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  1. Thermal Cycling-Driven Microstructural Changes of Eutectic Al-Si Phase Change Materials in SS304 Containers Revealed by Multi-Modal Imaging

    Aluminum-based Al-Si alloys are widely used as phase change materials (PCMs) in thermal energy storage (TES) systems owing to their high volumetric latent heat and superior thermal conductivity. However, their long-term reliability is limited by degradation processes that remain insufficiently understood. In this work, we employ a multimodal, correlative characterization framework to systematically resolve the degradation behavior of eutectic Al-Si PCMs in contact with SS304 containers under repeated thermal cycling. By integrating high-resolution electron microscopy, three-dimensional X-ray fluorescence (3D XRF) imaging, and differential scanning calorimetry (DSC), we directly link spatially resolved compositional and microstructural evolution to changes in thermophysical properties.more » The correlative analysis reveals that elemental leaching of Fe, Cr, and Ni from the stainless-steel container into the PCM drives the formation of intermetallic compounds (IMCs) both at the interface and within the bulk PCM, leading to pronounced compositional heterogeneity. These interfacial reactions and diffusion-induced transformations progressively destabilize the Al-Si eutectic, reducing the effective phase-transforming fraction. Consistent with these observations, DSC measurements show a decrease in melting temperature and latent heat of fusion with thermal cycling. These results underscore the critical influence of interfacial reactions and material compatibility on the stability, durability, and overall performance of Al-Si-based TES systems.« less
  2. Mechanistic Transition of Stainless Steel 304L Corrosion in MgCl2 Phase Change Material Under Thermal Cycling

    Magnesium chloride (MgCl2)-based molten salt phase change materials (PCMs) are promising candidates for thermal energy storage (TES) owing to their advantageous thermophysical properties, however, their high corrosivity in the molten state limits material compatibility. In this study, the corrosion behavior of 304?L stainless steel (SS304L) exposed to MgCl2 PCM was investigated as a function of thermal cycling (up to 9000 cycles) relevant to PCM-based TES systems. Microstructural changes and elemental redistribution at the alloy-salt interface under thermal cycling conditions were characterized using synchrotron-based X-ray fluorescence (XRF) and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS). Results show thatmore » corrosion is governed by selective Cr-dissolution and elemental diffusion near the interface and grain boundaries. A clear transition in the dominant corrosion mechanism is observed with increasing thermal cycles. Surface corrosion is the dominant mechanism up to 1000 cycles, whereas intergranular corrosion becomes the primary degradation mode beyond 2000 cycles. These mechanistic changes are interpreted in terms of evolving interfacial chemistry, microstructure and the diffusion-driven redistribution of alloying elements.« less
  3. Roadmap to 100 GWDC: Scientific and supply chain challenges for CdTe photovoltaics

    This roadmap highlights pathways to expand the CdTe module manufacturing capacity per year to 100 GWDC by 2030 by improving Te extraction from existing supply chains, minimizing Te usage in modules by leveraging thinner absorbers, and focusing research efforts in key areas to improve module efficiencies. Both scientific and supply chain innovations will be necessary to maintain the high compound annual growth rate of the CdTe photovoltaic (PV) industry and cement its role as a key technology for multi-TW-scale PV deployment.
  4. Revealing Progressive Degradation of Cobalt Oxide Nanoparticles During Thermochemical Redox Cycling via Operando STEM-EELS

    Metal oxides are promising materials for long-duration thermochemical energy storage. Efforts to characterize their reaction kinetics, conversion rate, and morphological evolution during thermochemical cycling have largely focused on bulk and microscale measurements. However, the design of nanostructured metal oxides could improve the reaction reversibility and kinetics, warranting the development of platforms to investigate how these materials behave at the nanoscale. Here, we demonstrate the use of correlative, time-resolved electron energy loss spectroscopy and imaging in an environmental transmission electron microscope for studying the thermochemical cyclability of cobalt oxide nanoparticles with high spatial and temporal resolution. The spectroscopic data reveal amore » striking decrease in reaction kinetics after the first cycle, resulting from sintering-driven nanostructural densification. Comparison between cycling in humid and dry air shows that atmospheric conditions can modulate reaction transition temperatures but have limited effects on sintering over multiple cycles, suggesting long-term durability will instead rely on synthetic and/or nanostructural modifications.« less
  5. Operando X-ray imaging reveals size-dependent evolution of cobalt oxide thermochemical material during thermal redox cycles

    Multivalent metal oxides are promising thermochemical materials (TCMs) for energy storage and conversion owing to their high energy density, air compatibility, and high-temperature stability. Co3O4 serves as a model system for examining particle-size- and structure-dependent redox behavior. While particle size and porosity are known to affect performance, their interplay and the kinetics of pore formation during cycling remain unclear. Here we show the chemical and 3D morphological evolution of Co3O4 micro- and nanoparticles during redox cycles at 800–900 °C using thermal analysis, in-situ synchrotron transmission X-ray microscopy (TXM), and scanning electron microscopy. Thermal analysis shows that nanoparticles re-oxidize more rapidlymore » than microparticles at 800 °C. In-situ nanotomography and chemical imaging reveals that nanoparticles undergo redox conversion without forming internal pores, whereas microparticles develop isolated porosity during reduction. These pores persist through re-oxidation, correlating to a lower conversion rate in subsequent cycles. Our results demonstrate distinct degradation kinetics in Co3O4 micro- and nanoparticles, underscoring the critical role of particle size and porosity in redox performance and informing strategies to enhance the long-term efficiency of metal oxide TCMs.« less
  6. Upgrading polycrystalline battery cathodes to single-crystal NMC622 via morphology-controlled recycling

    The importance of recycling lithium-ion batteries is growing within the battery supply chain as a promising answer to economic and environmental challenges. Many initiatives are in progress to improve battery recycling technologies, as existing methods encounter major obstacles. Here, in this study, we report a polyol-metallurgical recycling process to upgrade polycrystalline cathodes to single-crystal cathodes, while detailing the coprecipitation and cathode resynthesis steps. Using citric acid and ethylene glycol enables effective leaching, simple separation, and controlled coprecipitation. Leveraging the distinct poly-esterification reactions in the precipitation phase, we achieve precise control over morphology and particle sizes. Using the coprecipitates, we havemore » successfully resynthesized a LiNi0.6Co0.2Mn0.2O2 cathode with a similar elemental composition compared to the pristine cathode, free of impurities, and exhibiting a single-crystal morphology featuring grain sizes in the range of 10 μm. The study showcases the potential of polyol metallurgy as a novel and efficient method for recycling lithium-ion batteries and synthesizing advanced cathode materials.« less
  7. Structural stability, elemental ordering, and transport properties of layered ScTaN2

    Ternary transition metal (TM) nitrides have gained significant attention in thin film research due to their promising properties for a broad range of applications. Particularly, some of the ternary TM nitrides have been predicted to adopt layered structures that make them interesting for thermoelectric conversion and quantum materials applications. Unfortunately, synthesis of TM ternary nitride films by physical vapor deposition often favors disordered 3D structures rather than the predicted 2D-like layered structure. In this study, we investigate the structural interplay in the Sc-Ta-N ternary system using a combinatorial approach. Combinatorial libraries S⁢c𝑥⁢T⁢a1−𝑥⁢N are synthesized following a two-step method: First, depositmore » film precursors by cosputtering and then process the resulting 3D-structured samples with rapid thermal annealing. Synchrotron grazing-incidence wide-angle x-ray scattering on films annealed at 1200 ⁢°⁢C for 20 min leads to the nucleation of ScTaN2 layered structure (𝑃⁢63/𝑚⁢𝑚⁢𝑐) near stoichiometry. We find that the layered structure can accommodate large off-stoichiometry in the Ta-rich region (𝑥 < 0.5), facilitated by the alloying with quasi-isostructural Ta5⁢N6 compound that exists on a composition tie line at 𝑥 = 0. While focusing on ScTaN2, we estimate the long-range order parameter in near-stoichiometric films to be 0.86, corresponding to a fraction of Sc/Ta antisites of 7%. Transport measurements on ScTaN2 reveal a nearly temperature-independent high carrier density (1021 c⁢m−3), suggesting a heavily doped semiconductor or semimetallic character, consistent with a small positive Seebeck coefficient of +19 µV/K. The carrier mobility at 2 K is relatively small (9.5c⁢m2 V−1 s−1) and the residual-resistivity ratio is minor, suggesting that electrical conduction is dominated by defects or disorder. Measured magnetoresistance suggests possible weak antilocalization at 2 K. This paper highlights the interplay between ScTaN2 and Ta5⁢N6 crystal structures in stabilizing layered materials, emphasizes the importance of cation order/disorder for potential tunable alloys, and suggests that ScTaN2 is a promising platform for exploring electronic properties.« less
  8. UV + Damp Heat Induced Power Losses in Fielded Utility N-Type Si PV Modules

    A recent trend in commercial PV modules is a transition to n-type silicon cells, including passivated emitter rear totally diffused (n-PERT), tunnel oxide passivated contact (TOPCon), and silicon heterojunction (SHJ). There is evidence via lab studies that some of these cells are more susceptible to UV induced degradation (UVID), yet there is a lack of confirmation that such degradation occurs in the field. Current IEC standards designed to screen for early module failures require only minimal UV exposure (15 kWh/m2 280-400 nm, ~2-3 months equivalent outdoor exposure). Here, we investigate fielded n-PERT silicon (Si) modules from a commercial utility thatmore » show power losses of ~2%/year. We present a comprehensive picture of the physics and chemistry of degradation supported by both module and cell electronic characterization (EL, PL, IV, EQE, and DLIT) and materials-level morphological and chemical analysis (SEM, EDS, XPS, FTIR, and HPLC). All sampled site modules show short circuit current (Isc) and open circuit voltage (Voc) losses when compared to unfielded spares, with the most severely degraded also having losses in fill factor (FF). We identify two different degradation modes contributing to overall power loss: (1) external quantum efficiency (EQE) measurements show losses in the blue range of the spectra, indicative of cell surface recombination losses, and (2) variations in high series resistance (Rs) at the cell level that are correlated with compositional differences in cell metallization. Using unfielded spares, we were able to reproduce Voc, Isc, and EQE losses via a minimum UV stress of 67.5 kWh/m2 (280-400 nm), 4.5x the exposure currently required in IEC 61215-2 (MQT 10). Degradation continued with additional UV dosage equivalent to the fielded modules (405 kWh/m2 total), with power loss leveling out at an average of 6.1%. Subsequent 1000 h of 85% RH/85degrees C damp heat testing showed that cells exposed to UV underwent additional severe series resistance degradation, even those without the susceptible paste composition seen in the field, whereas non-UV exposed cells saw little change. We attribute this to higher concentrations of acetic acid generated on the UV exposed area of the module, leading to degradation of the gridline/cell interface and high Rs. This study is unique in that it reproduces field observed utility scale UVID with an accelerated test and supports the need for standards development for longer UV exposure combined with other stress factors to catch materials interplay within a module package.« less
  9. Influence of Electrolyte Additives on Interfacial Stability of Manganese-Rich Lithium-Ion Battery Cathodes

    Affordable, long-lasting energy storage has become critical to support increased electricity demand in recent years. Cobalt-free, lithium- and manganese-rich lithium nickel manganese oxide (LMR-NM) cathodes stand to reduce cost and supply-chain concerns associated with traditional cobalt-containing cathodes for lithium-ion batteries by leveraging more earth-abundant materials; however, they have shown issues with long-term cycling stability. Here, we investigate lithium difluoro(oxalate)borate (LiDFOB), tris(trimethylsilyl) phosphite (TMSPi), and vinylene carbonate (VC) electrolyte additives for their ability to improve cycling performance of LMR-NM (0.3 Li2MnO3 + 0.7 LiMn0.5Ni0.502) cells. Cryogenic scanning transmission electron microscopy (cryo-STEM) with electron energy loss spectroscopy enables the construction of amore » structure–function relationship between cathode electrolyte interphase (CEI) characteristics and the electrochemical performance of cells aged with these additives. We find the combination of 2 wt % TMSPi + 1 wt % LiDFOB performs better than any single additive, achieving a 28% improvement in specific capacity over the baseline electrolyte after long-term cycling. We attribute this to LiDFOB mitigating Mn ion dissolution, with cryo-STEM showing Mn stabilized up to the CEI surface, coupled with improved CEI structure and chemistry enabled by TMSPi, evidenced by a moderately thick (∼7–15 nm) CEI that appears to protect against further electrolyte reactions with the particle. These results, achieved through site-specific nanoscale characterization, directly reveal mechanisms through which electrolyte engineering can improve the performance of earth-abundant cathodes, enabling informed development of more affordable and reliable batteries to meet future energy storage needs.« less
  10. ZnGa2Te4 thin-film absorbers for photoelectrochemical CO2 reduction

    Photoelectrochemical (PEC) carbon dioxide reduction reaction (CO2RR) has been considered as a promising route to convert and store solar energy into chemical fuels. It is crucial to find suitable photoelectrode materials that are photo-catalytically active and exhibit excellent photochemical stability. One of the promising contenders is ZnTe with the ∼2.26 eV band gap and prolonged stability under CO2RR PEC conditions. Herein, a new telluride based thin-film ZnGa2Te4 photocathode with lower band gap and stronger visible light absorption compared to ZnTe is synthesized and characterized using a combinatorial sputtering technique. A two-step annealing method with excess Te supply is implemented tomore » synthesize nearly stoichiometric ZnGa2Te4 absorber material with a zincblende-derived tetragonal crystal structure confirmed by synchrotron X-ray and electron diffraction. Theoretical calculations show that ZnGa2Te4 has suitable direct bandgap (∼1.86 eV) and high absorption coefficient ∼105 cm−1, in agreement with experimentally prepared films. Transient absorption spectroscopy reveals the biexponential decay dynamics, with time constants, τ1 ∼ 0.04, and τ2 ∼ 0.65 μs in microsecond time scales and provides the optical transition pathways for this semiconductor thin film. PEC measurements show that the ZnGa2Te4 photocurrent densities are comparable to the widely investigated ZnTe photocathodes or even surpass it under simulated sunlight condition. ZnGa2Te4 samples demonstrate promising photoelectrochemical stability, maintaining consistent performance under illumination. The inclusion of diaryliodonium additive substantially increases its CO2RR selectivity to ∼60%. These findings open a new avenue for the synthesis of telluride-based thin-film photocathodes for further exploration and will motivate future research to integrate this potential photocathode material into PEC devices.« less
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