEMENT OF SIGNIFICANCE: This paper presents the first comprehensive study of the anisotropic nature of microfracture, crack propagation and deformation in elephant dentin using time-lapse X-ray nano-computed tomography. To unravel the interplay of collagen fibrils and local deformation, digital volume correlation (DVC) has been applied to map the local strain field while the crack initiation and propagation is tracked in real time. Our results highlight the intrinsic and extrinsic shielding mechanisms and correlate the crack growth behavior in nature to the service requirement of dentin to resist catastrophic fracture. This is of wide interest not just in terms of understanding dentin fracture but also can extend beyond dentin to other anisotropic structural composite biomaterials such as bone, antler and chitin.

Design of next-generation ceramic fuel cells and real-time characterization with synchrotron X-ray diffraction computed tomography.

Ceramic fuel cells offer a clean and efficient means of producing electricity through a variety of fuels. However, miniaturization of cell dimensions for portable device application remains a challenge, as volumetric power densities generated by readily-available planar/tubular ceramic cells are limited. Here, we demonstrate a concept of 'micro-monolithic' ceramic cell design. The mechanical robustness and structural integrity of this design is thoroughly investigated with real-time, synchrotron X-ray diffraction computed tomography, suggesting excellent thermal cycling stability. The successful miniaturization results in an exceptional power density of 1.27 W cm-2 at 800 °C, which is among the highest reported. This holistic design incorporates both mechanical integrity and electrochemical performance, leading to mechanical property enhancement and representing an important step toward commercial development of portable ceramic devices with high volumetric power (>10 W cm-3), fast thermal cycling and marked mechanical reliability.

Effect of hydration and crack orientation on crack-tip strain, crack opening displacement and crack-tip shielding in elephant dentin.

OBJECTIVES: To quantify the extent of crack-tip plasticity, crack opening displacement (COD) and crack bridging for crack growth perpendicular (HAH) and parallel (RAR) to the tubules in elephant dentin under both hydrated and dry conditions to better understand their influence on intrinsic and extrinsic toughening during crack growth. METHODS: Compact tension test-pieces were prepared from a tusk of African elephant ivory. Crack-tip strain mapping and COD measurements by digital image correlation (DIC) technique were made under incremental loading and unloading of cracks for hydrated and dry dentin of different orientations. RESULTS: For the RAR test-piece the plastic zones were significantly larger in the hydrated condition compared to when dry. By contrast, the plastic strains in the HAH test-piece were negligible in both wet and dry conditions. In the RAR condition the crack front was broken up into overlapping longitudinal 'fingers' with crack bridging regions in between, the ligaments extending 400µm behind the crack front in the dry case. This could only be seen in 3D by X-ray CT. Extrinsic shielding reduces the crack-tip stresses by 52% and 40% for hydrated and dry RAR test-pieces respectively. No significant bridging was found in the HAH case. SIGNIFICANCE: For crack growth parallel to the tubules, collagen plasticity determines the intrinsic toughening, whereas microcracking from the tubules governs extrinsic shielding via ligament bridging, which is maintained further behind the crack in the hydrated case. For cracks grown perpendicular to the tubules, neither toughening mechanisms are significant.

A multi-site array for combined local electrochemistry and electrophysiology in the non-human primate brain.

BACKGROUND: Currently, the primary technique employed in circuit-level study of the brain is electrophysiology, recording local field or action potentials (LFPs or APs). However most communication between neurons is chemical and the relationship between electrical activity within neurons and chemical signaling between them is not well understood in vivo, particularly for molecules that signal at least in part by non-synaptic transmission. NEW METHOD: We describe a multi-contact array and accompanying head stage circuit that together enable concurrent electrophysiological and electrochemical recording. The array is small (<200 µm) and can be assembled into a device of arbitrary length. It is therefore well-suited for use in all major in vivo model systems in neuroscience, including non-human primates where the large brain and need for daily insertion and removal of recording devices places particularly strict demands on design. RESULTS: We present a protocol for array fabrication. We then show that a device built in the manner described can record LFPs and perform enzyme-based amperometric detection of choline in the awake macaque monkey. Comparison with existing methods Existing methods allow single mode (electrophysiology or electrochemistry) recording. This system is designed for concurrent, dual-mode recording. It is also the only system designed explicitly to meet the challenges of recording in non-human primates. CONCLUSIONS: Our system offers the possibility for conducting in vivo studies in a range of species that examine the relationship between the electrical activity of neurons and their chemical environment, with exquisite spatial and temporal precision.

Facile charge-displacement at silicon gives spaced-out reaction.

Adsorbates on metals, but not previously on semiconductors, have been observed to display long-range repulsive interactions. On metals, due to efficient dissipation, the repulsions are weak, typically on the order of 5 meV at 10 Å. On the 7×7 reconstruction of the Si(111) surface, charge transport through the surface has been demonstrated by others using charge injection by STM tips. Here we show that for both physisorbed brominated molecules, and for chemisorbed Br-atoms, induced charge-transfer in the Si(111)-7×7 surface can lead to a strong repulsive interaction between adsorbates, calculated as 200 meV at 13.4 Å. This large repulsive interaction must be channeled through the surface since it causes widely spaced "one-per-corner-hole" patterns of physisorption (three cases--directly observed here) and subsequent chemisorption (four cases observed). The patterns were observed by ultrahigh vacuum scanning tunneling microscopy for four different brominated hydrocarbon adsorbates; 1,2-dibromoethane, 1-bromopropane, 1-bromopentane, and bromobenzene, deposited individually on the surface. In every case, adsorbates were overwhelmingly more likely to be found singly than multiply adjacent to a corner-hole, constituting a distinctive pattern having a probability p = 7 × 10(-5) compared to a random distribution.

A reversible molecular switch based on pattern-change in chlorobenzene and toluene on a Si(111)-(7x7) surface.

A reversible molecular switch is proposed, based on an observed change in a physisorbed pattern of chlorobenzene or toluene at Si(111)-(7x7), from "triangles" to "circles". Electronic excitation, at an applied surface voltage of Vs = -2.0 V, caused molecular migration, by one atomic site, from under the tip (switch "off"). Thereafter, the adsorbate pattern reverted thermally from circles to triangles (switch "on") across a measured activation barrier of Ea = 0.3 eV for chlorobenzene and 0.2 eV for toluene.