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At least 775 records · Page 43

Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material

Layered Li-rich Ni, Mn, Co (NMC) oxide cathodes in Li-ion batteries provide high specific capacities (>250 mAh/g) via O-redox at high voltages. However, associated high-voltage interfacial degradation processes require strategies for effective electrode surface passivation. Here, we show that an acidic surface treatment of a Li-rich NMC layered oxide cathode material leads to a substantial suppression of CO 2 and O 2 evolution, ~90% and ~100% respectively, during the first charge up to 4.8 V vs. Li +/0 . CO 2 suppression is related to Li 2 CO 3 removal as well as effective surface passivation against electrolyte degradation. This treatment does not result in any loss of discharge capacity and provides superior long-term cycling and rate performance compared to as-received, untreated materials. We also quantify the extent of lattice oxygen participation in charge compensation (“O-redox”) during Li + removal by a novel ex-situ acid titration. Our results indicate that the peroxo-like species resulting from O-redox originate on the surface at least 300 mV earlier than the activation plateau region around 4.5 V. X-ray photoelectron spectra and Mn -L X-ray absorption spectra of the cathode powders reveal a Li + deficiency and a partial reduction of Mn ions on the surface of the acid-treated material. More interestingly, although the irreversible oxygen evolution is greatly suppressed through the surface treatment, our O K-edge resonant inelastic X-ray scattering shows the lattice O-redox behavior largely sustained. The acidic treatment, therefore, only optimizes the surface of the Li-rich material and almost eliminates the irreversible gas evolution, leading to improved cycling and rate performance. This work therefore presents a simple yet effective approach to passivate cathode surfaces against interfacial instabilities during high-voltage battery operation.

25 ENERGY STORAGE↗

Selective Bidentate Coordination Reconstructs Residual PbI 2 to Homogenize Interfacial Energetics in Perovskite Solar Cells

Spatially heterogeneous interfacial energetics, often originating from residual lead iodide (PbI 2 ), represent a fundamental bottleneck to both the efficiency and operational stability of perovskite photovoltaics. Conventional PbI 2 passivation strategies based on monodentate ligands or highly polar solvents either interact weakly with PbI 2 or undesirably perturb the underlying three-dimensional perovskite lattice. Here, we report a diammonium bidentate strategy that selectively reconstructs residual PbI 2 into corner-sharing PbI 6 octahedra while preserving the bulk perovskite. Enabled by dual-site coordination, a newly designed thiophene-based bidentate ligand (MeXT) stabilizes PbI 6 units during passivation and establishes spatially homogeneous interfacial energetics. Perovskite solar cells incorporating MeXT achieve 26.19% power conversion efficiency and retain over 80% of their initial efficiency after 1000 h of continuous 1-sun illumination at 75 °C. This dual-anchor coordination passivation strategy establishes a general design principle for selectively treating residual PbI 2 and creating electronically coherent and operationally stable interfaces in perovskite photovoltaics.

ligands↗

UV-Induced Degradation of High-Efficiency Solar Cells with Different Architectures

The ultraviolet-induced degradation (UVID) of solar panels is associated with the deterioration of cell performance and reduced reliability of packaging materials. Here we examine the UV stability of different architectures of high-efficiency solar cells without any encapsulation. Identical UV exposure tests were performed at two different labs using UVA-340 fluorescent lamps under different electrical bias configurations (open- or short-circuit) and irradiated cell surfaces (for bifacial technologies). Cell technologies, including heterojunction (HJ), interdigitated back-contact cells (IBC), passivated emitter rear contact (PERC), passivated emitter rear totally-diffused (PERT), are found to be more susceptible to UVID, leading to significant Isc loss (up to 4%) and P max loss (up to 15%) as compared to the conventional back surface field (Al-BSF) cells after exposure to UV irradiation of 8.92 MJ-m -2 -nm -1 at 340 nm. Additionally, the bifacial cells when irradiated from the backside exhibited greater photocurrent loss compared to the front side exposure, indicating potential sensitivity of rear surface passivation to UV radiation.

crystalline silicon↗

Thermal Modeling and Limitations for Power Electronics Embedded in Medium-Voltage Cables

As next-generation energy technologies gain traction and power demand increases, the existing electrical infrastructure faces significant stress, prompting innovative solutions to enhance the grid's capacity and lifespan. This work explores the possibility of embedding medium-voltage (MV) power electronics directly inline with the cable, and the resulting thermal challenges. Since the majority of power distribution cables installed in the U.S. are passively cooled, the work focuses primarily on passive cooling, with an emphasis on the limitations of axial heat spreading within the cable. To date, literature on axial spreading of high incident heat loads on cables and cable environments is limited, typically reporting cases with <10 W of incident heat load. This work will explore the considerations, limits, and tradeoffs of cable-embedded heat loads significantly larger than the cable losses. Both external and internal effects are modeled analytically in nondimensional terms via a Biot number analysis, allowing fundamental limits and tradeoffs to be derived. The work culminates in the design and experimental validation of a cable-embedded thermal system capable of passively dissipating 300 W of heat from a coaxial SiC mosfet switch module over a length of 20 cm, thus validating the possibility of MV cable-embedded power electronics from a thermal standpoint.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Nanoscale TiO 2 coating improves water stability of Cs 2 SnCl 6

To improve the stability of Cs 2 SnCl 6 under aqueous/moisture environments, we applied a concept of artificial passivation by depositing a protective TiO 2 coating of 10 nm on the surface of Cs 2 SnCl 6 . Static leaching experiments results indicate that the initial release rates of Cs + and Cl - are decreased by 20–30 times with TiO 2 coating, suggesting its possibility to improve the short-term water/environmental stability of Cs 2 SnCl 6 . An amorphous-to-crystalline phase transition in TiO 2 film was observed, possibly resulting in degradation of Cs 2 SnCl 6 . However, the crystalline TiO 2 film still remains after 21 days water exposure and can still act as an effective passivation layer to reduce the release rates of Cs + and Cl - by as much as about 17 and 7 times, respectively, relative to static leaching without artificial coatings. Therefore, the water/environmental stability of metal halide perovskite Cs 2 SnCl 6 , which is a highly soluble molecular salt, can be enhanced by the nanoscale TiO 2 coating as an artificial passivation film.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ion Pair Uptake in Ion Gel Devices Based on Organic Mixed Ionic–Electronic Conductors

Abstract In organic mixed ionic–electronic conductors (OMIECs), it is critical to understand the motion of ions in the electrolyte and OMIEC. Generally, the focus is on the movement of net charge during gating, and the motion of neutral anion–cation pairs is seldom considered. Uptake of mobile ion pairs by the semiconductor before electrochemical gating (passive uptake) can be advantageous as this can improve device speed, and both ions can participate in charge compensation during gating. Here, such passive ion pair uptake in high‐speed solid‐state devices is demonstrated using an ion gel electrolyte. This is compared to a polymerized ionic liquid (PIL) electrolyte to understand how ion pair uptake affects device characteristics. Using X‐ray photoelectron spectroscopy, the passive uptake of ion pairs from the ion gel into the OMIEC is detected, whereas no uptake is observed with a PIL electrolyte. This is corroborated by X‐ray scattering, which reveals morphological changes to the OMIEC from the uptake of ion pairs. With in situ Raman, a reorganization of both anions and cations is then observed during gating. Finally, the speed and retention of OMIEC‐based neuromorphic devices are tuned by controlling the freedom of charge motion in the electrolyte.

Quill, Tyler J.↗

Modeling of transport in carrier-selective contacts in silicon heterojunction solar cells

High-performance silicon heterojunction (SHJ) solar cells use carrier-selective contact structures based on hydrogentated amorphous Si (a-Si:H) to maximize collection of photogenerated carriers. The high open circuit voltages observed experimentally in SHJ cells require that the carrier-selective contacts provide selectivity and passivation. However, a microscopic understanding of the dynamics of carrier transport through the a-Si layer is currently lacking. In this paper, we explicitly simulate the transport of holes across the a-Si:H(i) layer using a novel kinetic Monte Carlo approach. The hole-selective contact structure investigated in this paper uses p-type doped a-Si:H(p) and intrinsic a-Si:H(i) on an n-type crystalline silicon wafer, where the selectivity is provided by the a-Si:H(p) and the passivation is provided by the a-Si:H(i). However, in addition to the passivation provided by the a-Si:H(i), this layer also creates a potential barrier to the collection of photogenerated holes. There have been experimental studies in the literature that have suggested that multi-phonon processes are the main transport mechanism that assists in the transport of holes across the intrinsic a-Si:H barrier. Simulations presented here show that multi-phonon injection of holes into the a-Si:H(i) layer is the rate limiting step for transport across the a-Si:H(i) layer. Our results indicate that multi-phonon transport is strongly dependent on the electric field at the a-Si:H(i)/c-Si heterointerface as well. Transport simulations presented in this paper are consistent with experimental findings that multi-phonon processes limit transport across the a-Si:H(i) layer and are responsible for photocurrent suppression at the a-Si:H(i)/c-Si heterointerface when these processes are slower than the associated incident hole flux due to photo-excitation.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Gamma-Ray and Cosmic Ray Muon Modalities for Cargo Inspection

Screening and inspection of cargo containers are two essential methods to nondestructively examine the contents of shipment. These methods enable the detection of illicit transportation of unauthorized materials such as nuclear and radioactive materials, explosives, drugs, and so on, typically at borders or secure facilities. Although high-energy X-ray transmission is a standard system and is widely used for cargo inspection, the inherent challenges of high false-positive rates and high attenuation factors necessitate the development of complementary techniques that can increase the detection efficiency and accuracy in large and dense materials. Gamma-rays, which possess higher penetration characteristics because of their high energy, offer an alternative nonintrusive modality for cargo scanning. They represent a promising inspection method when compared to X-rays for three reasons: (1) improved ability to detect nuclear and radioactive materials, (2) higher inspection throughput rates, and (3) lower false-positive rates. Currently, there are two main gamma-ray inspection techniques, active and passive interrogation. Active interrogation can be further grouped into (1) gamma-ray transmission imaging and (2) neutron-induced gamma-ray emission detection. Gamma-ray transmission imaging utilizes differences in material densities for mapping the shipment contents and detecting anomalies. It is analogous to the X-ray transmission method; however, the high-energy photons make it more difficult to shield against, which enables more efficient performance in large and dense material inspection. Neutron-induced gamma-ray emission inspection is designed for the detection of nuclear and radioactive material because those materials emit characteristic gamma-rays when they are activated by neutron absorption. On the other hand, passive interrogation techniques rely on high-efficiency detectors to detect radiation emitted from hidden special nuclear or other radioactive materials. Similar to passive interrogation, cosmic ray muon monitoring and imaging are relatively new techniques that do not require external radioactive sources. These techniques have received attention as a potential next-generation radiographic probe to identify illicit transportation of nuclear and radioactive materials in cargo containers. Cosmic ray muons have unique features, (1) much higher energies than X-rays or gamma-rays (on the order of 10−1—104 GeV), (2) enhanced penetration capability, and (3) natural occurrence, thereby eliminating the need for induced radiation sources. These features enable cosmic ray muons to be utilized for detection of special nuclear materials in high-background-noise environments. By analyzing incoming and outgoing muon trajectories, scattering angles, and energies, it has been shown that it would be possible to locate hidden and well-shielded materials in cargo containers via three-dimensional muon tomography images or signal analysis. Gamma-rays, cosmic ray muons, and other nonintrusive cargo inspection modalities are complementary to each other, allowing them to address various cargo inspection conditions (i.e., scanning time, cost, radiation exposure level, and types of target materials). This chapter presents a detailed review of the theoretical fundamentals and technical principles behind the current gamma-ray and cosmic ray muon modalities for cargo inspection. Additionally, critical assessments and suggestions for the future directions to advance the use of gamma and muon modalities are discussed.

Bae, Junghyun↗

Revisiting the equatorial Pacific sea surface temperature response to global warming

The relative roles of the oceanic and atmospheric processes in the pattern formation of the equatorial Pacific sea surface temperature (SST) response to global warming is investigated using a set of climate model experiments embedded with a novel partial coupling technique. Here, the modeling results show that the SST response experiences a transition from a La Niña-like warming pattern at the initial stage to an El Niño-like warming pattern at the quasi-equilibrium stage. By decomposing anomalous equatorial Pacific SST into atmosphere-forced passive component and ocean dynamics-induced active component, it is found that the SST warming pattern at both stages is entirely induced by its active component. Specifically, the meridional and vertical ocean circulation changes play a dominant role in forming the La Niña-like SST warming pattern at the initial stage, and the zonal and meridional ocean circulation changes are responsible for the formation of the El Niño-like SST warming pattern at the quasi-equilibrium stage. In contrast, the passive SST at both stages is characterized by a zonally uniform warming along the equator, which can be explained by a balance between the cooling effect associated with mean upwelling and the warming effect due to surface passive heat flux change. In addition, this study finds that it is the slowdown of the Pacific subtropical cells during the transition period that controls the evolution of the equatorial SST warming pattern by changing the meridional and vertical ocean heat transports.

54 ENVIRONMENTAL SCIENCES↗

A new perspective on the initial hydrogenation of $\mathrm{TiFe_{0.9}M_{0.1}}$ ($\mathrm{M = V, Cr, Fe, Co, Ni}$) gained from surface oxide analysis and nucleation thermodynamics

Despite the promise of TiFe-based alloys as low-cost solid-state hydrogen storage materials with mild operating conditions and reasonable hydrogen capacity, their initial hydrogenation process is difficult, hindering broad utilization. The effect of alloying element on the initial hydrogenation kinetics of TiFe alloys, TiFe 0.9 M 0.1 (M = V, Cr, Fe, Co and Ni), was evaluated by analyzing changes to the passivating surface oxide layer that inhibits hydrogen permeation, as well as the ease of initial-stage hydrogen absorption into the underlying matrix. X-ray photoelectron spectroscopy and atom probe tomography revealed key variations in surface oxide compositions and thinning of the passivating oxide layer compared to pure TiFe, which suggests suppressed oxide growth by alloying-induced elemental redistribution. At the same time, density functional theory calculations predicted exothermic formation of hydride nuclei when alloying with V or Cr, as well as a reduced nucleation barrier when alloying with Co or Ni. Overall, these results are consistent with the observed experimental trend of the activation kinetics. We propose that improvements in activation kinetics of TiFe with alloying arises from the combined effect of reduced passivating oxide thickness and easier hydride nucleation, offering a starting point for alloy design strategies towards further improvement.

25 ENERGY STORAGE↗

Nexus of thermal resilience and energy efficiency in buildings: A case study of a nursing home

Extreme weather events become more frequent and severe due to climate change. Although energy efficiency technologies can influence thermal resilience of buildings, they are traditionally studied separately, and their interconnections are rarely quantified. This study developed a methodology of modeling and analysis to provide insights into the nexus of thermal resilience and energy efficiency of buildings. In this work, we conducted a case study of a real nursing home in Florida, where 12 patients died during Hurricane Irma in 2017 due to HVAC system power loss, to understand and quantify how passive and active energy efficiency measures (EEMs) can improve thermal resilience to reduce heat-exposure risk of patients. Results show that passive measures of opening windows and doors for natural ventilation, as well as miscellaneous load reduction, are very effective in eliminating the extreme dangerous occasions. However, to maintain safe conditions, active measures such as on-site power generators and thermal storage are also needed. The nursing home was further studied by changing its location to two other cities: San Francisco (mild climate) and Chicago (cold winter and hot summer). Results revealed that the EEMs' impacts on thermal resilience vary significantly by climate and building characteristics. The study also estimated the costs of EEMs to help stakeholders prioritize the measures. Passive measures that may not save energy may greatly improve thermal resilience, and thus should be considered in building design or retrofit. Findings from this study indicate energy efficiency technologies should be evaluated not only by their energy savings performance but also by their influence on a building's resilience to extreme weather events.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Cool rooms for indoor heat resilience: Evaluating affordable cooling strategies in heat-stressed California homes

Extreme heat conditions pose significant indoor survivability challenges for resource-constrained communities, which often lack access to cooling, have poorly insulated homes, and face compounding socioeconomic vulnerabilities. Moreover, concurrent power outages worsen health risks and heat-related illnesses. It is therefore crucial to develop innovative and affordable cooling approaches to protect vulnerable populations. This study assesses the efficacy of “cool rooms”– a designated space within a home equipped with passive and low-power active cooling measures to maintain safe indoor temperatures during extreme heat events and power disruptions. Using a physics-based building energy modeling approach, we evaluate the efficacy of various retrofit packages in maintaining thermal safety within the cool room under recent extreme heat conditions. The results indicate that passive measures can reduce 64% of hours with unmet standard effective temperatures, while the combination of passive and low-power active measures with built-in batteries further cuts this to 86%. Nevertheless, these strategies remain insufficient to maintain indoor thermal safety during extended outages. In contrast, integrating a solar-powered mini-split heat pump, whose technical potential was evaluated in this study, reduces indoor air temperatures below the 28 °C overheating threshold and significantly improves indoor habitability. The localized cool room strategy also offers potential for grid resilience by reducing peak electricity demand by up to 70% compared to whole house cooling during heat waves. The findings can inform the development of actionable heat mitigation plans and retrofit policies for residential communities with relatively low adoption of air conditioning such as warm marine climates.

Cool room↗

Nucleation dependence of atomic layer deposition on diamond surface termination

Surface termination and interfacial interactions are critical for advanced solid-state quantum applications. Here, in this paper, we demonstrate that atomic layer deposition (ALD) can both provide valuable insight on the chemical environment of the surface, having sufficient sensitivity to distinguish between the common diamond (001) surface termination types and passivate these interfaces as desired. We selected diamond substrates exhibiting both smooth and anomalously rough surfaces to probe the effect of morphology on ALD nucleation. We use high resolution in situ spectroscopic ellipsometry to monitor the surface reaction with sub-angstrom resolution, to evaluate the nucleation of an ALD Al 2 O 3 process as a function of different ex and in situ treatments to the diamond surface. In situ water dosing and high vacuum annealing provided the most favorable environment for nucleation of dimethylaluminum isopropoxide and water ALD. Hydrogen termination passivated both smooth and rough surfaces while triacid cleaning passivated the smooth surface only, with striking effectiveness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of catalytic iron in enhancing volumetric sugar productivity during autothermal pyrolysis of woody biomass

Passivation of naturally occurring AAEM in biomass enhances sugar yields from the fast pyrolysis of biomass by preventing these metals from catalyzing the fragmentation of pyranose rings in cellulose and hemicellulose. However, because AAEM also catalyzes lignin depolymerization, its passivation can be accompanied by undesirable char agglomeration. Pretreatment of biomass with ferrous sulfate both passivates AAEM and substitutes ferrous ions as lignin depolymerization catalysts. This pretreatment has been particularly successful for high ash biomass like corn stover, but of limited value for low ash biomass like wood. This study explores the reasons for this discrepancy and offers a combined pretreatment of ferrous sulfate and ferrous acetate pretreatment to overcome char agglomeration in wood. Furthermore, this new pretreatment increased sugar yields from 4.4 wt% to 15.5 wt% and 5.4 wt% to 19.0 wt% for hardwood and softwood biomasses, respectively. This pretreatment produces an iron-rich biochar that catalyzes oxidation of the biochar under the oxygen-rich conditions of autothermal pyrolysis, which is preferentially consumed to provide the enthalpy for pyrolysis, preserving bio-oil as a more desirable energy product. Instead of producing carbon monoxide, which dominates oxidation of biochar from untreated biomass, the iron catalyzes oxidation to carbon dioxide, producing more energy per mole of oxygen consumed. In fact, oxygen demand to support autothermal pyrolysis of red oak and southern yellow pine was reduced 15% by the presence of iron in the biochar.

42 ENGINEERING↗

In situ probing the origin of interfacial instability of Na metal anode

The unstable and fragile solid electrolyte interphase (SEI) has restricted the application of Na metal anodes. Despite numerous research efforts being put into understanding its chemical composition and physical properties, direct observation of its formation remains a challenge due to the lack of temporal and spatial resolution. Here, through combined in situ probing techniques, we exhibit two pivotal stages associated with SEI instability during the often -neglected formation process. It is revealed that Na metal that is not uniformly passivated at the initial (passivating) stage will trigger unrestricted electrolyte decomposition and homogeneous components distribution during the subsequent (growing) stage. SEI with homogenously distributed components is found to have higher solubility than that with a layered structure evolved from a compact passivation layer. Furthermore, through demonstrating an SEI dissolution model that is closely related to its formation process and compositional distribution, this work sheds light on an uncharted territory of Na metal batteries.

25 ENERGY STORAGE↗

Natural carbonation of portland cement with synthetic zeolite Y as a supplementary cementitious material

Risks associated with carbonation are a key limitation to greater replacement levels of ordinary portland cement (OPC) by supplementary cementitious materials (SCMs). The addition of pozzolanic SCMs in OPC alters the hydrate assemblage by forming phases like calcium-(alumina)-silicate-hydrate (C-(A)-S-H). The objective of the present study was to elucidate how such changes in hydrate assemblage influence the chemical mechanisms of carbonation in a realistic OPC system. Here, in this paper, we show that synthetic zeolite Y (faujasite) is a highly reactive pozzolan in OPC that reduces the calcium content of hydration products via prompt consumption of calcium hydroxide from the evolving phase assemblage prior to CO 2 exposure. Suppression of portlandite at moderate to high zeolite Y content led to a more damaging mechanism of carbonation by disrupting the formation of a passivating carbonate layer. Without this layer, carbonation depth and CO 2 uptake are increased. Binders containing 12–18% zeolite Y by volume consumed all the calcium hydroxide from OPC during hydration and reduced the Ca/(Si+Al) ratio of the amorphous products to near 0.67. In these cases, higher carbonation depths were observed after exposure to ambient air with decalcification of C-(A)-S-H as the main source of CO 2 buffering. Binders with either 0% or 4% zeolite Y contained calcium hydroxide in the hydrated microstructure, had higher Ca/(Si+Al) ratios, and formed a calcite-rich passivation layer that halted deep carbonation. Although the carbonated layer in the samples with 12% and 18% zeolite Y contained 70% and 76% less calcite than the OPC respectively, their higher carbonation depths resulted in total CO 2 uptakes that were 12x greater than the OPC sample. Passivation layer formation in samples with calcium hydroxide explains this finding and was further supported by thermodynamic modeling. High Si/Al zeolite additives to OPC should be balanced with the calcium content for optimal carbonation resistance.

36 MATERIALS SCIENCE↗

Phase stabilization and oxidation of a continuous composition spread multi-principal element (AlFeNiTiVZr) 1-x Cr x alloy

Multi-Principal Element Alloys (MPEA) have been hypothesized to maintain a stable single alloy phase and resist corrosion at high temperatures, which are desirable in various functional applications, including material of turbine blades. However, studies into oxidation resistant alloys have been constrained to individual MPEA systems or a limited selection of compositions within those systems. Here, High-Throughput Experimental (HTE) techniques were utilized to rapidly assess phase stability and resistance to oxidation of an (AlFeNiTiVZr) 1-x Cr x continuous composition spread (CCS) thin-film alloy system. High-throughput synchrotron diffraction and Raman spectroscopy were used to identify phases, especially high symmetry structures and oxides, as a function of annealing time and composition. The formation of two distinct phase regions, R 1 and R 2 , across the CCS was observed. One of these phase regions, R 2 , exhibited a stable high symmetry BCC-like phase at Cr concentrations greater than 25.4 at%, and grew a passivating mixed metal surface oxide; whereas, the R 1 phase region, decomposed on oxidation to multiple oxides and reacted with the substrate to form silicides. The passivating mixed metal oxide layer appears to prevent destabilization of the (AlFeNiTiVZr) 1-x Cr x MPEA BCC solid solution. Furthermore, at longer annealing times the passivating phase was seen only above 29.2 at% Cr. High Cr-doped (AlFeNiTiVZr) 1-x Cr x appear to be a good candidate for high temperature, oxidation-resistant structural alloys.

36 MATERIALS SCIENCE↗