Tracking the Mn diffusion in the carbon-supported nanoparticles through the collaborative analysis of atom probe and evaporation simulation

Carbon-supported nanoparticles have been used widely as efficient catalysts due to their enhanced surface-to-volume ratio. To investigate their structure-property relationships, acquiring 3D elemental distribution is highly required. Here, the carbon-supported Pt, PtMn alloy, and ordered Pt3Mn nanoparticles are synthesized and analyzed with atom probe tomography as model systems. The significant difference of Mn distribution after the heat-treatment was found. Finally, the field evaporation behavior of the carbon support was discussed and each acquired reconstruction was compared with computational results from the evaporation simulation. This paper provides a guideline for studies using atom probe tomography on the heterogeneous carbon-nanoparticle system that leads to insights toward to a wide application in carbon-supported nano-catalysts

Facilitating the systematic nanoscale study of battery materials by atom probe tomography through in-situ metal coating

Through its capability for 3D mapping of Li at the nanoscale, atom probe tomography (APT) is poised to play a key role in understanding the microstructural degradation of lithium-ion batteries (LIB) during successive charge and discharge cycles. However, APT application to materials for LIB is plagued by the field induced delithiation (deintercalation) of Li-ions during the analysis itself that prevents the precise assessment of the Li distribution. Here, we showcase how a thin Cr-coating, in-situ formed on APT specimens of NMC811 in the focused-ion beam (FIB), preserves the sample's integrity and circumvent this deleterious delithiation. Cr-coated specimens demonstrated remarkable improvements in data quality and virtually eliminated premature specimen failures, allowing for more precise measurements via. improved statistics. Through improved data analysis, we reveal substantial cation fluctuations in commercial grade NMC811, including complete grains of LiMnO. The current methodology stands out for its simplicity and cost-effectiveness and is a viable approach to prepare battery cathodes and anodes for systematic APT studies

In-situ metallic coating of atom probe specimen for enhanced yield, performance, and increased field-of-view

Atom probe tomography requires needle-shaped specimens with a diameter typically below 100 nm, making them both very fragile and reactive, and defects (notches at grain boundaries or precipitates) are known to affect the yield and data quality. The use of a conformal coating directly on the sharpened specimen has been proposed to increase yield and reduce background. However, to date, these coatings have been applied ex-situ and mostly are not uniformly. Here, we report on the controlled focused ion beam in-situ deposition of a thin metal film on specimens immediately after specimen preparation. Different metallic targets e.g. Cr were attached to a micromanipulator via a conventional lift-out method and sputtered using the Ga or Xe ions. We showcase the many advantages of coating specimens from metallic to non-metallic materials. We have identified an increase in data quality and yield, an improvement of the mass resolution, as well as an increase in the effective field-of-view enabling visualization of the entire original specimen, including the complete surface oxide layer. The ease of implementation of the approach makes it very attractive for generalizing its use across a very wide range of atom probe analyses

Grain Boundary Phases in NbFeSb Half-Heusler Alloys: A New Avenue to Tune Transport Properties of Thermoelectric Materials

Many thermoelectric materials benefit from complex microstructures. Grain boundaries (GBs) in nanocrystalline thermoelectrics cause desirable reduction in the thermal conductivity by scattering phonons, but often lead to unwanted loss in the electrical conductivity by scattering charge carriers. Therefore, modifying GBs to suppress their electrical resistivity plays a pivotal role in the enhancement of thermoelectric performance, zT. In this work, different characteristics of GB phases in Ti-doped NbFeSb half-Heusler compounds are revealed using a combination of scanning transmission electron microscopy and atom probe tomography. The GB phases adopt a hexagonal close-packed lattice, which is structurally distinct from the half-Heusler grains. Enrichment of Fe is found at GBs in Nb0.95Ti0.05FeSb, but accumulation of Ti dopants at GBs in Nb0.80Ti0.20FeSb, correlating to the bad and good electrical conductivity of the respective GBs. Such resistive to conductive GB phase transition opens up new design space to decouple the intertwined electronic and phononic transport in thermoelectric materials

Novel Ni–Co-based superalloys with high thermal stability and specific yield stress discovered by directed energy deposition

We report on the rapid alloy screening of Ni–Co–Ti–Al–Mo superalloys with high thermal stability and specific yield stress by means of directed energy deposition. A laser directed energy deposition, a specific type of additive manufacturing, was employed using multiple powder feeders and elemental powders. Fifty superalloys of different compositions were deposited and the heat-treated microstructure and γ' solvus temperature were examined. The 43Ni–38Co–9Ti–6Al–4Mo superalloy (atomic percent composition) exhibited a uniform γ/γ' microstructure and a γ' solvus temperature of 1202°C. The beneficial properties of the superalloy were also found in the cast superalloy of identical composition. The cast superalloy exhibited a thermally stable γ/γ' microstructure with cuboidal γ' precipitates even after long-term aging heat treatments at 800°C, 900°C, and 1000°C up to 500 h. The γ'-coarsening mechanism was evaluated based on the Lifshitz–Slyozov–Wagner model and the trans-interface diffusion-controlled model. A transition between these two mechanisms was observed with an increase in aging temperature. Atom probe tomography analyses revealed that the sluggish interface diffusion of Co and corresponding reduction of the interfacial energy induced the transition of the γ'-coarsening mechanism. Moreover, the cast superalloy showed an enhanced specific yield stress attributed to its exceptionally low alloy density of 7.61 g/cm3

Tailoring nanostructured NbCoSn-based thermoelectric materials via crystallization of an amorphous precursor

Tailoring nanostructures is nowadays a common approach for enhancing the performance of thermoelectric Heusler compounds by decreasing the thermal conductivity without significantly affecting the electrical conductivity. However, the most widely reported method for obtaining nanostructured thermoelectrics, an approach based on crushing as-cast alloy ingots followed by sintering of the debris, only gives limited control of the final nanostructure due to residual elemental segregation after casting. Here, a novel approach for fabricating nanostructured Heusler compounds is presented, which is based on crystallizing an amorphous precursor of NbCo1.1Sn composition. This method yields two distinct nanostructures, namely one comprising only half-Heusler grains and another one comprising half-Heusler grains and full-Heusler nano-precipitates. The latter sample exhibits enhanced negative Seebeck coefficients as compared to the former over a wide temperature range. Using advanced characterization techniques, such as high-resolution transmission electron microscopy and atom probe tomography, in conjunction with ab initio density functional theory, detailed insights into the nanostructure and electrical properties of the specimens are provided. Filtering of low energy and mobility electrons at the half-Heusler and full-Heusler interface along with the formation of Co interstitial defects in the half-Heusler matrix are proposed to be the possible causes for the enhanced Seebeck coefficient of the nano-precipitate containing specimen.</p

Effect of Heat Treatment Temperature on the Crystallization Behavior and Microstructural Evolution of Amorphous NbCo_1.1Sn

Heat treatment-induced nanocrystallization of amorphous precursors is a promising method for nanostructuring half-Heusler compounds as it holds significant potential in the fabrication of intricate and customizable nanostructured materials. To fully exploit these advantages, a comprehensive understanding of the crystallization behavior of amorphous precursors under different crystallization conditions is crucial. In this study, we investigated the crystallization behavior of the amorphous NbCo1.1Sn alloy at elevated temperatures (783 and 893 K) using transmission electron microscopy and atom probe tomography. As a result, heat treatment at 893 K resulted in a significantly finer grain structure than heat treatment at 783 K owing to the higher nucleation rate at 893 K. At both temperatures, the predominant phase was a half-Heusler phase, whereas the Heusler phase, associated with Co diffusion, was exclusively observed at the specimen annealed at 893 K. The Debye–Callaway model supports that the lower lattice thermal conductivity of NbCo1.1Sn annealed at 893 K is primarily attributed to the formation of Heusler nanoprecipitates rather than a finer grain size. The experimental findings of this study provide valuable insights into the nanocrystallization of amorphous alloys for enhancing thermoelectric properties

Synthesis of Chemically Ordered Pt₃Fe/C Intermetallic Electrocatalysts for Oxygen Reduction Reaction with Enhanced Activity and Durability via a Removable Carbon Coating

Recently, Pt₃M (M = Fe, Ni, Co, Cu, etc.) intermetallic compounds have been highlighted as promising candidates for oxygen reduction reaction (ORR) catalysts. In general, to form those intermetallic compounds, alloy phase nanoparticles are synthesized and then heat-treated at a high temperature. However, nanoparticles easily agglomerate during the heat treatment, resulting in a decrease in electrochemical surface area (ECSA). In this study, we synthesized Pt–Fe alloy nanoparticles and employed carbon coating to protect the nanoparticles from agglomeration during heat treatment. As a result, Pt₃Fe L1₂ structure was obtained without agglomeration of the nanoparticles; the ECSA of Pt–Fe alloy and intermetallic Pt₃Fe/C was 37.6 and 33.3 m² g_Pt^–1, respectively. Pt₃Fe/C exhibited excellent mass activity (0.454 A mg_Pt^–1) and stability with superior resistances to nanoparticle agglomeration and iron leaching. Density functional theory (DFT) calculation revealed that, owing to the higher dissolution potential of Fe atoms on the Pt₃Fe surface than those on the Pt–Fe alloy, Pt₃Fe/C had better stability than Pt–Fe/C. A single cell fabricated with Pt₃Fe/C showed higher initial performance and superior durability, compared to that with commercial Pt/C. We suggest that Pt₃M chemically ordered electrocatalysts are excellent candidates that may become the most active and durable ORR catalysts available