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At least 91 records · Page 5

Irradiation induced void spheroidization, shrinkage and migration in Cu at elevated temperatures: An in situ study

We show understanding the void evolution in irradiation environment is of great interest and significance, as irradiation-induced voids typically lead to pronounced volumetric swelling and degradation of mechanical properties. In situ studies on the irradiation response of nanovoids at elevated temperature remain limited. In this work, we performed systematic in situ 1 MeV Kr ++ irradiations on Cu with nanovoids in a transmission electron microscope up to 350 °C. The in situ studies revealed intriguing void spheroidization, shrinkage and migration. Furthermore, the morphology evolution and migration of nanovoids showed a strong dependence on irradiation temperature and initial void size. Post-irradiation analyses identified defect clusters in the form of stacking fault tetrahedrons, and the remaining large faceted nanovoids. The underlying mechanisms of irradiation-induced void spheroidization and shrinkage were discussed based on phase-field modeling.

36 MATERIALS SCIENCE↗

Surface diffusion manifestation in electrodeposition of metal anodes

Metal anode-based battery systems have been deemed indispensable towards energy storage renaissance engendering extensive research into strategies countering dendritic growth of metal electrodeposition. Fundamentally, the morphological evolution of a material is uniquely characterized by the heights of its self-diffusion barrier across multiple pathways. Herein, based on a coarse-grained kinetic Monte Carlo method, we derive insights into the nucleation and growth of metallic electrodeposits in liquid electrolytes, governed by surface self-diffusion characteristics cognizant of the diverse diffusion routes including terrace, away from step and interlayer pathways. We deconvolve the roles played by each of these surface diffusion mechanisms in conjunction with the electrochemical reaction rate on the deposition morphology regime (film vs. mossy vs. fractal). We identify interlayer diffusion as the predominant morphology-determining mechanism; dendrite-free deposition even at moderate current rates constrains this diffusion barrier to an upper limit. Additionally, we highlight subtle features amidst the realm of the morphological growth assortment that connect to the cell's electrochemical performance. Finally, we delineate morphological features of Li, Na, Mg and Al based on their respective surface diffusion barriers and applied overpotentials, and provide a baseline for the interpretation of experimental observations. This fundamental study sheds light on the mesoscale underpinnings of morphological variances in mono-valent and multi-valent metal electrodeposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-assisted synthesis of iron sulfide motifs for electrochemical applications

Abstract The syntheses of FeS 2 and Fe 3 S 4 nanomaterials were optimized using a novel facile, surfactant-free, and microwave-assisted, one-pot synthesis method, run under ambient and reasonably mild reaction conditions. Synthetic parameters, such as metal precursor salt identity, reaction time, reaction temperature, metal:sulfur molar ratios, and solvent combinations, were all systematically investigated and optimized. A series of FeS 2 (pyrite) samples was initially fabricated using thioacetamide (TAA) as the sulfur precursor to generate a distinctive, uniform octahedra-based morphology. Switching the sulfur precursor from TAA to L-cysteine resulted in a corresponding transformation in not only chemical composition from FeS 2 to an iron thiospinel structure, Fe 3 S 4 (otherwise known as greigite), but also an associated morphological evolution from octahedra to nanosheet aggregates. The study of these materials has enabled crucial insights into the formation mechanisms of these materials under a relatively non-conventional microwave-assisted setting. Furthermore, in separate experiments, multi-walled carbon nanotubes (MWNTs) and graphene were added in with underlying metal sulfide species to create conductive Fe–S/MWNT composites and Fe–S/graphene composites, respectively. The method of addition of either MWNTs or graphene was also explored, wherein an ‘ ex-situ ’ synthetic procedure was found to be the least disruptive means of attachment and immobilization onto iron sulfide co-reagents as a means of preserving the latter’s inherent composition and morphology. The redox acidity for the parent material and associated composites demonstrates the utility of our as-developed synthetic methods for creating motifs relevant for electrochemical applications, such as energy storage.

25 ENERGY STORAGE↗

Exploring the Spatial Control of Topotactic Phase Transitions Using Vertically Oriented Epitaxial Interfaces

Engineering oxygen vacancy formation and distribution is a powerful route for controlling the oxygen sublattice evolution that affects diverse functional behavior. The controlling of the oxygen vacancy formation process is particularly important for inducing topotactic phase transitions that occur by transformation of the oxygen sublattice. Here we demonstrate an epitaxial nanocomposite approach for exploring the spatial control of topotactic phase transition from a pristine perovskite phase to an oxygen vacancy-ordered brownmillerite (BM) phase in a model oxide La 0.7 Sr 0.3 MnO 3 (LSMO). Incorporating a minority phase NiO in LSMO films creates ultrahigh density of vertically aligned epitaxial interfaces that strongly influence the oxygen vacancy formation and distribution in LSMO. Combined structural characterizations reveal strong interactions between NiO and LSMO across the epitaxial interfaces leading to a topotactic phase transition in LSMO accompanied by significant morphology evolution in NiO. Using the NiO nominal ratio as a single control parameter, we obtain intermediate topotactic nanostructures with distinct distribution of the transformed LSMO-BM phase, which enables systematic tuning of magnetic and electrical transport properties. The use of self-assembled heterostructure interfaces by the epitaxial nanocomposite platform enables more versatile design of topotactic phase structures and correlated functionalities that are sensitive to oxygen vacancies.

36 MATERIALS SCIENCE↗

Coalescence of GaP on V-Groove Si

In recent years, better understanding and control over the formation of crystalline defects during the direct epitaxy of III-V semiconductors on Si substrates via metal organic vapor phase epitaxy (MOVPE) has enabled large gains in III-V-on-Si solar cell efficiency, pointing to pathway to lower-cost, high-performance III-V solar cells. However, such results have only been achieved on costly chemo-mechanically-polished (CMP) Si wafers. The use of V-groove nanopatterned Si substrates has demonstrated similarly high-crystalline-quality III-V-on-Si epitaxy, but also can be combined with lower-cost polishing techniques. Although they offer a potential cost advantage, growth on V-groove substrates adds challenges not present for epitaxy on planar wafers (the III-V material must be coalesced into a thin film after an initial nucleation stage). MOVPE growth conditions that promote highly facet-selective lateral growth needed for coalescence are generally actively avoided for conventional thin fim growth, so growth conditions need to be re-developed for V-groove-based epitaxy. Additionally, coalescence add complexity to the dislocation dynamics related to lattice relaxation, so strategies used to keep threading dislocation density (TDD) low on planar substrates need to be re-tuned for V-grooves. We have studied the morphological evolution and dislocation dynamics of GaP grown on V-groove Si by MOVPE. Growth conditions of V/III=5,000 and Tg=800 degrees C were uniquely found to produce extremely smooth coalesced thin films, with an RMS roughness of 0.2 nm measured by AFM. Additionally, at this growth condition, we identified two regimes of growth determined by the width of the SiNx cap (a remnant of the nanopatterning process) at the top of the V-grooves. For narrow caps, the GaP coalesces into a thin film, and for wide caps, the GaP evolves into {1 1 1}-faceted diamonds that do not coalesce. We suggest the influence of Si from the sidewalls of the V-grooves on the surface reconstruction of the GaP as the mechanism for this effect, with reflection difference spectroscopy (RDS) and Si doping experiments supporting this theory. In addition to morphology, the dislocation dynamics of the system were studied with electron channeling contrast imaging (ECCI) and transmission electron microscopy (TEM). The TDD of the coalesced GaP films was found to be 5 x 10^7 cm^-2 after coalescence via ECCI, a level still too high for high-quality solar cells. However, misfit dislocations crossing multiple grooves greater than 20 micrometers long were observed in ECCI, suggesting that the V-grooves do not block dislocation glide. TEM prior to and after coalescence was used to distinguish between dislocation creation driven by growth conditions and coalescence. Finally, strategies to reduce the dislocation density to levels acceptable for solar cells will be discussed.

GaP↗

Pit rim decomposition into multiple quantum dots on surfaces of epitaxial thin films grown on pit-patterned substrates

Here, we report results of dynamical simulations according to an experimentally validated surface morphological evolution model on the formation of regular arrays of quantum dot molecules (QDMs) consisting of 1D arrays of smaller interacting quantum dots (QDs). These QD arrays form along the sides of each pit rim on the surface of a coherently strained thin film epitaxially deposited on a semiconductor substrate, the surface of which consists of a periodic pattern of inverted prismatic pits with rectangular pit openings. We find that this complex QDM pattern results from the decomposition of the pit rim from a “quantum fortress” with four elongated QDs into four 1D arrays of multiple smaller QDs arranged along each side of the pit rim. Systematic parametric analysis indicates that varying the pit opening dimensions and the pit wall inclination directly impacts the number of QDs in the resulting QDM pattern, while varying the pit depth only affects the dimensions of the QDs in the nanostructure pattern. Therefore, the number, arrangement, and sizes of QDs in the resulting pattern of QDMs on the film surface can be engineered precisely by proper tuning of the pit design parameters. Our simulation results are supported by predictions of morphological stability analysis, which explains the pit rim decomposition into multiple QDs as the outcome of a tip-splitting instability and provides a fundamental characterization of the post-instability nanostructure pattern. Our theoretical findings can play a vital role in designing optimal semiconductor surface patterns toward enabling future nanofabrication technologies.

36 MATERIALS SCIENCE↗

Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO 3 ) during their replacement by cerussite (PbCO 3 , an isomorph of aragonite) and otavite (CdCO 3 , an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb 2+ is reacted with either calcite or aragonite and when Cd 2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd 2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO 3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb 2+ and Cd 2+ can be determined by interplay between morphological and crystallographic properties of CaCO 3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

58 GEOSCIENCES↗

Dendrite Growth Morphology Modeling in Liquid and Solid Electrolytes

The main goal of this project is to develop a multi-scale modeling approach that connects micron-scale phase-field models and atomic-scale density functional theory (DFT)-based simulations via parameter- and relationship-passing in order to predict Li-metal dendrite morphology evolution, in both liquid and solid electrolytes. The key hypothesis of the DFT-informed phase-field multiscale modeling approach is that it can capture the electrochemical-mechanical driving forces and incorporate the roles of nano-meter-thin solid electrolyte interphase (SEI) in liquid electrolytes as well as of the microstructures of micro-meter-thick solid electrolytes (SEs) for all-solid-state batteries. In this project, we have formulated and implemented phase-field models to incorporate the electrochemical driving forces in liquid electrolytes and then incorporate mechanical driving forces to simulate dendrite growth in solid electrolytes with resolved microstructures. We have implemented two treatments for the SEI: an explicit model to include the microstructure of the SE or SEI in the phase field model and an implicit model to simulate the impact of nano-meter thick SEI in liquid electrolytes by varying the electrode/electrolyte interfacial properties. The key interfacial properties, including the electronic and ionic transport properties, the charge transfer reaction kinetics, and mechanical properties, were computed by DFT-based calculations. At the DFT-based model, one key advancement is to directly predict the charge transfer reaction kinetics at a complex Li/SEI/electrolyte interface by linking DFT with density functional tight binding (DFTB) calculations. As the main accomplishments, we have demonstrated two successful predictions in both solid electrolyte and liquid electrolyte based on this multiscale approach. The predicted intergranular Li dendrite growth in LLZO revealed the importance of trapped electrons at internal interfaces in the microstructure of LLZO. The predicted electroplating morphology of mossy Li and faceted Mg agreed well with experiments. The insights provided by the multiscale model and the model enabled electrolyte and SEI design will accelerate the development of Li-metal electrode for high energy density batteries, that meet DOE’s target on cell density (>350 Wh/kg) and cost below $100/kWhuse for EV applications.

25 ENERGY STORAGE↗

Boosting the H 2 –D 2 Exchange Activity of Dilute Nanoporous Ti–Cu Catalysts through Oxidation–Reduction Cycle–Induced Restructuring

The use of nanoporous metals as catalysts has attracted significant interest in recent years. Their high-curvature, nanoscale ligaments provide not only high surface area but also a high density of undercoordinated step edge and kink sites. However, their long-term stability, especially at higher temperatures, is often limited by thermal coarsening and the associated loss of surface area. Herein, it is demonstrated that the nanoscale morphology of nanoporous Cu can be regenerated by applying oxidation/reduction cycles at 250 °C. Specifically, the morphological evolution and H 2 dissociation activity of hierarchical nanoporous Cu catalysts doped with Ti during structural rearrangement triggered by oxidative and reductive atmospheres at elevated temperatures are studied. In addition to coarsening of the structure at elevated temperatures, oxidation at 400 °C causes an expansion of the ligaments. Further, subsequent reduction at 400 °C leads to the formation of particles and a drop in the H 2 dissociation activity compared the fresh catalyst. However, performing the redox cycle at 250 °C reverses coarsening and boosts the H 2 dissociation activity for the hydrogen–deuterium (H 2 –D 2 ) reaction. Herein, the possibility to reverse coarsening is demonstrated, thereby mitigating the loss of activity frequently observed in nanoporous catalysts.

36 MATERIALS SCIENCE↗

Unraveling the Crystallization Kinetics of 2D Perovskites with Sandwich-Type Structure for High-Performance Photovoltaics

2D perovskite solar cells with high stability and high efficiency have attracted significant attention. A systematical static and dynamic structure investigation is carried out to show the details of 2D morphology evolution. A dual additive approach is used, where the synergy between an alkali metal cation and a polar solvent leads to high-quality 2D perovskite films with sandwich-type structures and vertical phase segregation. Such novel structure can induce high-quality 2D slab growth and reduce internal and surface defects, resulting in a high device efficiency of 16.48% with enhanced continuous illumination stability and improved moisture (55-60%) and thermal (85°C) tolerances. Transient absorption spectra reveal the carrier migration from low n to high n species with different kinetics. An [PbI 6 ] 4- octagon coalescence transformation mechanism coupled with metal and organic cations wrapped is proposed. By solvent vapor annealing, a recrystallization and reorientation of the 2D perovskite slabs occurs to form an ideal structure with improved device performance and stability.

36 MATERIALS SCIENCE↗

Versatile Sequential Casting Processing for Highly Efficient and Stable Binary Organic Photovoltaics

Forming an ideal bulk heterojunction (BHJ) morphology is a critical issue governing the photon to electron process in organic solar cells (OSCs). Complementary to the widely-used blend casting (BC) method for BHJ construction, sequential casting (SC) can also enable similar or even better morphology and device performance for OSCs. Here, BC and SC methods on three representative donor:acceptor (D:A) blends are utilized, that is, PM6:PC 71 BM, PM6:IT-4F and PM6:L8-BO. Higher power conversion efficiencies (PCEs) in all cases by taking advantage of beneficial morphology from SC processing are achieved, and a champion PCE of 18.86% (certified as 18.44%) based on the PM6:L8-BO blend is reached, representing the record value among binary OSCs. The observations on phase separation and vertical distribution inspire the proposal of the swelling–intercalation phase-separation model to interpret the morphology evolution during SC processing. Further, the vertical phase segregation is found to deliver an improvement of device performance via affecting the charge transport and collection processes, as evidenced by the D:A-ratio-dependent photovoltaic properties. Besides, OSCs based on SC processing show advantages on device photostability and upscale fabrication. Finally, this work demonstrates the versatility and efficacy of the SC method for BHJ-based OSCs.

14 SOLAR ENERGY↗

High‐Speed Slot‐Die Coating with Donor‐Priority Rapid Aggregation Kinetics for Improved Morphology and Efficiency in Ecofriendly Organic Solar Cells

Abstract Solution‐processable organic solar cells (OSCs) represent a promising renewable photovoltaic technology with significant potential for eco‐compatible production. While high power conversion efficiencies (PCEs) have been achieved in OSCs, scaling this technology for high‐throughput manufacturing remains challenging. Key reason lies in the lack of efficient control strategies for the complex and long‐duration morphology evolution during high‐speed coating process with ecofriendly solvents. Here, a donor‐priority rapid aggregation process (DP‐RAP) scheme is proposed to solve this issue by adjusting the aggregation kinetics of donor and acceptor components. DP‐RAP enables blends with a nanoscale fiber network structure and favorable crystallinity, which contributes to balanced carrier transport and reduced recombination losses. As a result, the PCE is improved from 14.3% (reference) to 17.4% (DP‐RAP) for ultra‐high speed coated PM6:BTP‐eC9 devices in atmosphere, which is one of the highest values for non‐halogenated solvent‐processed solar cells at coating speeds of 500 mm s −1 . Moreover, the DP‐RAP based devices remain a stable PCE of approximately 17.4% across a broad range of coating speeds (20–500 mm s −1 ), illustrating its tolerance to the varied manufacturing conditions. This work highlights a promising avenue for the high‐speed, ecofriendly production of efficient OSCs, pushing the boundaries of practical manufacturing in renewable energy technologies.

Chemistry↗

Unlocking Failure Mechanisms and Improvement of Practical Li–S Pouch Cells through In Operando Pressure Study

For Lithium-sulfur (Li-S) battery commercialization, the study at a pouch cell level is essential, as some problems ignored or deemed minimal at the smaller level could have a greater effect on the performance of the larger pouch cell. Herein, the failure mechanisms of Li-S pouch cells are deeply investigated via in operando pressure analysis. It is found that highly porous structures of cathodes/separators and slow electrolyte diffusion through cathodes/separators can both lead to poor initial wetting. Additionally, Li-metal anode dominates the thickness variation of the whole pouch cell, which is verified by in situ measured pressure variation. Consequently, a real-time approach that combined normalized pressure with dP/dV analysis is proposed and validated to diagnose the morphology evolution of Li-metal anode. Moreover, applied pressure and porosity/tortuosity ratio of the cathode are both identified as independent factors that influence anode performance. In addition to stabilizing anodes, high pressure is proven to improve the cathode connectivity and avoid cathode cracking over cycling, which improves the possibility of developing cathodes with high sulfur mass loading. Here, this work provides insights into Li-S pouch cell design (e.g., cathode and separator) and highlights pathways to improve cell capacity and cycling performance with applied and monitored pressure.

25 ENERGY STORAGE↗

Intermetallics Based on Sodium Chalcogenides Promote Stable Electrodeposition–Electrodissolution of Sodium Metal Anodes

Sodiophilic micro-composite films of sodium-chalcogenide intermetallics (Na 2 Te and Na 2 S) and Cu particles are fabricated onto commercial copper foam current collectors (Na 2 Te@CF and Na 2 S@CF). For the first time a controllable capacity thermal infusion process is demonstrated. Enhanced wetting by the metal electrodeposition leads to state-of-the-art electrochemical performance. For example, Na 2 Te@CF-based half-cells demonstrate stable cycling at 6 mA cm -2 and 6 mAh cm -2 , corresponding to 54 µm of Na electrodeposited/electrodissolved by geometric area. Sodium metal batteries with Na 3 V 2 (PO 4 ) 3 cathodes are stable at 30C (7 mA cm -2 ) and for 10 000 cycles at 5C and 10C. Cross-sectional cryogenic focused ion beam (cryo-FIB) microscopy details deposited and remnant dissolved microstructures. Sodium metal electrodeposition onto Na 2 Te@CF is dense, smooth, and free of dendrites or pores. On unmodified copper foam, sodium grows in a filament-like manner, not requiring cycling to achieve this geometry. Substrate–metal interaction critically affects the metal–electrolyte interface, namely the thickness and morphology of the solid electrolyte interphase. Density functional theory and mesoscale simulations provide insight into support-adatom energetics, nucleation response, and early-stage morphological evolution. On Na 2 Te sodium atomic dispersion is thermodynamically more stable than isolated clusters, leading to conformal adatom coverage of the surface.

36 MATERIALS SCIENCE↗

Theoretical Investigation of the Adsorbate and Potential–Induced Stability of Cu Facets During Electrochemical CO 2 and CO Reduction

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO 2 RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO 2 RR conditions. Here we identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO 2 RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO 2 RR conditions is likely attributed to differences in CO* coverage between these facets.

30 DIRECT ENERGY CONVERSION↗

Three-dimensional phase field sintering simulations accounting for the rigid-body motion of individual grains

Sintering is a widely used powder processing technique in industrial applications. During sintering, atoms migrate to decrease the energy of the system via two main mechanisms: coarsening and densification, both of which lead to significant morphological variation of the sintered microstructure. When simulating sintering dynamics, the phase-field method has been broadly utilized because of its convenience in tracking morphology evolution. When a large number of grains is involved, it is common to use the same order parameter to describe multiple grains that are not in direct contact with one another (in order to reduce the computational memory demands). However, with this treatment it is difficult to handle the rigid-body motion of individual grains during densification. In this work, an implementation scheme is introduced to overcome the challenge of calculating individual particle motion based on existing equations. It uses a grouping algorithm and sets a cutoff radius on each grain for calculating the particle velocity during densification. This method allows for the incorporation of the densification mechanism, which has been commonly ignored in previous work, into phase-field sintering models in three-dimensional simulations with a large number of particles/grains. Moreover, through combination with the smoothed boundary method, material properties of sintered microstructures, such as the effective diffusivity and Young’s modulus, can be calculated during the sintering processes.

36 MATERIALS SCIENCE↗

High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode

The development of all-solid-state Li–S batteries has been greatly impeded by dendrite growth and dendrite penetration, which are both related to the Li metal anode. As a compromised alternative, we report lithium silicide (Li x Si) as a dendrite-free and high-capacity anode with Li source. Here, the as-synthesized Li x Si is relatively soft, highly electronically conductive, and with a high Li diffusivity. These distinctive properties make Li x Si anode viable as an “all-electrochem-active” electrode (consisted of 100 wt.% Li x Si). Compared with the typical composite electrode, the all-electrochem-active electrode not merely maximizes the electrode-level energy density but also minimizes the electrolyte-related interfacial degradation. Li x Si symmetric cell demonstrates a reversible cycling at 4 mA cm –2 for over 320 h. Stress change and morphological evolution of the Li x Si electrode are investigated upon dealloying/alloying. When paired with a S cathode (active mass loading of 3 mg cm –2 ), Li x Si–S full cell shows a good cycling behavior over 500 cycles and rate performance (69% capacity retained at 1.2C) even at 25 °C.

25 ENERGY STORAGE↗