Note: When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external site maintained by the publisher.
Some full text articles may not yet be available without a charge during the embargo (administrative interval).
What is a DOI Number?
Some links on this page may take you to non-federal websites. Their policies may differ from this site.
-
Free, publicly-accessible full text available April 1, 2027
-
A comprehensive understanding of the solid‐electrolyte interphase (SEI) in lithium‐ion batteries is crucial for improving energy efficiency, battery performance, and safety. In this study, a transformer‐based instance segmentation framework, integrating deep convolutional neural networks is introduced with a feature pyramid network (FPN), to quantitatively analyze High‐Resolution Transmission Electron Microscopy (HRTEM) images and explain the complex microstructural features of the SEI. The model is trained on a dataset of simulated HRTEM images generated using Density Functional Theory (DFT)‐optimized grain boundary (GB) structures and calibrated with experimental microscope parameters. The model achieves robust segmentation performance, with training and validation mean intersection over union (mIOU) values of 0.98 and 0.96, respectively. On unseen test data, the model attains mean area match (AM) scores of 91.4% for GBs, 92.3% for Li2CO3, 91.7% for LiF, 88.7% for LiOH, and 88.6% for Li2O. These quantitative results highlight the model's high fidelity and its ability to capture subtle variations in crystallographic orientations and material contrasts. By enabling detailed, statistically grounded segmentation of SEI components, the approach offers valuable insights into ion transport and degradation mechanisms, paving the way for more resilient and efficient energy storage solutions.more » « less
-
Understanding the nucleation and growth mechanisms of highentropy alloy (HEA) nanoparticles is crucial for developing functional nanocrystals with tailored properties. This study investigates the thermal decomposition of mixed metal salt precursors (Fe, Ni, Pt, Ir, Ru) on reduced graphene oxide (rGO) using in situ transmission electron microscopy (TEM) when heated to 1000 °C at both slow (20 °C min−1) and fast (103 °C s−1) heating/cooling rates. Slow heating to 1000 °C revealed the following: (1) The nanoparticles' nucleation occurred through multistage decomposition at lower temperatures (250−300 °C) than single metal salt precursors (300−450 °C). (2) Pt-dominant nanocrystals autocatalytically reduced other elements, leading to the formation of multimetallic FeNiPtIrRu nanoparticles. (3) At 1000 °C, the nanoparticles were single-phase with noble metals enriched compared to transition metals. (4) Slow cooling induced structural heterogeneity and phase segregation due to element diffusion and thermodynamic miscibility. (5) Adding polyvinylpyrrolidone (PVP) suppressed segregation, promoting HEA nanoparticle formation even during slow cooling by limiting atomic diffusion. Under fast heating/cooling, nanoparticles formed as a solid solution of fcc HEA, indicating kinetic control and limited atomic diffusion. The density function theory (DFT) calculations illustrate that the simultaneous presence of metal elements on rGO, as expected by the fast heating process, favors the formation of an fcc HEA structure, with strong interactions between HEA nanoparticles and rGO enhancing stability. This study provides insights into how heating rates and additives like PVP can control phase composition, chemical homogeneity, and stability, enabling the rational design of complex nanomaterials for catalytic, energy, and functional applications.more » « less
-
Metal‐catalyzed graphitization offers a low‐temperature route to crystalline carbon, yet the formation pathways of active catalysts on polymer‐derived carbons remain unclear. We utilized in situ heating scanning transmission electron microscopy to track the conversion of electrospun polyacrylonitrile nanofibers doped with cobalt acetate, nickel acetate, and iron chloride into medium‐entropy FeCoNi nanoparticles that catalyze graphitization. Scanning transmission electron microscopy imaging and chemical mapping reveal a sequential reduction and formation wherein Ni nuclei appear at approximately 300°C, alloy with Co between 400°C and 500°C to form CoNi particles, and incorporate Fe at 700°C–800°C to yield medium‐entropy FeCoNi nanoparticles. Density functional theory and ab initio molecular dynamics reproduce this order by showing facile ligand pyrolysis and rapid reduction for Ni and Co precursors, whereas FeCl3forms refractory oxide intermediates that reduce only at higher temperatures. Ab initio molecular dynamics reveals that smaller FeCoNi clusters exhibit lower thermal stability, becoming mobile at reduced temperatures. Electron diffraction and high‐resolution imaging reveal two graphitization pathways that operate in sequence: dissolution–precipitation at lower temperatures, followed by carbide formation and decomposition at higher temperatures, consistent with Fe3C‐like signatures near 700°C. Raman spectroscopy further reveals that FeCoNi nanoparticles exhibit higher structural graphite order and fewer defects than single‐metal nanoparticle samples, leading to enhanced catalytic performance.more » « lessFree, publicly-accessible full text available March 1, 2027
-
Electrowetting and wettability-driven spreading of liquids on porous and nonporous substrates was investigated using impact of drops of epoxy resin, epoxy hardener, and epoxy resin and hardener, as well as silicone and turpentine oils with oil-soluble aniline dyes onto balsa wood and polypropylene surfaces. The experimental results revealed that the electric field stretched drops of epoxy resin, epoxy hardener, and epoxy resin and hardener after impact on polypropylene substrate in the long-term. The spreading of drops of epoxy resin and turpentine oil with dyes after impact onto porous balsa wood under the action of a 10 kV applied voltage was relatively weak. In addition, the measured footprint areas corresponding to drops of epoxy resin, epoxy hardener, and epoxy resin and hardener demonstrated a significant increase in the wetted areas driven by the applied voltage of 10 kV on polypropylene substrate, whereas on balsa wood, the footprint is practically unaffected by the electric field. Furthermore, it was determined that surface wettability was the main mechanism of spreading of epoxy resin, as well as silicone and turpentine oils with aniline dyes on porous balsa without the electric field applied. On the other hand, insufficient concentration of ions and counterions in silicone oil was responsible for the absence of electrohydrodynamic effects after impact of such drops onto porous balsa substrate subjected to high potentials of 7 and 10 kV. Hence, wettability-driven spreading with imbibition on balsa wood was the only reason for an increase in the wetted area in the case of silicone oil.more » « less
-
Abstract This work investigates the application of poly(3,4‐ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) with polyethylene oxide (PEO) in lithium batteries (LIBs). This composite film comprising PEDOT:PSS and PEO was 3D printed onto a carbon nanofiber (CNF) substrate to serve as a layer between the polypropylene (PP) separator and the lithium anode in LIBs. The resulting CNF‐PEDOT:PSS‐PEO film exhibited superior mechanical and thermal properties compared to conventional PP separators. Mechanical tests revealed a high Young's modulus and puncture strength for the composite film. Thermal stability tests indicated that the CNF‐PEDOT:PSS‐PEO film remained stable at higher temperatures compared to the commercial PP separator, and combustion tests confirmed its superior fire‐resistance properties. In terms of conductivity, the composite film maintained comparable ionic conductivity to the commercial PP separator. Electrochemical tests demonstrated that LIBs incorporating the CNF‐PEDOT:PSS‐PEO film exhibited slight improvement in cycling performance, with a 7.9 % increase in long‐term cycling capacity compared to LIBs using only the commercial PP separator. These findings indicate that the developed CNF‐PEDOT:PSS‐PEO composite film holds promise to improve safety, while maintaining the electrochemical performance of LIBs by reducing dendrite formation and enhancing thermal stability.more » « less
-
Abstract The nucleation and growth of nanoparticles are critical processes determining the size, shape, and properties of resulting nanoparticles. However, understanding the complex mechanisms guiding the formation and growth of colloidal multielement alloy nanoparticles remains incomplete due to the involvement of multiple elements with different properties. This study investigates in situ colloidal synthesis of multielement alloys using transmission electron microscopy (TEM) in a liquid cell. Two different pathways for nanoparticle formation in a solution containing Au, Pt, Ir, Cu, and Ni elements, resulting in two distinct sets of particles are observed. One set exhibits high Au and Cu content, ranging from 10 to 30 nm, while the other set is multi‐elemental, with Pt, Cu, Ir, and Ni, all less than 4 nm. The findings suggest that, besides element miscibility, metal ion characteristics, particularly reduction rates, and valence numbers, significantly impact particle composition during early formation stages. Density functional theory (DFT) simulations confirm differences in nanoparticle composition and surface properties collectively influence the unique growth behaviors in each nanoparticle set. This study illuminates mechanisms underlying the formation and growth of multielement nanoparticles by emphasizing factors responsible for chemical separation and effects of interplay between composition, surface energies, and element miscibility on final nanoparticles size and structure.more » « less
-
Green synthesis of micro/nanomaterials, using glycerol as a sustainable solvent, offers environmentally and health-friendly pathways. Glycerol’s versatility in a solvothermal synthesis is effective for nanoparticle production, yet its mechanistic role in carbonate material formation is unexplored. This study investigates urchin-like strontium carbonate formation via a glycerol-mediated solvothermal synthesis, employing in situ transmission electron microscopy (in situ TEM), scanning electron microscopy, density function theory (DFT), scanning transmission electron microscopy, and X-ray diffraction. In situ TEM observations unveil the initial stages of strontium hydroxide nucleation and subsequent growth as an intermediate phase. The findings suggested that the hyperbranched polymerization of glycerol plays a pivotal role in the formation of urchin-like morphology. Furthermore, the synergistic effect of glycerol and CO2 is proposed as the primary driver for the formation of strontium carbonate. Notably, observations showed a morphological transition from spherical to urchin-like with increasing reaction time. DFT studies proposed glycerol as a coadsorbent, boosting the adsorption energy of CO2 and directing its interaction with Sr(OH)2 resulting in the stable formation of SrCO3. This research provides valuable insights into the urchin-like strontium carbonate formation in a time-dependent process driven by the polymerization of glycerol and its high reactivity with dissolved CO2 at elevated temperatures.more » « less
An official website of the United States government
