bluuebunny/crossref_metadata_2025_split huggingface dataset:
Computational Modeling and Machine Learning Approaches for Accelerated Materials Design
Authors: Matanovic Ivana , Davis Megan Christina , Kort-Kamp Wilton , Holby Edward F. , Klein Jeffrey Michael , Leonard Daniel P , Kim Yu Seung , Zelenay Piotr 
Published: August 2024

A substantial part of research in energy storage and conversion systems concerns the discovery and characterization of novel materials with improved performance, but most advancements are still generally attributed to costly and time-consuming trial-and-error experimentation. Computational chemistry methods combined with machine learning techniques offer paradigm shift in how materials are fundamentally understood and designed. Namely, high-throughput calculations combined with machine learning can help evaluate different properties of complex materials and efficiently screen millions of candidates to identify the ones with improved targeted properties, such as higher activity and selectivity and/or enhanced durability.
In this talk we will first illustrate the use of density functional theory (DFT) in the design of fuel cell and electrolyzer ionomers. More specifically, we will discuss how simple descriptors such as DFT-calculated adsorption energies and adsorption modes of polymer fragments can be used to guide the rational design of ionomers for anion exchange membrane fuel cells and alkaline membrane water electrolyzers. Our design principle has led to the synthesis of new polymers, e.g., poly(fluorene) and polynorbornene-based ionomers, with weak adsorption on the electrocatalyst surface and improved hydrogen oxidation reaction activity. We will further introduce the computational workflow that integrates high-throughput DFT calculations with machine learning with a goal of designing new amine-based CO2 adsorbents, as well as platinum group metal-free electrocatalysts for conversion of CO2 to value added products. In our workflow we use descriptors together with DFT-calculated binding energetics to train artificial neural networks for activity prediction. Our trained machine learning models are then used to screen millions of candidate chemistries and identify the ones with optimal activity. Descriptor importance evaluation provides additional design principles based on the structure to property relationships for the synthesis of targeted materials for CO2 capture and electro-conversion.
Shape Optimization for Lithium-Ion Battery with Porous Electrodes
Authors: Li Hanyu , Barrera Jorge-Luis , Roy Thomas 
Published: August 2024

In this presentation, we introduce a gradient-based shape optimization framework to design porous electrodes for maximum energy storage. Lithium-ion batteries are becoming an increasingly important energy source and storage device. Large surface area that advocates high reaction rates often leads to small porosities that deteriorate electrochemical transport, which significantly restricts ion penetration depth, limiting the material utilization in planar electrodes. Consequently, architected electrodes are required to optimize performance.
We consider a model with two materials, namely porous electrode and pure electrolyte. Density-based topology optimization with continuous material volume fraction has previously been implemented on lithium-ion battery system for both half-cell and full-cell model to maximizes its energy storage. Despite the capability of producing complex interdigitated structures, an appropriate penalization scheme for intermediate materials is required for the optimizer to provide near binary designs. Setting up such a penalization is often time-consuming due to the large number of design-dependent variables that affect the forward model differently. Alternatively, the shape optimization approach used in this work produces binary designs naturally by morphing conformal meshes, circumventing inaccuracies associated with fuzzy interfaces. Shape sensitivities are computed via the adjoint method and leveraging automatic differentiation. The optimization problem is solved using a nonlinear programming technique.
In this presentation, we perform shape optimization on a half-cell model to maximize its energy storage when a fixed charging current is applied. We study multiple arrangements of physical parameters and compare their performance against a monolithic electrode. Both 2D and 3D results are presented.
Quantifying Electrolyte Variation through Coupled Molecular Dynamics and Porous Electrode Modeling of Lithium-Ion Battery Cells
Authors: Dix Sean T. , Lowe Jeffrey , Rashvand Avei Mehdi , Garrick Taylor R. 
Published: August 2024

Lithium-ion battery cell modeling using physics-based approaches such as porous electrode theory is a powerful tool for battery design and performance analysis both at the beginning and end of life[1]. Cell metrics such as resistance and thermal performance[2-6] can be quickly calculated in a pseudo-two-dimensional (P2D) framework. For engineering of electric vehicle batteries, speed and fidelity of electrochemical models is paramount in a competitive landscape. Physics-based models[7, 8] allow for high fidelity but require detailed knowledge of the cell component material properties. Acquiring these material characteristics typically requires time-consuming and expensive experiments limiting the ability to quickly screen through cell designs. One approach to circumvent costly experiments is to use molecular dynamics[9, 10] to calculate electrolyte transport properties. We demonstrate how cell modeling using simulated transport properties enables predictions of cell level metrics, allowing for experiment-free component screening. We also show how the variation in transport property predictions from molecular dynamics affects the final cell level performance predictions.
References
1. U. Janakiraman, T. R. Garrick and M. E. Fortier, J Electrochem Soc, 167, 160552 (2020).
2. Y. Hu, S.-Y. Choe and T. R. Garrick, Electrochim Acta, 362, 137124 (2020).
3. M. Song, Y. Hu, S.-Y. Choe and T. R. Garrick, J Electrochem Soc, 167, 120503 (2020).
4. Y. Hu, S.-Y. Choe and T. R. Garrick, Applied Thermal Engineering, 189, 116709 (2021).
5. Y. Hu, S.-Y. Choe and T. R. Garrick, J Power Sources, 532, 231350 (2022).
6. M. Song, Y. Hu, S.-Y. Choe and T. R. Garrick, J Electrochem Soc, 169, 070502 (2022).
7. T. R. Garrick, J. Gao, X. Yang and B. J. Koch, J Electrochem Soc, 168, 010530 (2021).
8. J. S. Lopata, T. R. Garrick, F. Wang, H. Zhang, Y. Zeng and S. Shimpalee, J.
Electrochem. Soc., 170 (1) 020530 (2023)
9. S. T. Dix, J. S. Lowe, M. R. Avei and T. R. Garrick, J Electrochem Soc, 170, 083503 (2023).
10. T. R. Garrick, Y. Zeng, J. B. Siegel, and V. R. Subramanian, J. Electrochem. Soc., 170 113502 (2023)
Effect of Metal Work Function on Electron Transfer Kinetics in Electrochemical Reactions
Authors: Buckley D. Noel , Leddy Johna 
Published: August 2024

The longstanding problem of explaining the observed dependence of the kinetic rates of electrochemical reactions on the work function of the electrode material (metal) is revisited, based on a recent paper.1 It was proposed that this dependence could be explained in terms of the effect of the work function of the metal on the free energies of activation of the forward and backward electron transfer reactions. In this presentation, we will explore details of the proposed mechanism.
In essence, the mechanism is based on the effect of work function on the Galvani potential of the metal at any given applied potential. Even though the total electron energy (Fermi level) of an electron in the electrode must be the same, regardless of the metal, when it is at equilibrium with a given electrolyte, the manner in which that energy is partitioned between the effect of work function and the effect of potential is significantly different for different electrode materials. A higher work function leads to more stabilization of an electron in the metal (lower free energy) and, since the total free energy must remain the same, this lower free energy due to work function must be compensated by a more negative Galvani potential.
The classical analysis of the effect of a more negative potential is based on the theory that a change in potential has a greater effect on the initial (reactant) free energy than it does on the free energy of the transition state. Consequently, the activation energy of the forward (cathodic) reaction is decreased by some fraction α of the corresponding increase in electron energy in the metal. This type of analysis is generally used to quantify the effect of changes in applied voltage and derive current-voltage relationships. In this paper we extend the analysis to take account of changes in the (Galvani) potential ϕm of the metal due to changes in work function Φm.
It is reasonable to assume that a change in ϕm will have a similar effect whether it occurs due to a change in applied voltage or due to a change in the work function of the metal. This implies that an increase in work function with a corresponding negative shift in Galvani potential can lead to a lowering of activation energy and so to faster kinetics. However, we must also consider a possible change in activation energy arising from the decreased electron energy (increased stabilization) due to higher work function. If this caused a change in activation energy it would be expected to be in the opposite direction to the change due to Galvani potential, since it would be expected to lower the initial free energy by a greater amount than that of the transition state.
The presentation will consider in detail the interplay of these effects and the consequent implications for modelling electrode kinetics.

K. S. R. Dadallagei, D. L. Parr IV, J. R. Coduto, A. Lazicki, S. DeBie, C. D. Haas, and J. Leddy, J. Electrochem.
Soc.
170, 086508 (2023)
Origin of Stability and Activity Enhancements in Pt-Based Oxygen Reduction Reaction Catalysts Via Defect-Mediated Dopant Adsorption
Authors: Sawant Kaustubh NMI , Zeng Zhenhua , Greeley Jeffrey 
Published: August 2024

Platinum alloys are highly efficient electrocatalysts for the oxygen reduction reaction (ORR) in acidic conditions. However, these alloys are susceptible to metal loss through leaching and degradation, leading to reduced catalyst stability and activity. Recently, it has been shown that doping with oxophilic elements can significantly alleviate these problems, with a prominent example being Mo-doped Pt alloys. Here, to achieve atomic scale understanding of the exceptional activity and stability of these alloys, we present a detailed density functional theory description of the dopants’ structures and impact on electrocatalyst properties. Beginning with the Mo/Pt system, we demonstrate that Mo can be stabilized in the form of low-dimensional oxyhydroxide moieties on Pt defects. The resulting structures enhance stability and activity via distinct physical processes, with the Mo moieties both directly inhibiting Pt dissolution at defects and indirectly enhancing ORR activity by generation of strain fields on surrounding Pt terraces. We then generalize these analyses to other metal dopant elements, and we demonstrate that similar low-dimensional oxyhydroxide structures control the electrocatalytic properties through an intricate interplay of the structures’ acid stability, intrinsic activity for the ORR, and ability to induce ORR-promoting strain fields on Pt.
Reference:
Sawant, K., Zeng, Z. & Greeley, J., Angew. Chem., Int. Ed., 10.1002/anie.202312747
Modeling of Fluidized Bed Molten Carbonate Direct Carbon Fuel Cell: Effect of Reverse Boudouard Reaction
Authors: Suarez Errol John Elizondo , Ortenero Joseph Rempillo 
Published: August 2024

Direct carbon fuel cells (DCFCs) are an alternative technology to coal-fired power plants for converting the chemical energy of abundant carbon-rich fuel into electrical energy. DCFCs have higher electrical efficiency and lower greenhouse emissions, which are easier to separate and capture. In the transition to renewable sources of energy, efficient and low-emission technologies need to be explored. Since DCFC technologies are in their early stages of development, modeling and simulation studies are needed to reduce costs and aid in experimental design. In this study, an electrochemical and transport model for a fluidized bed molten carbonate DCFC (FBMCDCFC) is developed. The performance of the fuel cell is evaluated through the polarization losses. This study expounds on recent developments in DCFCs by considering the effect of the reverse Boudouard reaction and the 2-electron oxidation of CO alongside the 4-electron oxidation of carbon at higher temperatures. The electrolyte used is a 62 : 38 mol % Li2CO3/K2CO3 eutectic mixture, while the fuel is activated carbon impregnated by HNO3. The results show that the greatest polarization losses for the FBMCDCFC are from anode activation overpotential and ohmic overpotential. The cathode activation and concentration overpotentials are relatively small. Increasing the reaction temperature results in a greater decrease in anode activation overpotential than ohmic overpotential, despite the increase in CO formation from the reverse Boudouard reaction. The peak power density of the FBMCDCFC is 434.437 W m-2 when operated at 923 K and a gas flow rate of 30 mL min-1. The peak power density of the FBMCDCFC is greater with higher temperatures, where the peak increases to 584.802 W m-2 when operated at 1023 K. The peak power density is greater with lower gas flow rates, where the peak increases to 458.175 W m-2 at a gas flow rate of 25 mL min-1. The mathematical model can aid in optimizing the performance of FBMCDCFCs, such as how increasing the operating temperature favorably increases anode reaction kinetics and reduces ohmic resistances in the cell. Future work will focus on improving the model correlations to close the gap between the results of modeling and actual experiments.
Figure 1. a) Power curves at different temperatures, 823 K to 1323 K (30 mL min-1 flow rate, 1 atm total pressure); b) Power curves at different gas (O2 and CO2) flow rates (923 K, 1 atm total pressure)

Figure 1
Novel Fast-X-Ray Reflectivity Setup for Studying Electrochemical Interfaces
Authors: Corts Wieland , Ge Xiaokun , Matar Toka , Steinruck Hans-Georg , Frücht Sebastian , Bertram Florian , Lippmann Milena 
Published: August 2024

A fundamental understanding of atomic scale processes occurring at electrochemical interfaces is crucial for advancing the development of energy-related electrochemical systems such as ion batteries or fuel cells. For this purpose, operando experiments are imperative. X-ray reflectivity (XRR) is a non-destructive technique that enables operando analysis of buried structures with atomic resolution [1,2]. However, the time-resolution of typical XRR setups of minutes per XRR scan is limited by diffractometer motor motion and detector read-out times; this resolution is in many cases too slow to observe interfacial electrochemical phenomena [1,2].
To overcome these limitations, we developed a novel fast-XRR setup, which employs a fast quasi-continuous rotation stage in combination with a stationary, high frame rate area detector. With this setup, the sample can be rotated with a frequency of up to 10 Hz, yielding sub-second time resolution for an individual XRR scan. In contrast to complementary fast-XRR setups [3,4], the presented setup can easily be combined with complex sample environments, as typically required for the investigation of electrochemical interfaces.
We present first fast-XRR results obtained at PETRA III beamline P08 at DESY using 18 keV and a Dectris Eiger1M detector. We reached a time resolution below one second for an incident angular range between 0° – 6° (≙ 0 – 2 Å-1, i.e., covering the Fresnel XRR range). We measured several multilayer samples (e.g., 2 nm Ti / 20 nm Au coating on a Si substrate) and benchmarked the results to “standard” XRR measurements, where the measurements took several minutes. We find good agreement and conclude, that our novel setup provides significant XRR data within less than one second, demonstrating its usability for operando XRR measurements.
Literature:
[1] C. Cao, H.-G. Steinrück, Encyclopedia of Solid-Liquid Interfaces, 391–416, Elsevier, 2024.
[2] C. Cao, H.-G. Steinrück et al., Nano Letters, 16, 12, 7394–7401, 2016.
[3] M. Lippmann et al. Review of Scientific Instruments, 87, 113904, 2016.
[4] H. Jorres et al., Applied Physics Letters, 114, 081904, 2019.
Investigation of 40 Ah Prismatic Batteries Operating Under Fast-Charge Conditions Using Operando Synchrotron XRD Technique
Authors: Alrifai Bouthayna , Vincent Remi , Mirolo Marta , Jacquet Quentin , Charbonnel Juliette , Genies Sylvie , Daniel Lise 
Published: August 2024

The pressing challenges posed by the energy crisis and the impact of climate change have forced a gradual replacement of traditional internal combustion engine (ICE) automobile powertrains with electrochemical energy storage devices. However, a boost of the electric vehicles (EVs) market, by significant battery performance enhancements are consistently required, primarily due to numerous persistent concerns. One of the key features targeted by battery and EVs industries is the rapid charging capability, making EVs more competitive with the quick refueling of traditional gasoline vehicles. Notably, despite the clear benefits of fast charging technology, the accelerated battery degradation after fast and extreme fast charging raises on top of the drawbacks of this technology. Therefore, understanding of heterogeneity and structural transformations within battery systems is of high interest.
In this regard, we attempt to investigate the structural properties of a LiNi1/3Mn1/3Co1/3O2 (NMC111) /graphite fresh industrial prismatic cell using synchrotron XRD under fast charge conditions. The investigated battery is a PHEV cell with an experimental capacity of 40 Ah. It was taken from a range rover vehicle pack after being disassembled. The evolution of the composite anode and cathode structures was followed by operando wide-angle X-ray scattering (WAXS). Using this approach, we were able to measure and quantify the different phases of graphite and NMC111 lithiation/delithiation at various potentials by analyzing the corresponding Bragg peaks. By that, we were able to detect some heterogeneities in the degree of lithiation/delithiation within the cell upon charge. In addition, a comparison between a fresh cell and another aged cell, with a state of health (SOH) of 88%, was made in order to investigate the effect of aging under fast charging conditions on the performance of the industrial LIBs.
Operando X-Ray Scattering for Electrocatalysis and Beyond
Authors: Ennaji Meryem , Gasmi Amir , Amigues Simon , Jones Deborah J. , Jaouen Frederic , Drnec Jakub , Chattot Raphael 
Published: August 2024

The energy transition stands as one of the greatest challenges of today’s society. In this context, electrocatalyst materials at the heart of electrochemical energy conversion devices such as fuel cells and water electrolyzers are expected to play an increasing crucial role in the near future. The urgent bottleneck to be overcome in electrocatalyst materials development to allow the widespread deployment of electrochemical systems is thus reaching combined high activity and long-term stability at low cost. Despite the diversity in electrocatalyst materials, the latter being largely imposed by the various types of electrochemical systems (noble vs. non-noble metals in acidic vs. alkaline media for example) and the prerequisites of the different electrochemical processes (oxidation or reduction reactions of various species at different electrode potential ranges), most activity and stability properties of electrocatalysts directly derive from their (surface) chemistry and structure [1]. Such properties (and their temporal evolution) can thus be directly investigated by means of in situ or operando high energy X-ray scattering (XRD) technique [2].
In this presentation, the versatility of in situ and operando XRD technique in addressing key bottlenecks in electrocatalyst materials development, notably by probing adsorption and oxidation trends [3], will be showcased. After an overview of previous contributions from the literature, the talk will focus on our ongoing works which encompass the study of Pt-based nanocatalysts for the oxygen reduction reaction (ORR) at proton-exchange membrane fuel cells (PEMFCs) anode, carbon-capped Ni@C catalyst for the hydrogen oxidation reaction (HOR) at anion-exchange membrane fuel cells (AEMFCs) anode and IrCu unsupported aerogel catalyst for the oxygen evolution reaction (OER) at proton-exchange membrane water electrolyzers (PEMWEs) anode.
Finally, the ability of operando XRD to provide device-relevant insights at the macroscale (such as ionomer hydration in PEMFCs or water distribution in AEMFCs) beyond electrocatalysts microstructural properties will be presented. References
[1] Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, and T. F. Jaramillo. Combining theory and experiment in electrocatalysis: Insights into materials design. Science, 355(6321): eaad4998, 2017.
[2] Magnussen, O. M., Qiu, C., Drnec, J., Martens, I., Jared Huang, J., Chattot, R., & Singer, A. (2023). In situ and operando X-ray scattering methods in electrochemistry and electrocatalysis. Chemical Reviews, Accepted.
[3] Chattot, R., Martens, I., Mirolo, M., Ronovsky, M., Russello, F., Isern, H., Braesch, G., Hornberge, E., Strasser, P., Sibert, E., Chatenet, M., Honkimäki, V., Drnec, J. (2021). Journal of the American Chemical Society, 1, 17068-17078.
Approaching the Multiphase Interface of Ir-Based PEM Electrolyzers Using Operando ‘Tender’ X-Ray AP-XPS
Authors: Hamlyn Rebecca , Crumlin Ethan J. 
Published: August 2024

Electrochemical water splitting is a promising pathway for the renewable production of hydrogen as an alternative fuel and chemical feedstock. Yet, the process is plagued by slow kinetics of the essential oxygen evolution reaction at the anode. Further, large-scale hydrogen production from such devices will require reduced platinum group metal (PGM) loadings (often iridium-based anodes) and/or new materials due to factors such as PGM scarcity, cost and loss during operation. In the hopes of enabling progress of rational design for OER catalysts, effective characterization of the electrode-liquid interface is crucial. Synchrotron-based X-ray Photoelectron Spectroscopy (XPS) offers a versatile way to obtain surface chemical and elemental characterization of these materials. The use of X-rays in the ‘tender’ regime (~2-6 keV) allows for deeper probing than the conventional ‘soft’ x-ray (< 2000 eV) set up that is common at synchrotrons and lab-based sources. The photoelectrons generated from tender x-rays have enough energy to penetrate tens of nanometers through low density components such as a layer of liquid or polymeric electrolyte. This opens the door to access the chemistry at the interface of liquid and ionomer electrolyte-electrocatalyst materials. With the use of a fully operational two-electrode system, we are able to study these membrane electrode assemblies under active water splitting conditions.
My talk will explain our specific approach, which is often crucial for successful collection of accurate data, highlighting elements of cell design and experimental setup that are helpful for this process. I will also show recent AP-XPS results on iridium-based polymer electrolyte membranes for water splitting. With application of elevated potential, we can correlate the iridium valency and surface species with the appearance of product traces in a mass spectrum.

Figure 1