Ab initio modeling and experimental analysis of electronic conductivity in PEDOT:PSS-PEO films for extrusion-based manufacturing.

In this study, a combination of ab initio modeling and experimental analysis is presented to investigate and elucidate the electronic conductivity of films composed of conducting polymer blend PEDOT:PSS-PEO. Detailed density functional theory (DFT) calculations, aligned with experimental data, aided at profound understanding of the chemical composition, band structure, and the mechanical behavior of these composite materials. Systematic evaluation across diverse ratios of PEDOT, PSS, and PEO revealed a pronounced transformation in electronic properties. Specifically, the addition of PEO into the polymer matrix remarkably changes the band gap, with a marked alteration observed near a PEO concentration of 52 wt-%. This adjustment led to a substantial enhancement in the electrical conductivity, exhibiting an increase by a factor of approximately 20, compared to the original PEDOT:PSS polymer. The present investigation determined the crucial role of the PEDOT to PSS ratio in band gap determination, emphasizing its significant impact on the material's electrical conductivity. Concurrently, the mechanical property analysis unveiled a consistent increase in Young's modulus, reaching up to 765.93 MPa with increased PEO content, signifying a notable mechanical stiffening of the blend. The obtained combined theoretical and experimental insights illustrate a detailed perspective on the conductivity anomalies observed in PEDOT:PSS-PEO systems, establishing a robust framework for designing highly conducting and mechanically stable polymer blends. This comprehensive approach elucidates the interplay between chemical composition and electronic behavior, offering a strategic pathway for extrusion-based manufacturing techniques such as Direct Ink Writing (DIW).

A Smart Lithium Battery with Shape Memory Function.

Rapidly growing flexible and wearable electronics highly demand the development of flexible energy storage devices. Yet, these devices are susceptible to extreme, repeated mechanical deformations under working circumstances. Herein, the design and fabrication of a smart, flexible Li-ion battery with shape memory function, which has the ability to restore its shape against severe mechanical deformations, bending, twisting, rolling or elongation, is reported. The shape memory function is induced by the integration of a shape-adjustable solid polymer electrolyte. This Li-ion battery delivers a specific discharge capacity of ≈140 mAh g-1 at 0.2 C charge/discharge rate with ≈92% capacity retention after 100 cycles and ≈99.85% Coulombic efficiency, at 20 °C. Besides recovery from mechanical deformations, it is visually demonstrated that the shape of this smart battery can be programmed to adjust itself in response to an internal/external heat stimulus for task-specific and advanced applications. Considering the vast range of available shape memory polymers with tunable chemistry, physical, and mechanical characteristics, this study offers a promising approach for engineering smart batteries responsive to unfavorable internal or external stimulus, with potential to have a broad impact on other energy storage technologies in different sizes and shapes.

Evolution and Shape of Two-Dimensional Stokesian Drops under the Action of Surface Tension and Electric Field: Linear and Nonlinear Theory and Experiment.

The creeping-flow theory describing evolution and steady-state shape of two-dimensional ionic-conductor drops under the action of surface tension and the subcritical (in terms of the electric Bond number) electric field imposed in the substrate plane is developed. On the other hand, the experimental data are acquired for drops impacted or softly deposited on dielectric surfaces of different wettability and subjected to an in-plane subcritical electric field. Even though the experimental situation involves viscous friction of drops with the substrates and wettability-driven motion of the contact line, the comparison to the theory reveals that it can accurately describe the steady-state drop shape on a non-wettable substrate. In the latter case, the drop is sufficiently raised above the substrate, which diminishes the three-dimensional effects, making the two-dimensional description (lacking the no-slip condition at the substrate and wettability-driven motion of the contact line) relevant. Accordingly, it is demonstrated how the subcritical electric field deforms the initially circular drops until an elongated steady-state configuration is reached. In particular, the surface tension tends to round off the non-circular drops stretched by the electric Maxwell stresses imposed by the electrodes. A more pronounced substrate wettability leads to more elongated steady-state configurations observed experimentally than those predicted by the two-dimensional theory. The latter cases reveal significant three-dimensional effects in the electrically driven drop stretching. In the supercritical electric fields (corresponding to the supercritical electric Bond numbers), the electrical stretching of drops predicted by the present linearized two-dimensional theory results in splitting into two separate droplets. This scenario is corroborated by the predictions of the fully nonlinear results for similar electrically stretched bubbles in the creeping-flow regime available in the literature as well as by the present experimental results on a substrate with slip.

Computer simulation of the SARS-CoV-2 contamination risk in a large dental clinic.

COVID-19, caused by the SARS-CoV-2 (severe acute respiratory syndrome coronavirus 2) virus, has been rapidly spreading worldwide since December 2019, causing a public health crisis. Recent studies showed SARS-CoV-2's ability to infect humans via airborne routes. These motivated the study of aerosol and airborne droplet transmission in a variety of settings. This study performs a large-scale numerical simulation of a real-world dentistry clinic that contains aerosol-generating procedures. The simulation tracks the dispersion of evaporating droplets emitted during ultrasonic dental scaling procedures. The simulation considers 25 patient treatment cubicles in an open plan dentistry clinic. The droplets are modeled as having a volatile (evaporating) and nonvolatile fraction composed of virions, saliva, and impurities from the irrigant water supply. The simulated clinic's boundary and flow conditions are validated against experimental measurements of the real clinic. The results evaluate the behavior of large droplets and aerosols. We investigate droplet residence time and travel distance for different droplet diameters, surface contamination due to droplet settling and deposition, airborne aerosol mass concentration, and the quantity of droplets that escape through ventilation. The simulation results raise concerns due to the aerosols' long residence times (averaging up to 7.31 min) and travel distances (averaging up to 24.45 m) that exceed social distancing guidelines. Finally, the results show that contamination extends beyond the immediate patient treatment areas, requiring additional surface disinfection in the clinic. The results presented in this research may be used to establish safer dental clinic operating procedures, especially if paired with future supplementary material concerning the aerosol viral load generated by ultrasonic scaling and the viral load thresholds required to infect humans.

Beyond Volume Variation: Anisotropic and Protrusive Lithiation in Bismuth Nanowire.

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. In this work, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li-Bi alloying process exhibits a two-step transition, that is, Bi-Li1Bi and Li1Bi-Li3Bi. Interestingly, the Bi-Li1Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li1Bi nanograins as a result of anisotropic Li-Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li1Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li1Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li1Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

Reopening dentistry after COVID-19: Complete suppression of aerosolization in dental procedures by viscoelastic Medusa Gorgo.

The aerosol transmissibility of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has impacted the delivery of health care and essentially stopped the provision of medical and dental therapies. Dentistry uses rotary, ultrasonic, and laser-based instruments that produce water-based aerosols in the daily, routine treatment of patients. Abundant aerosols are generated, which reach health care workers and other patients. Viruses, including SARS-CoV-2 virus and related coronavirus disease (COVID-19) pandemic, continued expansion throughout the USA and the world. The virus is spread by both droplet (visible drops) and aerosol (practically invisible drops) transmission. The generation of aerosols in dentistry-an unavoidable part of most dental treatments-creates a high-risk situation. The US Centers for Disease Control and The Occupational Safety and Health Administration consider dental procedures to be of "highest risk" in the potential spreading of SARS-CoV-2 and other respiratory viruses. There are several ways to reduce or eliminate the virus: (i) cease or postpone dentistry (public and personal health risk), (ii) screen patients immediately prior to dental treatment (by appropriate testing, if any), (iii) block/remove the virus containing aerosol by engineering controls together with stringent personal protective equipment use. The present work takes a novel, fourth approach. By altering the physical response of water to the rotary or ultrasonic forces that are used in dentistry, the generation of aerosol particles and the distance any aerosol may spread beyond the point of generation can be markedly suppressed or completely eliminated in comparison to water for both the ultrasonic scaler and dental handpiece.

Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials.

Despite their high energy densities, Li- and Mn-rich, layered-layered, xLi2MnO3·(1 - x)LiTMO2 (TM = Ni, Mn, Co) (LMR-NMC) cathodes require further development in order to overcome issues related to bulk and surface instabilities such as Mn dissolution, impedance rise, and voltage fade. One promising strategy to modify LMR-NMC properties has been the incorporation of spinel-type, local domains to create "layered-layered-spinel" cathodes. However, precise control of local structure and composition, as well as subsequent characterization of such materials, is challenging and elucidating structure-property relationships is not trivial. Therefore, detailed studies of atomic structures within these materials are still critical to their development. Herein, aberration corrected-scanning transmission electron microscopy (AC-STEM) is utilized to study atomic structures, prior to and subsequent to electrochemical cycling, of LMR-NMC materials having integrated spinel-type components. The results demonstrate that strained grain boundaries with various atomic configurations, including spinel-type structures, can exist. These high energy boundaries appear to induce cracking and promote dissolution of Mn by increasing the contact surface area to electrolyte as well as migration of Ni during cycling, thereby accelerating performance degradation. These results present insights into the important role that local structures can play in the macroscopic degradation of the cathode structures and reiterate the complexity of how synthesis and composition affect structure-electrochemical property relationships of advanced cathode designs.

Non-Dendritic Zn Electrodeposition Enabled by Zincophilic Graphene Substrates.

Rechargeable zinc (Zn) batteries suffer from poor cycling performance that can be attributed to dendrite growth and surface-originated side reactions. Herein, we report that cycling performance of Zn metal anode can be improved significantly by utilizing monolayer graphene (Gr) as the electrodeposition substrate. Utilizing microscopy and X-ray diffraction techniques, we demonstrate that electrodeposited Zn on Gr substrate has a compact, uniform, and nondendritic character. The Gr layer, due to its high lattice compatibility with Zn, provides low nucleation overpotential sites for Zn electrodeposition. Atomistic calculations indicate that Gr has strong affinity to Zn (binding energy of 4.41 eV for Gr with four defect sites), leading to uniform distribution of Zinc adatoms all over the Gr surface. This synergistic compatibility between Gr and Zn promotes subsequent homogeneous and planar Zn deposits with low interfacial energy (0.212 J/m2) conformal with the current collector surface.

Slow Discharge Theory and Calculation of the Potential Drop across the Compact Layer at High Electrode Voltages.

A novel approach presented in this work allows one to calculate the potential drop across the compact layer in electrostatic atomization with high voltages applied at the electrode. Ionic conductor liquids employed in electrostatic atomization have a low dielectric constant, which causes almost all of the potential drop across the double layer to occur inside the compact layer. In the previous article of this group (Sankarn, A., et al. Langmuir 2017, 33, 1375-1384), it was shown that faradaic reactions in the kinetics-limited regime are responsible for liquid electrification in electrostatic atomization. Here, we apply the Frumkin slow discharge theory to calculate the electric potential at the interface of the compact and diffuse layers. The electric potential value at the interface of the compact and diffuse layers is required in computational models accounting for the discharge of counterions due to faradaic reactions when solving the ionic transport equations. The activation energy of the electron transfer reaction is calculated through the Marcus theory. Knowing the counterion flux value at the electrode surface from the concurrent experimental measurements, the ionic concentration and net charge distribution across the polarized diffuse layer are also found from the numerical simulations. Considering canola oil to be the ionic conductor liquid, two different examples are used to demonstrate the application of this approach to calculate the electric potential at the interface of compact and diffuse layers.

Theoretical and Numerical Study of Formation of Near-Electrode Layers in Ionic Conductor Liquids at High Voltages.

A novel approach is developed to predict the thickness of the equivalent one-dimensional Stern layer near conducting electrodes subjected to high voltage and carrying electric current. The nonspecific (nonelectric) ion adsorption responsible for the formation of the Stern compact layer at the electrode surface is attributed to the Langmuir-Brunauer-Emmett-Teller mechanism. The compact Stern layer is implied to be intrinsically two-dimensional and forming on the oxide or impurity islands on the electrode surface, which prevents electron transfer to or from the adsorbed ions. On the other hand, electrons are transferred through the open parts of the metallic electrode surface by electron transfer faradaic reactions characterized by the Frumkin-Butler-Volmer kinetics. Then, the one-dimensional Stern layer appears to be an approximation of the abovementioned two-dimensional model. In the framework of this model, the equivalent one-dimensional Stern layer thickness is predicted, rather than used as an adjustable parameter, as frequently done in the literature.

Tuning Li2O2 Formation Routes by Facet Engineering of MnO2 Cathode Catalysts.

In lithium-oxygen batteries, the solubility of LiO2 intermediates in the electrolyte regulates the formation routes of the Li2O2 discharge product. High-donor-number electrolytes with a high solubility of LiO2 tend to promote the formation of Li2O2 large particles following the solution route, which eventually benefits the cell capacity and cycle life. Here, we propose that facet engineering of cathode catalysts could be another direction in tuning the formation routes of Li2O2. In this work, ß-MnO2 crystals with high occupancies of {111} or {100} facets were adopted as cathode catalysts in Li-O2 batteries with a tetra(ethylene)glycol dimethyl ether electrolyte. The {111}-dominated ß-MnO2 catalyzed the formation of the Li2O2 discharge product into large toroids following the solution routes, while {100}-dominated ß-MnO2 facilitated the formation of Li2O2 thin films through the surface routes. Further computational studies indicate that the different formation routes of Li2O2 could be related to different adsorption energies of LiO2 on the two facets of ß-MnO2. Our results demonstrate that facet engineering of cathode catalysts could be a new way to tune the formation route of Li2O2 in a low-donor-number electrolyte. We anticipate that this new finding would offer more choices for the design of lithium-oxygen batteries with high capacities and ultimately a long cycle life.

Plastic recovery and self-healing in longitudinally twinned SiGe nanowires.

This paper reports on plastic recovery and self-healing behavior in longitudinally-twinned and [112] orientated SiGe nanowire (NW) beams when they are subjected to large bending strains. The NW alloys are comprised of lamellar nanotwin platelet(s) sandwiched between two semi-cylindrical twins. The loading curves, which are acquired from atomic force microscope (AFM) based three-point bending tests, reveal the onset of plastic deformation at a characteristic stress threshold, followed by further straining of the NWs. This ductility is attributed to dislocation activity within the semi-cylindrical crystal portions of the NW, which are hypothesized to undergo a combination of elastic and plastic straining. On the other hand, the lamellar nanoplatelets undergo purely elastic stretching. During the unloading process, the release of internal elastic stresses enables dislocation backflow and escape at the surface. As a result, the dislocations are predominantly annihilated and the NW samples evidenced self-healing via plastic recovery even at ultra-large strains, which are estimated using finite-element models at 16.3% in one of the tested devices. Finite element analysis also establishes the independence of the observed nanomechanical behavior on the relative orientation of the load with respect to the nanoplatelet. This first observation of reversible plasticity in the SiGe material system, which is aided by a concurrent evolution of segmented elastic and plastic deformation within its grains during the loading process, presents an important new pathway for mechanical stabilization of technologically important group-IV semiconductor nanomaterials.

Modeling of Droplet Impact onto Polarized and Nonpolarized Dielectric Surfaces.

This paper is concerned with simulation of the droplet impact on a dielectric surface, referred to as the dynamic electrowetting-on-dielectric (DEWOD). In particular, we seek to shed more light on the fundamental processes occurring during the impact of an electrically conducting droplet onto a dielectric surface with and without an applied voltage. The liquid in the droplet is an ionic conductor (a leaky dielectric). This work employs an approach based on Cahn-Hilliard-Navier-Stokes (CHNS) modeling. The simulations are validated by predicting the equilibrium contact angle, droplet oscillations, and charge density estimation. Then, four cases of droplet impact are studied, namely, the impact onto a surface with no voltage applied and the impacts onto the surfaces with 2, 4, and 6 kV applied. The modeling results of water droplet impact allow for direct comparison with the experimental results reported by Lee et al. [ Langmuir 2013, 29, 7758]. The results reveal the electric field, the body forces acting on the droplet, the velocity and pressure fields inside and outside the droplet, as well as the free charge density and the electric energy density. The model predicts the droplet shape evolution (e.g., the spreading distance over the surface and the rebound height) under different conditions that are consistent with the experimental observations. Thus, our findings provide new qualitative and quantitative insights into the droplet manipulation that can be used in novel applications of the DEWOD phenomenon.

Long-Range Self-Assembly via the Mutual Lorentz Force of Plasmon Radiation.

Long-range interactions often proceed as a sequence of hopping through intermediate, statistically favored events. Here, we demonstrate predictable mechanical dynamics of particles that arise from the Lorentz force between plasmons. Even if the radiation is weak, the nonconservative Lorentz force produces stable locations perpendicular to the plasmon oscillation; over time, distinct patterns emerge. Experimentally, linearly polarized light illumination leads to the formation of 80 nm diameter Au nanoparticle chains, perpendicularly aligned, with lengths that are orders of magnitude greater than their plasmon near-field interaction. There is a critical intensity threshold and optimal concentration for observing self-assembly.

Facet-Dependent Thermal Instability in LiCoO2.

Thermal runaways triggered by the oxygen release from oxide cathode materials pose a major safety concern for widespread application of lithium ion batteries. Utilizing in situ aberration-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) at high temperatures, we show that oxygen release from LixCoO2 cathode crystals is occurring at the surface of particles. We correlated this local oxygen evolution from the LixCoO2 structure with local phase transitions spanning from layered to spinel and then to rock salt structure upon exposure to elevated temperatures. Ab initio molecular dynamics simulations (AIMD) results show that oxygen release is highly dependent on LixCoO2 facet orientation. While the [001] facets are stable at 300 °C, oxygen release is observed from the [012] and [104] facets, where under-coordinated oxygen atoms from the delithiated structures can combine and eventually evolve as O2. The novel understanding that emerges from the present study provides in-depth insights into the thermal runaway mechanism of Li-ion batteries and can assist the design and fabrication of cathode crystals with the most thermally stable facets.

Selective Ionic Transport Pathways in Phosphorene.

Despite many theoretical predictions indicating exceptionally low energy barriers of ionic transport in phosphorene, the ionic transport pathways in this two-dimensional (2D) material has not been experimentally demonstrated. Here, using in situ aberration-corrected transmission electron microscopy (TEM) and density functional theory, we studied sodium ion transport in phosphorene. Our high-resolution TEM imaging complemented by electron energy loss spectroscopy demonstrates a precise description of anisotropic sodium ions migration along the [100] direction in phosphorene. This work also provides new insight into the effect of surface and the edge sites on the transport properties of phosphorene. According to our observation, the sodium ion transport is preferred in zigzag edge rather than the armchair edge. The use of this highly selective ionic transport property may endow phosphorene with new functionalities for novel chemical device applications.

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO2 Nanowires.

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122̅) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO2 structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

Twin boundary-assisted lithium ion transport.

With the increased need for high-rate Li-ion batteries, it has become apparent that new electrode materials with enhanced Li-ion transport should be designed. Interfaces, such as twin boundaries (TBs), offer new opportunities to navigate the ionic transport within nanoscale materials. Here, we demonstrate the effects of TBs on the Li-ion transport properties in single crystalline SnO2 nanowires. It is shown that the TB-assisted lithiation pathways are remarkably different from the previously reported lithiation behavior in SnO2 nanowires without TBs. Our in situ transmission electron microscopy study combined with direct atomic-scale imaging of the initial lithiation stage of the TB-SnO2 nanowires prove that the lithium ions prefer to intercalate in the vicinity of the (101̅) TB, which acts as conduit for lithium-ion diffusion inside the nanowires. The density functional theory modeling shows that it is energetically preferred for lithium ions to accumulate near the TB compared to perfect neighboring lattice area. These findings may lead to the design of new electrode materials that incorporate TBs as efficient lithium pathways, and eventually, the development of next generation rechargeable batteries that surpass the rate performance of the current commercial Li-ion batteries.

Lithiation-induced shuffling of atomic stacks.

In rechargeable lithium-ion batteries, understanding the atomic-scale mechanism of Li-induced structural evolution occurring at the host electrode materials provides essential knowledge for design of new high performance electrodes. Here, we report a new crystalline-crystalline phase transition mechanism in single-crystal Zn-Sb intermetallic nanowires upon lithiation. Using in situ transmission electron microscopy, we observed that stacks of atomic planes in an intermediate hexagonal (h-)LiZnSb phase are "shuffled" to accommodate the geometrical confinement stress arising from lamellar nanodomains intercalated by lithium ions. Such atomic rearrangement arises from the anisotropic lithium diffusion and is accompanied by appearance of partial dislocations. This transient structure mediates further phase transition from h-LiZnSb to cubic (c-)Li2ZnSb, which is associated with a nearly "zero-strain" coherent interface viewed along the [001]h/[111]c directions. This study provides new mechanistic insights into complex electrochemically driven crystalline-crystalline phase transitions in lithium-ion battery electrodes and represents a noble example of atomic-level structural and interfacial rearrangements.

Atomic-scale observation of lithiation reaction front in nanoscale SnO2 materials.

In the present work, taking advantage of aberration-corrected scanning transmission electron microscopy, we show that the dynamic lithiation process of anode materials can be revealed in an unprecedented resolution. Atomically resolved imaging of the lithiation process in SnO2 nanowires illustrated that the movement, reaction, and generation of b = [1[overline]1[overline]1] mixed dislocations leading the lithiated stripes effectively facilitated lithium-ion insertion into the crystalline interior. The geometric phase analysis and density functional theory simulations indicated that lithium ions initial preference to diffuse along the [001] direction in the {200} planes of SnO2 nanowires introduced the lattice expansion and such dislocation behaviors. At the later stages of lithiation, the Li-induced amorphization of rutile SnO2 and the formation of crystalline Sn and LixSn particles in the Li2O matrix were observed.