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Microstructure control of in situ metal matrix nanocomposites (MMNCs) poses a barrier to their large-scale production. Here, we interrogate in unprecedented detail the formation mechanisms, morphologies, and microstructures of an in situ Al/TiC MMNC processed via salt flux reaction. Through synchrotron-based X-ray nanotomography (TXM) and scanning and transmission electron microscopy, we visualize in over five orders-of-magnitude of length-scale the TiC nanoparticles, Al_3Ti intermetallics, and their co-locations. 3D reconstructions from TXM revealed a surprising variety of Al_3Ti morphologies, including an orthogonal plate structure. By combining our experimental results with phase-field simulations, we demonstrate that this growth form originates from the intermetallic nucleating epitaxially on a TiC particle which is larger than a critical size at a given undercooling. Yet TiC particles that are too small to nucleate Al_3Ti can also impact the growth of the intermetallic, by splitting the intermetallic plates during solidification. These insights on the divalent roles of the nanoparticles offer general guidelines for the synthesis and processing of MMNCs. 

Grain boundaries can greatly affect the transport properties of polycrystalline materials, particularly when the grain size approaches the nanoscale. While grain boundaries often enhance diffusion by providing a fast pathway for chemical transport, some material systems, such as those of solid oxide fuel cells and battery cathode particles, exhibit the opposite behavior, where grain boundaries act to hinder diffusion. To facilitate the study of systems with hindered grain boundary diffusion, we propose a model that utilizes the smoothed boundary method to simulate the dynamic concentration evolution in polycrystalline systems. The model employs domain parameters with diffuse interfaces to describe the grains, thereby enabling solutions with explicit consideration of their complex geometries. The intrinsic error arising from the diffuse interface approach employed in our proposed model is explored by comparing the results against a sharp interface model for a variety of parameter sets. Finally, two case studies are considered to demonstrate potential applications of the model. First, a nanocrystalline yttria-stabilized zirconia solid oxide fuel cell system is investigated, and the effective diffusivities are extracted from the simulation results and are compared to the values obtained through mean-field approximations. Second, the concentration evolution during lithiation of a polycrystalline battery cathode particle is simulated to demonstrate the method’s capability.

 

We present a phase-field (PF) model to simulate the microstructure evolution occurring in polycrystalline materials with a variation in the intra-granular dislocation density. The model accounts for two mechanisms that lead to the grain boundary migration: the driving force due to capillarity and that due to the stored energy arising from a spatially varying dislocation density. In addition to the order parameters that distinguish regions occupied by different grains, we introduce dislocation density fields that describe spatial variation of the dislocation density. We assume that the dislocation density decays as a function of the distance the grain boundary has migrated. To demonstrate and parameterize the model, we simulate microstructure evolution in two dimensions, for which the initial microstructure is based on real-time experimental data. Additionally, we applied the model to study the effect of a cyclic heat treatment (CHT) on the microstructure evolution. Specifically, we simulated stored-energy-driven grain growth during three thermal cycles, as well as grain growth without stored energy that serves as a baseline for comparison. We showed that the microstructure evolution proceeded much faster when the stored energy was considered. A non-self-similar evolution was observed in this case, while a nearly self-similar evolution was found when the microstructure evolution is driven solely by capillarity. These results suggest a possible mechanism for the initiation of abnormal grain growth during CHT. Finally, we demonstrate an integrated experimental-computational workflow that utilizes the experimental measurements to inform the PF model and its parameterization, which provides a foundation for the development of future simulation tools capable of quantitative prediction of microstructure evolution during non-isothermal heat treatment.

 

Electrochemical impedance spectroscopy (EIS) is a powerful technique for material characterization and diagnosis of the solid oxide fuel cells (SOFC) as it enables separation of different phenomena such as bulk diffusion and surface reaction that occur simultaneously in the SOFC. In this work, we simulate the electrochemical impedance in an experimentally determined, three-dimensional (3D) microstructure of a mixed ion-electron conducting (MIEC) SOFC cathode. We determine the impedance response by solving the mass conservation equation in the cathode under the conditions of an AC load across the cathode’s thickness and surface reaction at the pore/solid interface. Our simulation results reveal a need for modifying the Adler-Lane-Steele model, which is widely used for fitting the impedance behavior of a MIEC cathode, to account for the difference in the oscillation amplitudes of the oxygen vacancy concentration at the pore/solid interface and within the solid bulk. Moreover, our results demonstrate that the effective tortuosity is dependent on the frequency of the applied AC load as well as the material properties, and thus the prevalent practice of treating tortuosity as a constant for a given cathode should be revised. Finally, we propose a method of determining the aforementioned dependence of tortuosity on material properties and frequency by using the EIS data. 

Most research on the electrochemical dynamics in materials for high‐energy Li‐ion batteries has focused on the global behavior of the electrode. This approach is susceptible to misleading analyses resulting from idiosyncratic kinetic conditions, such as surface impurities inducing an apparent two‐phase transformation within LiNi_0.8Co_0.15Al_0.05O₂. Here, nano‐focused X‐ray probes are used to measure delithiation operando at the scale of secondary particle agglomerates in layered cathode materials during charge. After an initial latent phase, individual secondary particles undergo rapid, stochastic, and largely uniform delithiation, which is in contrast with the gradual increase in cell potential. This behavior reproduces across several layered oxides. Operando X‐ray microdiffraction (‐XRD) leverages the relationship between Li content and lattice parameter to further reveal that rate acceleration occurs between Li‐site fraction (x_Li) ≈0.9 and ≈0.5 for LiNi_0.8Co_0.15Al_0.05O₂. Physics‐based modeling shows that, to reproduce the experimental results, the exchange current density (i₀) must depend onx_Li, and thati₀should increase rapidly over three orders of magnitude at the transition point. The specifics and implications of this jump ini₀are crucial to understanding the charge‐storage reaction of Li‐ion battery cathodes.

 

The Materials Genome Initiative (MGI) advanced a new paradigm for materials discovery and design, namely that the pace of new materials deployment could be accelerated through complementary efforts in theory, computation, and experiment. Along with numerous successes, new challenges are inviting researchers to refocus the efforts and approaches that were originally inspired by the MGI. In May 2017, the National Science Foundation sponsored the workshop “Advancing and Accelerating Materials Innovation Through the Synergistic Interaction among Computation, Experiment, and Theory: Opening New Frontiers” to review accomplishments that emerged from investments in science and infrastructure under the MGI, identify scientific opportunities in this new environment, examine how to effectively utilize new materials innovation infrastructure, and discuss challenges in achieving accelerated materials research through the seamless integration of experiment, computation, and theory. This article summarizes key findings from the workshop and provides perspectives that aim to guide the direction of future materials research and its translation into societal impacts.

 

1D materials, such as nanofibers or nanoribbons are considered as the future ultimate limit of downscaling for modern electrical and electrochemical devices. Here, for the first time, nanofibers of a solid solution transition metal trichalcogenide (TMTC), Nb_1‐xTa_xS₃, are successfully synthesized with outstanding electrical, thermal, and electrochemical characteristics rivaling the performance of the‐state‐of‐the art materials for each application. This material shows nearly unchanged sheet resistance (≈740 Ω sq⁻¹) versus bending cycles tested up to 90 cycles, stable sheet resistance in ambient conditions tested up to 60 days, remarkably high electrical breakdown current density of ≈30 MA cm⁻², strong evidence of successive charge density wave transitions, and outstanding thermal stability up to ≈800 K. Additionally, this material demonstrates excellent activity and selectivity for CO₂conversion to CO reaching ≈350 mA cm⁻²at −0.8 V versus RHE with a turnover frequency number of 25. It also exhibits an excellent performance in a high‐rate Li–air battery with the specific capacity of 3000 mAh g⁻¹at a current density of 0.3 mA cm⁻². This study uncovers the multifunctionality in 1D TMTC alloys for a wide range of applications and opens a new direction for the design of the next generation low‐dimensional materials.