bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Best Student Presentation) Accurate First-Principle Study of High-Entropy Materials for Lithium-Ion Batteries
Authors: Ting Yin-Ying , Kowalski Piotr M. 
Published: September 2023

The availability of well performing and cost efficient energy storage devices is of utmost importance for a smooth transition to sustainable energy. Lithium-ion batteries (LIBs) have been successfully commercialized and widely used in various portable devices. Functional materials with higher voltages and greater capacity are needed to further boost the energy density of these batteries. Recently, high-entropy materials (HEMs), with their unique structural characteristics and tunable functional properties, are actively investigated by several research groups [1]. High-entropy alloys (HEAs) with superior mechanical properties were first reported about a decade ago. Afterwards, the concept was adapted to high-entropy ceramic (HECs), such as high-entropy oxides, which are promising materials for electrodes as well as electrolytes in LIBs [2-4]. These materials usually contain more than 5 metals in a single disordered phase [5]. HECs are constructed with different type of cations and anions. Their structural and electronic complexity represent a challenge to the computational methods. We discuss the refined Density Functional Theory (DFT)-based methods that are able to successfully describe the electronic structure of these materials. The correct assignment of oxidation states of transition metals is one of the challenges, and we will show importance of correct description of d orbitals for achieving this task. Besides, we will also discuss the cycling performance, as well as thermodynamic aspects of selected HECs [6,7]. Last but not least, we will briefly discuss how accurate atomistic simulations could accelerate design of high-performance materials for Li-ion batteries of the future.
[1] Zhang, R.-Z. & Reece, M. J. Review of high entropy ceramics: design, synthesis, structure and properties. J. Mater. Chem. A 7, 22148–22162 (2019).
[2] Lun, Z. et al. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries. Nat. Mater.
20, 214–221 (2021).
[3] Sarkar, A. et al. High entropy oxides for reversible energy storage. Nat Commun
9, 3400 (2018).
[4] Jung, S.-K. et al. Unlocking the hidden chemical space in cubic-phase garnet solid electrolyte for efficient quasi-all-solid-state lithium batteries. Nat Commun
13, 7638 (2022).
[5] Rost, C. M. et al. Entropy-stabilized oxides. Nat Commun
6, 8485 (2015).
[6] Cui, Y. et al. High entropy fluorides as conversion cathodes with tailorable electrochemical performance. Journal of Energy Chemistry 72, 342–351 (2022).
[7] Ting,Y. & Kowalski, P., Refined DFT+U method for computation of layered oxide cathode materials, Electrochimica Acta, in press.
Development of PCL-Based Gel Polymer Electrolyte for Li-Sulfur Batteries
Authors: Gomes Luisa Larissa Arnaldo , Mukerjee Sanjeev , Maxwell Derrick , Yang Kevin 
Published: September 2023

Li-Sulfur batteries offer the next generation of energy storage beyond the current state of the art based on Li-intercalation with their high energy density (2640 Wh/kg) and S relative abundance on the earth's crust. Nevertheless, most Li-Sulfur battery systems use liquid electrolytes, which results in the formation of Li-metal dendrites and polysulfide redox shuttles resulting in the instability of the solid electrolyte interface layer, short-circuiting, poor cyclability, and self-discharge1. Our presentation will focus on efforts to create a polycaprolactone (PCL)-based gel polymer electrolyte (GPE) for Li-S batteries. GPE combines the high ionic conductivity of a liquid electrolyte with the polymer electrolytes' ability to block the redox shuttle and limit the Li-metal dendritic growth2. Furthermore, PCL provides for high electrochemical stability window (~5V vs. Li/Li+)3 and biodegradability that could ease the negative environmental impact associated with the battery industry.
Moreover, effect of ceramic additives like LiNO3 and Li7La3Zr2O12 for enhancing ionic conductivity, mechanical stability and minimize the redox shuttle effect is also examined. We anticipate that the gel can be engineered to provide the high conductivity of a liquid electrolyte and the solid-state properties needed to block the polysulfide redox shuttle and limit dendrite growth. By determining the optimal ratio of polymer, additives, and solvent in the PCL gel formulation, we hope to benefit from hybridized ceramic/polymer electrolytes: nanocomposites engineered to optimize the advantages of polymers and ceramics while minimizing their weaknesses.

References

Pervez, Syed Atif, et al. Journal of Materials Chemistry A32 (2020): 16451-16462.

Cui, Yingyue, et al. Chemistry–An Asian Journal(2022): e202200746.

Fonseca, C. Polo, et al. " J. Electrochem. Sci2.2007 (2007): 52.
Some Thoughts on Magnetoelectrocatalysis of Small Molecules
Authors: Leddy Johna 
Published: September 2023

Electrons have properties of mass, charge, and spin. Spin engenders magnetic effects on electron transfer reactions. Many electron transfer reactions of small molecules such as oxygen, carbon dioxide and other molecules with a single carbon, and simple nitrogen species are slow.
Electrochemical potentials characterize transition state for electron transfer processes. This includes gradients in electrical potential and magnetic fields at the electrode solution interface.
Rates of reaction for small molecules at electrodes are considered in light of these gradients and recently developed quantitative models. Means to increase rates of electrocatalysis and magnetoelectrocatalysis are suggested. In some cases, slow electron transfer rates may be set by the inherent spin properties of the electrolysis reactants and products.
Thanks to the National Science Foundation (CHE-0809745 and CHE-1309366) and Army Research Office (W911NF-19-1-0208)) for support of this work.
Insights into the Reaction Energetics and Phase Stability of Electrocatalysts for Upgrading Sustainable Alcohols
Authors: Prajapati Aditya , Govindrajan Nitish , Sun Wenyu , Feaster Jeremy , Akhade Sneha A , Hahn Christopher 
Published: September 2023

The energy efficiency of ambient electrolyzers is currently impacted by oxygen evolution reaction (OER) which not only consumes a significant amount of energy, but also produces oxygen, an intrinsically low value product. When paired with a desired cathodic reaction, such as CO2 conversion to value-added hydrocarbons, it is imperative to choose an anodic reaction that can utilize the energy supplied to the electrolyzer efficiently. Biomass alcohol oxidation has the potential to not only decrease the overall electrolyzer energy input by >50%, but also address critical needs for biomass conversion, another important 21st century non-fossil carbon resource. Here, we present the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) as an alternative to OER, as this pathway not only decreases the theoretical overall energy input into the electrolyzer, but also produces FDCA, an important biomass-derived chemical building block for the sustainable polyester PEF, a compelling alternative to fossil-based PET which has a global market size of >30 Mt/yr. In this work, we show a synergistic experimental and computational catalysis framework to gain mechanistic insights into the reaction energetics of HMF oxidation on Ni-based catalysts. We experimentally evaluate the redox features of Ni on supports such as Au in a pH range of 10-13 as a function of Ni film thickness (<1-5 nm) to understand the intrinsic kinetics of HMF oxidation and the support effects on the reaction. Computationally, we compare the reaction energetics of OER and hydride transfer reaction of the HMF oxidation to understand the competing pathways on the anode and perform a bulk Pourbaix analysis as a function of strain caused by the presence of the support lattice to understand the phase stability of Ni oxides under oxidizing conditions. This systematic analysis could potentially serve as new guiding principles to design more energy efficient anodes to upgrade sustainable alcohols.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Flips: Fluidic Integration of Printed Sensors
Authors: Anderson Morgan J , Blair Jeffrey , Shimada Jared , Koehne Jessica E. , Ricco Antonio 
Published: September 2023

As NASA’s manned exploration programs advance toward more challenging missions including Martian spaceflight and long-term space habitation, novel technologies must be adapted for astronaut health monitoring and diagnostics. Among the technologies currently under development, In-Space Manufacturing (ISM) is an attractive approach because it mitigates the need to include multiple prefabricated sensors in spaceflight payloads instead allowing production of sensors on an as-needed basis by additive manufacturing techniques such as 3D-printing and inkjet printing. Several examples of ISM sensors have been demonstrated recently. However, liquid sample handling in microgravity environments produces several challenges, and consequently all liquid handling must be contained in a closed environment to prevent sample loss and contamination of crew quarters.

Here we demonstrate the development of an ISM-compatible manifold for the fluidic integration of printed sensors (FLIPS). Our approach to the development of the FLIPS manifold is to identify components that cannot be manufactured using ISM techniques, and to fabricate all other components using flight-heritage 3D-printing and CNC cutting. FLIPS includes a mounted peristaltic pump and switch valve with measurements performed on off-the-shelf screen-printed carbon electrodes. We demonstrate the performance of the manifold with a model redox species (ferrocene carboxylic acid). Finally, we show the potential application as an integrated healthcare diagnostic system by detection of a renal health biomarker, alkaline phosphatase.
This capability is necessary to ensure the success of ISM sensors for liquid samples and allows further customization of sensor architectures. The FLIPS platform demonstrates the applicability of ISM to complex fluid handling that will be adopted in future NASA missions.
Ni-YSZ Electrode Stability in Solid Oxide Electrolysis Cells Operated in 90-98% Steam
Authors: Le Long , Coyle Christopher , Seymour Lorraine , Zaengle John , Escobar Julian , Liu Tian , Bao Jie , Meinhardt Kerry , Marina Olga A 
Published: September 2023

Ni-YSZ electrode-supported SOECs were tested at 750 and 800oC using extremely high steam concentrations, 90, 95, and 98%. The performance was compared to SOECs tested in 50% steam with 50% hydrogen. Multiple cells were tested simultaneously with several repeats, all cells configured into a single furnace for each test to ensure a reasonable side-by-side comparison and results reproducibility. The Ni/YSZ electrodes was reduced by hydrogen in situ at each operating temperature and then 50-98% steam was added. Cells were tested at a fixed current or voltage for 1000-3000 hours. The electrochemical impedance data was periodically collected followed by the DRT analyses to identify any changes in polarization losses in time. Minimal to no changes in cell performance in time was observed when compared cell operation in 90+% steam vs 50% steam. Slightly higher degradation was seen for cells tested at 800oC vs those tested at 750oC during the initial 500 hours. After the initial break-in period, the degradation rates for all cells in the following >1000 hours remained the same.
A separate set of tests was performed to characterize break-in period and to understand how the initial Ni thermal aging at different temperatures affects the time to a pseudo steady-state, i.e., if the Ni aging/conditioning could be used to accelerate the initial degradation and shorten break-in. Symmetrical cells with two Ni-YSZ electrodes on each side of 10 micron YSZ electrolyte were also tested.
The extensive SEM/EDS analyses were performed on all cells to quantify the Ni particle size and describe any microstructural changes. The 2-dimensional SEM images were reconstructed into the 3D microstructures to calculate the triple phase boundary density, species transport paths tortuosity, and particle/pore size distribution.
Scale Up and Coupling of the MOXIE Solid Oxide Electrolyzer for Both Terrestrial and Space Applications
Authors: Hollist Michele , Larsen Dennis , Gomez Abel , Hafen Tyler , Czernichowski Piotr , Valdez Skyler , Lingen Jeffrey , Izatt Becca , Pike Jenna , Hartvigsen Joseph , Elwell Jessica , Elangovan S 
Published: September 2023

The Mars Oxygen ISRU Experiment (MOXIE) is a first of its kind demonstration of in-situ resource utilization technology to produce propellant and breathable oxygen from the Mars ambient carbon dioxide. The use of Lunar and Martian resources represents a significant opportunity to reduce the cost of launch from Earth, enabling propellant production for space refueling, and allowing for life support of manned missions to the Lunar and Martian surfaces.
Since developing the Solid OXide Electrolysis (SOXE) stacks for the Mars 2020 MOXIE program in 2017, the OxEon team has made significant advancements in scale and capabilities of the SOXE stack technology used in that system. Newer variants have a five-fold larger cell area and a 6.5-fold increase in cells per stack, for a stack scaled 33-times the 0.5% scale of the device in MOXIE. Six of these OxEon mission-scale SOXE stacks will produce 30 tons of propellant oxygen to fuel a Mars Ascent Vehicle (MAV) in the 19-month window between landing an unfueled MAV pre-supply mission and the next launch opportunity for the first crewed Mars Mission, meeting target requirements for a return mission. OxEon has built and demonstrated systems with mission-scale stacks for both Lunar and Martian applications. A system for the production of propellant H2 and O2 from Lunar ice was successfully tested in a cryo-vac chamber at the Colorado School of Mines in 2022. Another mission-scale demonstration system is scheduled to demonstrate production of O2 and methane from Martian H2O and atmospheric CO2 at Jet Propulsion Laboratory in 2022.
In addition to SOXE/SOFC systems, the OxEon technology portfolio also consists of a low energy plasma reformer capable of producing sygnas from a variety of hydrocarbons and a modular-scale Fischer-Tropsch reactor for the production of liquid fuels from syngas. These technologies allow OxEon to provide a wide range of terrestrial energy solutions. A DOE Bioenergy Technologies Office (BETO) funded system is currently being fabricated to demonstrate the conversion of both CO2 and CH4 in anaerobic digester gas to liquid transportation fuels. This will be accomplished using an SOEC system to convert steam and CO2 to synthesis gas. OxEon’s plasma reformer will be used to convert methane to synthesis gas, using the plasma to catalyze the reaction of methane with steam and oxygen, supplied in part by the byproduct oxygen from the electrolysis system. The syngas from the plasma reformer and electrolysis systems are then combined to produce liquid fuels in the Fischer-Tropsch (FT) reactor.

Figure 1
Exploring Solid Oxide Electrolysis Cell Design for an Optimal Flow Distribution and Thermal Management
Authors: Jimenez-Martín Gonzalo , Judez Xabier , Aguado Mónica , Garbayo Iñigo 
Published: September 2023

Climate crisis and the subsequent increase of fossil fuels prices have encouraged the search for alternative and renewable energy sources. In this scenario, the use of hydrogen as green energy carrier is nowadays regarded as one of the keys to achieve the transition to a fully renewable energy system. Among the existent and commercial technologies to produce green hydrogen, solid oxide electrolysis (SOE) outstands due to their high efficiency and the possibility of operate in reversible mode, i.e on electrolysis mode to produce hydrogen and on fuel cell mode (SOFC) to generate power from stored hydrogen. However, large-scale commercialization of these devices is still to-be-realized, mainly hindered by their short life time caused by degradation problems.
Apart from a correct materials selection and optimal microstructural design, uniform gas flow distribution along the cell is necessary. This is not only essential to reach higher performance but also to ensure good temperature distribution and minimize hotspots that would accelerate degradation. Therefore, cell design should be carefully optimized. For this purpose, replacing experimental cell design by computer modeling and simulation has been presented as a cost-effective alternative. In this sense, computational fluid dynamics (CFD) is a powerful tool that accurately predicts the behavior of the cells in diverse scenarios. CFD uses numerical analysis to solve the equations that define the behavior within the cells, including mass, species, momentum, energy and current conservation as well as electrochemical and heat transfer models that govern SOE behavior.
In this work, strategies to optimize cell design and their implementation by means of ANSYS Fluent® commercial CFD software are presented. These strategies have been classified into two categories: i) modifying gas manifolds and ii) modifying internal gas channels. On one hand, the strategies related to manifold design include acting on the number of inlets, outlets and its type (i.e open to ambient or pipes). On the other hand, the strategies related to internal gas channels design involve using different interconnect plate geometric features such as rectangular or cylindrical ribs. By changing these cell features, significant improvements in flow distribution and minimized thermal gradients and pressure drop are observed. Simulations conclude that manifolds are the most influential cell feature in terms of flow, thermal and pressure drop distribution, obtaining that a simple modification in the number of inlets and outlets can conduct to normalized mass flows near to the unit, thermal gradients below 1 K/cm and a negligible pressure drop.

Figure 1
Oxygen Non-Stoichiometry and Point Defect Equilibria in (La1/6Pr1/6Nd1/6Gd1/6Ba1/6Sr1/6)MnO3-
δ
Authors: Bishop Sean R , Zhang Dawei , Liu Cijie , Li Wei , Salinas Perla A , Smith Andrew I , Coker Eric N , De Santiago Héctor A , Liu Xingbo , McDaniel Anthony H , Luo Jian 
Published: September 2023

Compositionally complex oxides (CCOs), also referred to as high entropy oxides, have several different cations (typically 5 or more) occupying a single site. CCOs have shown unique dielectric, ionic conductivity, and thermal conductivity properties, in addition to promising electrochemical properties for solid oxide fuel cells (SOFCs) [1,2]. In this work, the A-site of the common SOFC cathode La0.8Sr0.2MnO3-δ (LSM) is modified with additional lanthanide and alkali elements, resulting in the composition (La1/6Pr1/6Nd1/6Gd1/6Ba1/6Sr1/6)MnO3-
δ. Typically, the average lattice parameter is correlated with bond length and strength, and thus energetics of oxygen vacancy formation energy. In the compositionally complex system, there is a wide range of cation radii on the A-site and so bond strengths are expected to vary significantly, resulting in a distribution of oxygen vacancy formation energies. Initial results have shown that the amount of oxygen released during reduction is significantly greater for the studied CCO in comparison with La2/3Sr1/3MnO3-δ, the latter having the same amount of total acceptor dopant and with a similar lattice parameter as the CCO. The significant enhancement in oxygen loss is an indicator of a lower reduction enthalpy and suggests a significant impact from atomic structure that is not captured in long-range structure parameters (i.e., average lattice parameter). The oxygen non-stoichiometry measured by thermogravimetric analysis in ~10-5 – 1 atm O2 at 1200 oC – 1450 oC will be presented and the point defect equilibria analysis will be discussed. Comparisons with existing high temperature experimental and modeling studies on LSM will also be discussed.
SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525
References
[1] Xu, Y., et al., J. Adv. Ceram., 11 (2022) 794, DOI:10.1007/s40145-022-0573-7
[2] J. Dabrowa, et al., J. Mater. Chem. A, 8 (2020) 24455; DOI:10.1007/s40145-022-0573-7
Numerical Analysis of Humidification Condition Effects on Protonic Ceramic Fuel Cell Performance Considering Concentration Overpotential
Authors: Li Kunpeng , Ryogo Takatera , Nagata Yohei , Murakami Takeru , Araki Takuto , Okuyama Yuji , Mori Masashi 
Published: September 2023

Protonic ceramic fuel cells (PCFCs) show relatively high performance at intermediate temperature range (400–600 °C) due to high proton conductivity in electrolyte. However, besides proton, other charges such as electron hole and oxygen vacancy can also be conductive in PCFCs. Especially, the hole conductivity will induce a hole current leakage so that current efficiency and power density will decrease. Besides the operating temperature, the conductivities of proton and hole are also strongly affected by the partial pressures of steam and oxygen in the PCFC [1,2]. Higher steam partial pressure leads higher proton conductivity, so that a higher power density can be expected. However, other influences such as concentration overpotential may be non-negligible. Furthermore, the proton and hole current density are affected by defect concentrations differences between two surfaces of the electrolyte membrane. Numerical simulation method is powerful tool for dealing with the complicated conditions in a PCFC mentioned above.
In the present study, the influences of steam partial pressure on a BaZr0.8Yb0.2O3−
δ

(BZYb20) electrolyte are investigated. Specifically, to reveal the currents induced by the electrostatic potential and gas concentrations, Nernst-Planck model is selected. To relatively obviously reveal the steam concentration influences on the PCFC performances, low (3%) and high (69%) humidification conditions of H2 fuel gas are adopted. The results in Fig. 1(a) and 1(b) show the simulation and experimental current-voltage characteristics under 3% and 69% humidification conditions, respectively. The green solid and dotted lines are external and proton current densities considering concentration overpotential influence, respectively. The blue lines express external current density when no concentration overpotential in the numerical model. The red circles are the measured data. At low steam partial pressure, the simulation results well reproduced the experimental data without concentration overpotential consideration. However, an obvious deviation was found between simulation and experimental results when neglecting concentration overpotential in the simulation model. The performances such as open circuit voltage (OCV) and hole current leakage (difference between proton and external current density) are influenced by the steam partial pressure.

References

[1] K. Li
et al
., Int. J. Hydrogen Energy, 45 (2020), 34139-149.
[2] Y. Okuyama,
et al
., J. Hydrogen Energy, 39 (2014), 20829-36.

Figure 1