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At least 577 records · Page 32

Electronic mobility, doping, and defects in epitaxial BaZrS 3 chalcogenide perovskite thin films

We present the electronic transport properties of BaZrS 3 thin films grown epitaxially by gas-source molecular beam epitaxy. We observe n-type behavior in all samples, with carrier concentration ranging from 4 × 10 18 to 4 × 10 20 cm −3 at room temperature (RT). We observe a champion RT Hall mobility of 11.1 cm 2 V −1 s −1 , which is competitive with established thin-film photovoltaic absorbers. Temperature-dependent Hall mobility data show that phonon scattering dominates at room temperature, in agreement with computational predictions. X-ray diffraction data illustrate a correlation between mobility and antiphase boundary concentration, illustrating how microstructure can affect transport. Despite the well-established environmental stability of chalcogenide perovskites, we observe significant changes to electronic properties as a function of storage time in ambient conditions. With the help of secondary ion mass spectrometry measurements, we propose and support a defect mechanism that explains this behavior: as-grown films have a high concentration of sulfur vacancies that are shallow donors (V ⋅ S or V ⋅⋅ S ), which are converted into neutral oxygen defects (O$^{×}_{S}$) upon air exposure. We discuss the relevance of this defect mechanism within the larger context of chalcogenide perovskite research, and we identify means to stabilize the electronic properties.

Van Sambeek, Jack [Massachusetts Institute of Tech↗

Insights into the Assembly and Conformation of Nanoparticle Organic Hybrid Materials (NOHMs) in Solution with Varying Grafting Type

Recently, nanoparticle organic hybrid materials (NOHMs) have been considered promising electrolytes for energy storage applications due to their unique combination of properties, which include high thermal stability, negligible vapor pressure, and easy synthesis. However, the structural features of NOHMs in electrochemical systems are not well understood. Hence, we investigate the impact of grafting type (ionic vs covalent) on the structure and performance of NOHMs that consist of a silica core and grafted HPE polymer (Jeffamine M2070) in aqueous solution with and without the presence of the supporting electrolyte (0.1 M KHCO 3 ) using small-angle neutron scattering. Careful analyses of the results indicate that even at low grafting density (0.8 chains nm –2 ) and concentration (1–3 wt %), ionic NOHMs solutions contain a free polymer that may interact with the grafted polymer, altering the assembly of NOHMs in solution. Our investigation also elucidates that the covalent NOHM solutions consist of both aggregated and dispersed NOHMs in the solution. Moreover, the addition of the supporting electrolyte affects the assembly and structure of the polymer in the ionic NOHMs solution significantly, whereas only a slight change in the conformation of the grafted polymer is observed for covalent NOHMs. These conformational changes alter the performance of the NOHMs solution, resulting in a dramatic change in viscosity. Careful analysis shows that this significant alteration of solution viscosity in the ionic NOHMs can be traced back to the presence of the free polymer that interacts with the grafted layer and the attenuation of this interaction between the free and grafted polymers with the addition of salt. Furthermore, these studies elucidate the impact of grafting type on the overall structure, assembly, and performance of functionalized NOHMs in aqueous solution and explicitly correlate the structure and assembly of NOHMs to their transport properties and must be considered when designing functional systems that incorporate NOHMs.

25 ENERGY STORAGE↗

Monitoring Offshore CO 2 Sequestration Using Marine CSEM Methods; Constraints Inferred from Field- and Laboratory-Based Gas Hydrate Studies

Offshore geological sequestration of CO 2 offers a viable approach for reducing greenhouse gas emissions into the atmosphere. Strategies include injection of CO 2 into the deep-ocean or ocean-floor sediments, whereby depending on pressure–temperature conditions, CO 2 can be trapped physically, gravitationally, or converted to CO 2 hydrate. Energy-driven research continues to also advance CO 2 -for-CH 4 replacement strategies in the gas hydrate stability zone (GHSZ), producing methane for natural gas needs while sequestering CO 2 . In all cases, safe storage of CO 2 requires reliable monitoring of the targeted CO 2 injection sites and the integrity of the repository over time, including possible leakage. Electromagnetic technologies used for oil and gas exploration, sensitive to electrical conductivity, have long been considered an optimal monitoring method, as CO 2 , similar to hydrocarbons, typically exhibits lower conductivity than the surrounding medium. We apply 3D controlled-source electromagnetic (CSEM) forward modeling code to simulate an evolving CO 2 reservoir in deep-ocean sediments, demonstrating sufficient sensitivity and resolution of CSEM data to detect reservoir changes even before sophisticated inversion of data. Laboratory measurements place further constraints on evaluating certain systems within the GHSZ; notably, CO 2 hydrate is measurably weaker than methane hydrate, and >1 order of magnitude more conductive, properties that may affect site selection, stability, and modeling considerations.

58 GEOSCIENCES↗

Combined Cycle Integrated Thermal Energy Storage “CiTES” (Final Scientific/Technical Report)

The Phase I of this project confirmed the technical feasibility of a Combined Cycle integrated Thermal Energy Storage “CiTES” system, calculated the key performance parameters like power efficiency and costs, and proved its commercial value with full-year simulations for several US electricity markets with high degree of variable renewable generation and volatile hourly electricity prices. The core element of this project is the Electro Thermal Energy Storage (ETES) technology from Siemens Gamesa Renewable Energy GmbH, using thermally stable and inexpensive volcanic rocks as storage material and air as heat transfer medium. This technology is backed by more than 10 years of experience and a 440MMBTU (130MWh-th) pilot plant in Hamburg, Germany, which is in operation since 2019. The integration of this thermal storage in an existing combined cycle power plant (CCPP) is typical power plant technology without any major technology risks. It allows the storage of inexpensive renewable energy during times of surplus renewable generation and the discharge of this energy in times of high energy demand when the fossil plant is in operation. This supplements the fossil power generation with CO2-emission-free energy. The secondary effect of the CiTES system is that a small part of the stored thermal energy is used to keep the heat recovery steam generator (HRSG) and steam turbine (ST) of the combined cycle power plant in hot and ready-to-start condition. This enables the plant to start rapidly when fossil generation is required to satisfy demand as soon variable generation drops off in the evenings or during cloud cover and calm wind periods. Without pre-warming of the HRSG and ST, the CCPP would need several hours for a cold or warm start, burn a lot of gas and release high NOx emissions during start and wouldn’t be able to use the short times of high energy prices in an efficient or economical manner. The economic parameters of CiTES were determined by a full year “8760” simulation using a data set calculation for each of the hours of the year, and historical electricity and gas prices. For consistency, the simulations were focused on the pre-COVID year 2019. The financially most attractive markets were in the Energy Reliability Council of Texas (ERCOT) region, which allowed substantial value generation with arbitrage (charge with cheap energy during renewable surplus times and discharge when energy is needed and expensive). The improvement of flexibility with the CiTES system by pre-heating and warm-keeping of the CCPP allowed for additional power generation during short time periods when demand is high but renewable generation is down; when the hourly energy prices are highest in these markets. The simulations are based on 2019 data, when ERCOT had 27GW of installed photovoltaic (PV) and wind generation. They showed that the created revenue with the prototypically sized CiTES system of 1,000MMBTU (300MWh-th) falls a little bit short of what is expected from a commercially viable investment. The system has optimization opportunities for cost reduction and increased effectiveness which will be realized during a potential Phase II Pre-FEED study following this project. Furthermore, it is safe to assume that a lot of renewable generation capacity will be added all over the US in the coming years. As an example, ERCOT is predicting to more than double its renewable generation from 27GW in 2019 to a forecasted 63GW in 2023. This will increase the amount of renewable overproduction exponentially. This rapid increase of local overproduction and the need to curtail renewable generation is well documented by the California ISO (www.CAISO.com / managing oversupply). However, the simulations also revealed a weakness in the structure of the electricity markets in the US. More specifically, when electricity prices are very low and approaching negative levels, the owners of Variable Renewable Energy (VRE) will curtail a part of their facility to stabilize the price by reducing supply. This results in a situation in which storage facilities, which are integrated in existing fossil assets and don’t have the behind-the-meter benefit of a VRE, won’t be able to purchase low cost – otherwise curtailed – renewable energy off the grid. A special tariff, which motivates VRE owners to sell otherwise curtailed renewable energy to storage facilities (Hydrogen, thermal, pumped hydro, etc.) can solve this issue. The implementation of such a regulating tariff by Independent System Operators, thus avoiding renewable curtailment, is a pre condition for successful commercialization for renewable energy storage technologies. With this advancement of design and technology and improvements in the market environment, it can be expected that the Combined Cycle integrated Thermal Energy Storage proves itself as an important innovation to keep highly efficient, natural gas-based power generation economically successful and relevant for the power industry in the United States of America.

Wolf, Thorsten↗

Study to determine and improve design for lithium-doped solar cells

Solar cell experiments show that a single lithium density parameter, the lithium density gradient, calculated from nondestructive capacitance measurements, provides the basis for accurate predictions of lithium cell behavior in a 1-MeV electron environment for fluences ranging between 3 X 10 to the 13th power e/sq cm and 3 X 10 to the 15th power/e sq cm. The oxygen-rich (quartz crucible) lithium cell with phosphorous starting dopant and lithium gradient between approximately 5 X 10 to the 18th power and 1.5 x 10 to the 19th power/cm to the 4th power was found superior in performance to the commercial 10 ohm-cm n/p control cells. Post-recovery stability of oxygen-rich cells was satisfactory. An average post-recovery current drop of approximately 1 mA was observed for 70 crucible cells after 1 year-equivalent storage time at 80 C. In contrast the oxygen-poor (float zone and Lopex) lithium cells displayed spotty initial performance and stability problems at room temperature.

Brucker, G.↗

An overview of cobalt-free, nickel-containing cathodes for Li-ion batteries

The need for high-energy, low-cost batteries is projected to grow dramatically in the next decade due to electrification of the transportation market. Such demands are straining Li-ion supply chains for critical materials including lithium, nickel, and cobalt. Price instability, environment toxicity, and limits in the absolute supply lead to great concern for the continued use of cobalt. Similar to cobalt, the required grade of nickel for batteries, known as Class 1 nickel, has also been declining due to geological scarcity and low incentive prices. Herein, this review summarizes alternative cathode chemistries with no cobalt and reduced nickel content for high-energy Li-ion batteries targeting sustainable growth in the electric vehicle market. Further, the primary challenges associated with each material system are generally classified as being related to four common categories: (1) ion instability during charging, (2) poor electronic conductivity, (3) poor ionic conductivity, and (4) poor thermal stability.

25 ENERGY STORAGE↗

FLAW STABILITY ANALYSIS OF SURFACE CRACKS IN DOE STANDARD CANISTERS UNDER OPERATION LOADS AND WELDING RESIDUAL STRESSES

There are over 3000 commercial spent nuclear fuel (SNF) storage canisters that are made of stainless steel and planned for multi-purpose functions of SNF handling: interim storage, transportation, and ultimate disposal at a future SNF disposition location. To date, many multi-purpose canisters (MPC) are located in coastal regions for long-term storage. The canisters are fabricated by welding, and post-welding heat treatment is not required for relieving welding residual stresses (WRS). As a result, these canisters may be susceptible to chloride induced stress corrosion cracking (CISCC) due to the chloride-bearing marine salts. The flaw stability analysis of MPC canisters was performed at SRNL (i.e., PVP2016-4935 and PVP2016-63887) for through-wall flaws and for surface flaws respectively, where WRS was considered, and the failure assessment diagram (FAD)-based fracture mechanics method codified by API 579-1/ASME FFS-1-2007 Edition was adopted.

DOE standard canister↗

Fluorine-Substituted Lithium Chloride Solid Electrolytes for High-Voltage All-Solid-State Lithium-Ion Batteries

Lithium ternary halides are promising solid electrolytes, owing to their high ionic conductivity and reasonably high oxidative and chemical stability. Recently, fluorine substitution in Li 3 MCl 6 has been suggested as a promising approach for further enhancing oxidation stability. Accordingly, this study outlines a material design strategy for F-substituted Li 3 MCl 6 through systematic theoretical analyses. Calculations reveal that the mixing limit of F in Li 3 MCl 6–x F x is in the range of 0.5–1.5, and the resulting Li 3 MCl 6–x F x phases can retain ionic conductivity above 1 mS/cm up to x = 1.0. Additionally, the calculations also predict that the formation of F-containing passivating phases could increase the oxidation potential for Li3MCl5F to ~6.3 V. The proposed material design strategy is validated through the synthesis of Li 3 YCl 5 F, which is confirmed to show both high ionic conductivity and enhanced oxidation stability. The design guidelines presented herein can accelerate the potential use of halide-based electrolyte chemistries in high-voltage all-solid-state batteries.

25 ENERGY STORAGE↗

Hydride-Based Interlayer for Solid-State Anode-Free Battery

Solid-state batteries (SSBs) are considered a promising approach to realizing an anode-free concept with high energy densities. However, the initial Coulombic efficiency (ICE) has remained insufficient for anode-free batteries using sulfide-based solid electrolytes (SEs). Herein, we incorporated a hydride-based interlayer, 3LiBH 4 -LiI (LBHI), between a typical sulfide SE, Li 6 PS 5 Cl, and the Cu current collector. Further, by investigating the Li plating and stripping behaviors and the (electro)chemical stability between SEs and plated Li, we demonstrated that LBHI can effectively improve interfacial stability, leading to an ICE exceeding 94% in anode-free half cells. This interlayer also improves Coulombic efficiencies and specific capacities in anode-free full cells. Furthermore, the utilization of LBHI enables one to study Li plating behaviors without interference from interfacial (electro)chemical instabilities. The analysis of stack pressure evolution during electrochemical cycling reveals that soft shorting in SSBs arises from both dendrite formation and deformation, offering insights into further optimizing solid-state anode-free batteries.

25 ENERGY STORAGE↗

Linking the Spin Transition of Ferric Iron in δ‐(Al,Fe)OOH to Water Storage in the Lower Mantle

As the most massive geochemical reservoir, the lower mantle affects the Earth's budget of volatile elements, including hydrogen or H 2 O. The properties of minerals in the lower mantle are further affected by changes in the electronic configurations of iron cations, that is, by spin transitions. The feedback between spin transitions and potential storage of H 2 O in solid hydrous phases in the lower mantle, however, remains unexplored. By combining high‐pressure nuclear resonant inelastic X‐ray scattering and high‐pressure high‐temperature X‐ray diffraction experiments, we constrained the thermal equation of state of δ‐(Al,Fe)OOH, a member of the phase H solid solution. Based on the derived thermal equation of state of δ‐(Al,Fe)OOH and the underlying thermodynamic model, we calculate the excess Gibbs free energy that arises from the spin transition of ferric iron in this compound and evaluate the effect on phase equilibria. The results of our analysis show that the spin transition of ferric iron in phase H may significantly reduce the thermodynamic activity and hence the concentration of H 2 O in a coexisting hydrous melt. As a consequence, nominally anhydrous minerals of the lower mantle may become dehydrated in the presence of phase H. Our analysis further suggests that, under certain conditions, the spin transition may expand the thermal stability of Fe 3+ ‐bearing phase H and create a geochemical link between the storage of H 2 O in phase H and ferric iron in the lower mantle.

Buchen, Johannes [Univ. of Bayreuth (Germany); Cal↗

A State-Space Model for Stability Boundary Analysis of Grid-Following Voltage Source Converters Considering Grid Conditions

With the growing significance of renewable energy resources and energy storage systems, the number of grid-connected inverters has been rising at an increasingly rapid pace. Generally, these inverters are directly integrated with the distribution network by synchronizing with the grid voltage at the point of common coupling. However, the low grid strength and varying R/X ratios, as the common characteristics of most distribution networks or weak grids, can lead to dynamic interactions that comprise stability and limit the power transfer capacity of grid-connected inverters. To ensure stable operation of the inverters, researchers must determine the stability boundary, described as the maximum power transfer capacity of grid-connected inverters under the premise of maintaining system small-signal stability. For this purpose, we propose to formulate a state-space model of the system in the synchronously rotating dq-frame of reference and perform eigenvalue analysis to determine the stability boundary. With a detailed model of the control structure and parameters of the grid-connected inverters, the stability boundary is identified as a surface with respect to different grid strengths and R/X ratios. Case study results of proposed eigenvalue analysis are compared with those of admittance model-based stability analysis as well as time-domain simulation using a switching model in Matlab/Simulink, validating the effectiveness and accuracy of the proposed eigenvalue analysis for stability boundary identification.

grid-connected inverters↗

Food Fortification Stability Study

NASA has established the goal of traveling beyond low-Earth orbit and extending manned exploration to Mars. The extended length of a Mars mission, along with the lack of resupply missions increases the importance of nutritional content in the food system. The purpose of this research is to assess the stability of vitamin supplementation in traditionally processed spaceflight foods. It is expected that commercially available fortificants will remain stable through long-duration missions if proper formulation, processing, and storage temperatures are all achieved. Five vitamins (vitamin E, vitamin K, pantothenic acid, folic acid, and thiamin) were blended into a vitamin premix (DSM, Freeport, TX); premixes were formulated to be compatible with current processing techniques (retort or freeze-dried), varied water activities (high or low), and packaging material. The overall goal of this process is to provide 25% of the recommended daily intake of each vitamin (per serving), following processing and two years of ambient storage. Four freeze-dried foods (Scrambled Eggs, Italian Vegetables, Potatoes Au Gratin, Noodles and Chicken) and four thermostabilized foods (Curry Sauce with Vegetables, Chicken Noodle Soup, Grilled Pork Chop, Rice with Butter) were produced (with and without the vitamin premix), to assess the impact of the added fortificant on color and taste, and to determine the stability of supplemental vitamins in spaceflight foods. The use of fortification in spaceflight foods appears to be a plausible mitigation step to inadequate nutrition. This is due to the ease of vitamin addition as well as the sustainability of the premixes through initial processing steps. Postprocessing analysis indicated that vitamin fortification with this premix did not immediately impact organoleptic properties of the food. At this stage, the largest hurdle to fortification is the preciseness to which vitamins can be added; the total amount of vitamins required for production is 10 - 20 grams, a minor percentage of the formulation. As demonstrated by the over-fortification measured in Italian Vegetables and Grilled Pork Chop, homogeneity may be difficult to achieve with such small amounts. Thus, pouch-to-pouch variability, over-fortification, and underfortification may ensue if a method for precise addition is not identified. Stability will continue to be evaluated over two years of storage at three temperatures, and future analysis should reveal the extent to which this issue should be a concern

Abdulmalik, T. O.↗

Williston Basin Resource Study for Commercial-Scale Subsurface Hydrogen Storage

The Energy & Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL), the EERC’s State Energy Research Center (SERC), MPLX Operations LLC, and TC Energy Development Holdings Inc. (a subsidiary of TC Energy Corporation), studied the potential for subsurface hydrogen storage and recovery in the Williston Basin of western North Dakota. The project’s goal was to evaluate the feasibility of large-scale, secure geologic H 2 storage to support future hydrogen generation, storage, and use. This work included laboratory testing, H 2 –rock–fluid exposure experiments, literature reviews on H 2 embrittlement, and reservoir modeling and simulations. The study included an assessment of storage potential across three types of storage reservoirs using both reservoir simulation and DOE’s web-based tool SHASTA-HELP (Subsurface Hydrogen Assessment, Storage, and Technology Acceleration – Hydrogen Estimator for Logistical Planning), as well as investigation of potential H 2 production and markets for commercial-scale deployment. Building on prior EERC gas storage research, three storage options were selected for detailed evaluation: the Broom Creek Formation (a clastic saline reservoir), the Dickinson Lodgepole Mounds (DLM) complex (carbonate mud mound structures) of the Lodgepole Formation (an active oil and gas producing reservoir), and the Dunham Salt Interval of the Piper Formation (to be used for engineered salt cavern development). These targets were prioritized based on prior EERC research using datasets related to seal capacity, reservoir quality, mechanical integrity, and injectivity. Exposure tests on Broom Creek and DLM samples showed mineral dissolution and precipitation that increased brine salinity and altered reservoir rock surfaces. Although these results provide useful insight, they are limited by small sample sizes and short-term (30-day) exposure, requiring further study to assess long-term storage integrity. Salt formations were not tested because of their known nonreactivity and established mechanical stability. Results of reservoir simulations performed for a single site demonstrated that the Broom Creek Formation may be capable of receiving up to 42,000 tonnes of injected H 2 over 7 months via one well. H 2 recovery took place over 5 months, resulting in approximately 26,000 tonnes (~62% without cushion gas [CG]). This work suggests water production may be important and subsequent cycles of injection and production may perform more efficiently; however, significant site-specific work in the future is needed to assess actual reservoir performance of injection and withdrawal of H 2 storage. For oil reservoir potential, a multiple-well model was used to simulate injection of approximately 32,000 tonnes of H 2 into a single wellbore while simultaneously producing in place reservoir fluids from four offset wells to maintain reservoir pressure. The simulation results suggested a high recovery (~98%); in addition, cost advantages through existing infrastructure could be realized. Challenges in this reservoir include vi managing gas purity and leakage risks. In both scenarios, production of H 2 takes place in a single-well scenario with 10 cycles (7 months of injection and 5 months of production) over 10 years. Finally, the use of engineered caverns in the Dunhan Salt was evaluated, and the results suggest that while they have a smaller capacity (<1000 tonnes per cavern), they exhibit nearly complete gas recovery (>99%), fast response times, and low purity risk. While caverns in North Dakota may be smaller in capacity, fields can be developed in galleries to accommodate the volumetric needs and rapid turnaround times necessary to meet market demands. Geographic limitations and thin salt intervals in North Dakota may represent less total storage potential than salt domes elsewhere, but significant opportunities exist to expand this market for gas storage in North Dakota. A basinwide assessment was performed to estimate a first-of-its-kind value for H 2 storage on a large scale. DOE’s SHASTA-HELP, combined with EERC simulation work, was used to perform the assessment. Estimated H 2 storage potential varied widely for each formation type. The Broom Creek saline formation was estimated to have a storage potential of approximately 1.7–90.5 million tonnes (MMt). The DLM oil reservoirs were estimated to have 0.07–0.19 MMt of capacity. Notably, each of these estimates relies on significant assumptions regarding reservoir thickness, porosity, permeability, and CG needed for operation. Much research is needed to understand the true site-specific storage resource potential of each formation. Using the Dunham Salt Interval for cavern development may result in as much as 4.79 MMt (up to 2.87 MMt working gas) of H 2 storage potential. An important note for consideration is that the values presented here need significantly more geological characterization and engineering assessments prior to gaining confidence in performance. This will be a focal point for future research and development needs. The basinwide evaluation also indicated that North Dakota has significant H 2 generation potential, with estimates up to a possible 13 MMt annually, suggesting a substantial opportunity for H 2 market development and thus the need for commercial-scale H 2 storage to facilitate growth and resilience. Key Recommendations 1. Conduct detailed site characterization (3D seismic, well logs, core sampling) to reduce geologic uncertainty. 2. Perform techno-economic analyses incorporating market, regulatory, and incentive frameworks. 3. Investigate long-term interactions among H 2 , CGs, well materials, and formations to assess risks. 4. Develop pilot- and field-scale demonstrations to validate models and establish best practices.

03 NATURAL GAS↗

Feasibility of Prelithiation in LiFePO 4

Lithium iron phosphate (LiFePO 4 ) is widely applied as the cathode material for the energy storage Li-ion batteries due to its low cost and high cycling stability. However, the low theoretical specific capacity of LiFePO 4 makes its initial capacity loss more concerning. Therefore, lithium compensation by way of prelithiation and applications of sacrificial Li-rich additives in LiFePO 4 is imminent in elevating the energy density and/or prolonging the lifetime of the LiFePO 4 -based Li-ion batteries (LIBs). Prelithiation in LiFePO 4 is herein carried out by electrochemical and chemical methods and its feasibility is proved on the basis of the electrochemical evaluations such as the initial charge capacity and the cycling stability. In addition, the site of the pre-intercalated Li-ions is found via comprehensive physical characterizations and the density functional theory (DFT) calculations. Furthermore, these findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high-energy-density batteries.

36 MATERIALS SCIENCE↗

Enhancing Crystallization in Hybrid Perovskite Solar Cells Using Thermally Conductive 2D Boron Nitride Nanosheet Additive

Controlling crystallization and grain growth is crucial for realizing highly efficient hybrid perovskite solar cells (PSCs). In this work, enhanced PSC photovoltaic performance and stability by accelerating perovskite crystallization and grain growth via 2D hexagonal boron nitride (hBN) nanosheet additives incorporated into the active perovskite layer are demonstrated. Specifically, in situ X-ray scattering and infrared thermal imaging during the perovskite annealing process revealed the highly thermally conductive hBN nanosheets promoted the phase conversion and grain growth in the perovskite layer by facilitating a more rapid and spatially uniform temperature rise within the perovskite film. Complementary structural, physicochemical, and electrical characterizations further showed that the hBN nanosheets formed a physical barrier at the perovskite grain boundaries and the interfaces with charge transport layers, passivating defects, and retarding ion migration. As a result, the power conversion efficiency of the PSC is improved from 17.4% to 19.8%, along with enhanced device stability, retaining ≈90% of the initial efficiency even after 500 h ambient air storage. Here, the results not only highlight 2D hBN as an effective additive for PSCs but also suggest enhanced thermal transport as one of the pathways for improved PSC performance by 2D material additives in general.

2D materials↗

A tailored multi-functional catalyst for ultra-efficient styrene production under a cyclic redox scheme

Abstract Styrene is an important commodity chemical that is highly energy and CO 2 intensive to produce. We report a redox oxidative dehydrogenation (redox-ODH) strategy to efficiently produce styrene. Facilitated by a multifunctional (Ca/Mn) 1− x O@KFeO 2 core-shell redox catalyst which acts as (i) a heterogeneous catalyst, (ii) an oxygen separation agent, and (iii) a selective hydrogen combustion material, redox-ODH auto-thermally converts ethylbenzene to styrene with up to 97% single-pass conversion and >94% selectivity. This represents a 72% yield increase compared to commercial dehydrogenation on a relative basis, leading to 82% energy savings and 79% CO 2 emission reduction. The redox catalyst is composed of a catalytically active KFeO 2 shell and a (Ca/Mn) 1− x O core for reversible lattice oxygen storage and donation. The lattice oxygen donation from (Ca/Mn) 1− x O sacrificially stabilizes Fe 3+ in the shell to maintain high catalytic activity and coke resistance. From a practical standpoint, the redox catalyst exhibits excellent long-term performance under industrially compatible conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-temperature sprayed SnO x nanocomposite films with enhanced hole blocking for efficient large area perovskite solar cells

Scalable fabrication of charge transport layers with high uniformity and compactness is essential for the commercialization of perovskite solar cells (PSCs). Cost-effective deposition of high-quality electron transport layers (ETLs) is a particularly important step to achieve low-cost, efficient and large-area PSCs. Here, an open-air (relative humidity of 40–50%) and low-temperature (≤100 °C) ultrasonic spray coating of tin oxide (SnO 2 ) nanocomposite films incorporating nanocrystalline SnO 2 nanoparticles in an amorphous SnO x matrix is demonstrated to fabricate large-area ETLs for planar PSCs. The optimized SnO 2 /SnO x nanocomposite exhibits significantly enhanced hole-blocking and high-power conversion efficiencies of 18% and 16% for planar PSCs with an active area of 0.2 cm 2 and 1 cm 2 , respectively. More importantly, the devices show little current–voltage hysteresis as well as good shelf-life stability by maintaining ~90% of the initial performance without encapsulation after 2500 hours storage under inert conditions. Additionally, high voltages of >6.0 V have been obtained for solar modules of 2.1 cm 2 aperture area comprising six sub-cells in series, suggesting that the low-temperature, open-air and fast spray coating is suitable and transferable to deposit large-area charge transport layers for scalable PSCs or other optoelectronic devices.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗