bluuebunny/crossref_metadata_2025_split huggingface dataset:
Triple-Phase Pore Network for Oxygen and Proton Transport Model in the Cathode Catalyst Layer of Proton Exchange Membrane Fuel Cells
Authors: Ince Alper Can , Serincan Mustafa Fazil , Holby Edward F. , Spendelow Jacob S. , Pasaogullari Ugur , Kort-Kamp Wilton 
Published: November 2022

Improvement in the mass transport overpotentials of the oxygen reduction reaction provides a pathway for reducing the high cost associated to platinum group metal loading as well as enhancing the lifetime of electrodes in proton exchange membrane fuel cells (PEMFCs). State-of-the-art PEMFCs typically have Pt loadings of the order of 0.3 mgPtcm-2, which is the main part of the estimated stack cost of $55/kW. Understanding transport phenomena at triple phase boundaries that consist of a (solid) electrocatalyst, ionomer, and (gas-phase) oxygen, where the electrochemical reactions occur has gained importance to improve electrocatalyst accessibility. Mathematical models that address transport of electrons, protons, and oxygen in the cathode is critical for an effective catalyst layer design. Modeling of this multiphysics phenomena is further complicated due to multiscale effects. Pore network model (PNM) is a promising technique to tackle these challenges because of its capability of resolving porous networks locally in greater detail. Moreover, improvements in microscopic imaging techniques (e.g., SEM, TEM, and nano CT) enable the generation of realistic pore networks of the catalyst layers that can be directly integrated into PNM. Most modeling studies to date focus on single networks for oxygen transport in the open pore space, or transport of oxygen and water. A pore network that describes oxygen, proton, and electron transport simultaneously remains uncharted. Here, we construct a triple-phase pore network model using nano CT images of heterogeneous porous catalyst layers. Binary images of solid-open pore space and ionomer-catalyst support are generated, which are then overlapped to create ternary images. Pores and throats are then fit to these
images to create pore-networks that describe open-pores for oxygen and water transport, ionomer pores for proton transport, and a solid network for electron transport. A schematic of the approach is shown in Figure 1.
The study offers a new method that constructs a triple pore network for a porous material in which two levels of open space porosity (micro and macro) exist in connection with solid and ionomer networks. Therefore, a
realistic pore network is obtained to be further modeled through the approach presented.

Figure 1
Model Development for Temperature-Dependent Degradation in Large Format Lithium-Ion Batteries
Authors: Mishra Lubhani , Subramaniam Akshay , Jang Taejin , Garrick Taylor R. , Subramanian Venkat R. 
Published: November 2022

Large-format cells are achieving increasing popularity for Electric Vehicle (EV) applications to maximize volumetric and gravimetric energy densities. These large batteries are often characterized by spatial non-uniformities in temperature and resulting difficulties in maintaining uniform temperature distribution. This poor thermal management is a primary reason for the inefficient performance and safety risks associated with these large format batteries and battery packs. Further, there have been several reported degradation mechanisms which are responsible for the capacity fade within Lithium-ion (Li-ion) batteries over multiple charge/discharge cycles. In particular, the presence of thermal gradients and consequent non-uniformities greatly exacerbates degradation, and poses serious safety risks. Thus, it is imperative to identify and study the degradation mechanisms coupled with the thermal effects by incorporating detailed physics-based models to characterize the cell-level phenomena.
This work aims to perform a detailed model-based study on the combined effects of battery degradation and temperature inhomogeneities within large-format Li-ion cells and battery packs. This simultaneous analysis for temperature-dependent degradation will be performed with a state-of-the-art electrochemical model like the classic pseudo-two-dimensional (p2D) model to be able to present a comprehensive analysis of the battery performance parameters. These models will be augmented to include thermal effects and various degradation mechanisms for Solid Electrolyte Interphase (SEI) formation and Lithium plating. The proposed numerical framework will be validated with experimental data for the loss in battery capacity over cycles. In addition, the model development, especially the weak form for model equations and their implementation in a finite-element solver, COMSOL Multiphysics, will be discussed in detail.
This study primarily focusses on certain important aspects of temperature-dependent degradation, viz., (a) cell-to-cell temperature variation, (b) operating conditions for current, (c) topology for the cell arrangement within the battery module, and (d) choice of the degradation mechanism. The delineation of the effects of these complex factors on the cell-level signatures will be of significant utility in monitoring and identifying the performance limitations of individual cells, and thereby help maximize the performance of large format cells and battery packs.
The ultimate goal is the design of a simple yet efficient numerical model with fast and robust simulations for the analysis of the temperature-dependent degradation of the Li-ion battery packs over a wide range of operating and design conditions. The proposed model will be developed to be computationally feasible for an adoption and implementation in a battery thermal management system.
Enhanced Multi-Carbon Selectivity Via Tandem CO2 Electroreduction
Authors: Xia Rong , Jiao Feng 
Published: November 2022

Electrifying chemical production is a potential approach to decarbonizing the chemical industry. Currently, 21% of the global greenhouse gas emissions come from the industry sector, while chemical manufacturing accounts for the largest share of industrial carbon emissions1. The electrochemical processes, when powered by renewable electricity, have lower carbon footprints than conventional thermochemical routes. The rapid development of renewable energy provides opportunities for electrifying chemical production and decarbonizing the chemical industry. Among these, electrochemical CO2 reduction reaction (CO2RR) attracted much attention as a potential pathway for carbon utilization and sustainable chemical production. In this presentation, I would like to present a tandem CO2 electroreduction scheme for multicarbon production. A molecular tuning strategy is applied to tune the intermediate binding energy and thus enhance the CO selectivity in the first step2. Then CO2 and CO electroreduction to C2+ products in alkaline conditions are compared, with particular emphasis on carbonate formation and carbon efficiency (i.e., the amount of carbon ended in the desired products divided by the total amount of CO2 consumed)3. The conclusion is that CORR shows specific advantages over CO2RR in the aspects of C2+ selectivity, stability, carbon efficiency, and single-pass conversion. Then oxide-derived Cu plates are chosen for the second step in tandem reduction, which shows a C2+ Faradaic efficiency of 83% at -0.59 V vs RHE. Lastly, we further extend our tandem system to electrocatalytic–thermocatalytic reaction for CO2 conversion to C3 oxygenate4. A 25 cm2 membrane electrode assembly device is coupled with a thermochemical hydroformylation reactor to produce 1-propanol and propanal. A total C3 oxygenate selectivity of ~18% is achieved in the tandem reaction.
References:

Xia, R.; Overa, S.; Jiao, F., Emerging Electrochemical Processes to Decarbonize the Chemical Industry. JACS Au 2022, 2 (5), 1054-1070.

Xia, R.; Zhang, S.; Ma, X.; Jiao, F., Surface-functionalized palladium catalysts for electrochemical CO2
J. Mater. Chem. A 2020, 8 (31), 15884-15890.

Xia, R.; Lv, J.; Ma X.; Jiao, F., Enhanced multi-carbon selectivity via CO electroreduction approach. Catal. 2021, 398, 185-191.

Biswas, A. N.; Xie, Z.; Xia, R.; Overa, S.; Jiao, F.; Chen, J. G., Tandem Electrocatalytic–Thermocatalytic Reaction Scheme for CO2 Conversion to C3
ACS Energy Letters 2022, 2904-2910.
Novel Ni-V-Y Electrocatalysts for Hydrogen Evolution Reaction
Authors: Storimans Emma Adriana , Thorpe Steven 
Published: November 2022

Generation of renewable energy is improving globally, the ability to store generated energy remains an issue. A new class of water electrolysers that utilize anion exchange membranes (AEMs) are effective at converting water to hydrogen gas which can be used as fuel. Novel electrocatalysts are required for AEMs to be active, stable, and cost effective when used in AEM water electrolysers. Previously, S. Ghobrial investigated the Ni-Nb-Y alloy system as an electrocatalyst for the hydrogen evolution reaction, with Ni and Y components contributed to electrocatalytic activity [1]. Nb phase did not contribute to electrochemical activity and behaved only as a glass former. For the second-generation alloy, V replaced Nb to create a Ni-V-Y alloy. Thermodynamic modelling via FactSage was used to develop the amorphous alloy system. To create the amorphous alloys, a two-step ball milling process was used. Elemental powders were mechanically alloyed and amorphized under cryogenic conditions. The micron sized alloyed powder was size reduced to nanoparticles suitable for use as electrocatalysts via surfactant assisted high energy ball milling (SA-HEBM). Both micron powders and nanoparticles were structurally characterized using X-ray diffraction and SEM. The catalytic activity of the electrocatalysts were electrochemically characterized using steady state polarization to determine Tafel slopes and exchange current densities. A Ni-V-Y alloy was successfully produced via cryomilling and SA-HEBM. The combination of the NiVY amorphous phase + Ni3V + Ni5Y phases in the micron and nanopowders improved activity relative to the intermetallics alone via the spillover effect. The surfactant used in SA-HEBM is not completely removed by the current centrifugation process leading to lower-than-expected activity and marginal spillover enhancement in nanoparticles. With an improved cleaning process, it is predicted the nanoparticles will have higher activities than their micron powder counterparts.
[1] - S. Ghobrial, Amorphous Ni-Nb-Y Alloys as Hydrogen Evolution Electrocatalysts, Toronto: University of Toronto, 2019.
(Invited) Chemistry Effects on the Electrodeposition of Re, Co, and Alloys
Authors: Huang Qiang 
Published: November 2022

Electrodeposition has been adopted in various metallization processes. It allows conformal and super-conformal deposition on curved and recessed substrates, enables the fabrication of metals and alloys with well controlled composition, impurity, and grain structure, and provides fast growth rate, high throughput, and low cost of ownership. Organic additives have been used in electrolytes to tune not only the growth behavior, but also the impurity and grain structure of the deposited material. The most well-known cases are those used for magnetic alloy plating[1,2] in storage and MEMS industry and for damascene copper plating[3,4] in microelectronic industry. On the other hand, the electrolyte itself has largely remained aqueous for most cases. Organic solvents, room temperature ionic liquids, and deep eutectic systems have been widely studied with, however, relatively limited success in large scale adoption.
The first part of this talk will introduce some studies on the electrodeposition of Cobalt as an alternative metal for semiconductor interconnect applications. Organic additives that tailor the deposition rate of cobalt are used to enable the Co filling in sub-micron structures. The effect of such additives on the impurity incorporation and film grain structure will be discussed. The second part of the talk will discuss some recent studies on the electrodeposition from “water-in-salt” electrolytes, where the hydration of a super high concentration of supporting salt depletes the free water molecules in the aqueous solution, thus limiting the hydrogen evolution reaction. The discussion will be in a context of Re and ReCo alloy deposition for superconducting connector applications for quantum devices.

REFERENCES

T. Osaka, M. Takai, K. Hayashi, K. Ohashi, M. Saito, and K. Yamada, A soft magnetic CoNiFe film with high saturation magnetic flux density and low coercivity, Nature, 1998, 392(6678), 796.

E.I. Cooper, C. Bonhôte, J. Heidmann, Y. Hsu, P. Kern, J.W. Lam, M. Ramasubramanian, N. Robertson, L.T. Romankiw, and H. Xu, Recent developments in high-moment electroplated materials for recording heads, IBM Journal of Research and Development, 2005, 49(1), 103.

P. Andricacos, C. Uzoh, J. Dukovic, J. Horkans, and H. Deligianni, Damascene copper electroplating for chip interconnections, IBM Journal of Research and Development, 1998, 42(5), 567.

T.P. Moffat, J.E. Bonevich, W.H. Huber, A. Stanishevsky, D.R. Kelly, G.R. Stafford, and D. Josell, Superconformal Electrodeposition of Copper in 500–90 nm Features, Journal of The Electrochemical Society, 2000, 147, 4524.
(Invited) In-Situ Observation of Copper Electroplating with Additives Using Micofluidic Devices
Authors: Hayase Masanori , Akita Takanori 
Published: November 2022

Recent advances in integrated circuit have been driven by packaging technology. 3D packaging using TSV (Through-Silicon Via) is becoming common in commercial products. TSVs are formed by filling deep holes with a conductive material. Copper is widely used as the conductive material, since filling the deep holes with copper is enabled by bottom-up electrodeposition using a combination of several additives. Suppressors, levelers, and accelerators are well known categories of additive to acid copper sulfate plating solutions. Bottom-up deposition is realized by various additive formulas. Using leveler alone as additive, extreme bottom-up filling has been demonstrated, and levelers are considered to be essential for bottom-up deposition. But the mechanism is not yet clear with multiple additives addition.
Therefore, understanding of additive behaviors is important. Cyclic voltammetry using a rotational disk electrode has been widely used in additive studies, but interpretation of the results is not easy because adsorption occurs simultaneously with deactivation. The history of additive supply onto the plating surface also influences the hysteretic behavior. Recently, we constructed a microfluidic device in which flow cell experiments and rapid switching of the plating solution are enabled. Using the device, characteristic behavior of leveler, strong suppression and rapid deactivation, was directly observed optical microscopically and electrochemically, and difference with levelers and suppressors was clarified. Further, a TSV-like structure with similar dimensions to real TSVs was constructed in a microchannel, and real-time optical observation of bottom-up deposition was demonstrated.
References

T. Akita, et al., J. Electrochem. Soc., 166(1), D3058 (2019)

M. Tomie, et al., J. Electrochem. Soc., 167, 082513 (2020)

T. Akita, Y. Otsuka, M. Hayase, J. Electrochem. Soc., 167, 162515 (2020)
(Invited) Investigation of Pt-Alloy and Strained Pt As Electrocatalysts
Authors: McKeown Cian , Rhen Fernando M. F. 
Published: November 2022

The need to replace conventional sources of energy has driven the development of fuel cell technology. The polymer electrolyte membrane fuel cells (PEMFCs) show high performance and are important power sources for hydrogen fuel cell vehicles due to the fact that the cells can operate at relatively low temperatures (50 - 90 oC) , has high energy efficiency and only emits water as a byproduct. Furthermore, the direct methanol fuel cell emerge as an important technology for the green energy transition with the use methanol fuel. The most important electrocatalyst for the fuel cells is platinum and efforts are made to enhance its performance and reduce its requirement by alloying with other metals. Therefore, novel approaches are required to develop electrocatalysts for the oxygen reduction reaction (ORR) and methanol oxidation using reduced amounts of Pt for use at PEMFC cathodes with high electrocatalytic activity.
Investigation of alloying Pt with transition metals (Ni, Co, Fe) has demonstrated increased electrocatalytic activity and is attributed to changes in the Pt-Pt atomic interaction distances. The electrocatalytic activity is linked to the adsorption of molecular oxygen to the electrocatalytic sites, which is a process enhanced by creating favorable Pt-Pt distances at the electrocatalyst. It is also understood that Pt-alloys have an increased density of d-band vacancies, resulting in stronger binding of OH species to catalyst surfaces. Furthermore, the use of alloying metals causes distortions in the atomic lattice, resulting in compressive strain in the lattice, which increases orbital overlap, widens the d-band, lowers the d-band centre and affects electrocatalytic performance. In addition, enhanced methanol oxidation on strained pure Pt platinum was recently demonstrated and is associated with the preferential absorption of reactant at optimum Pt-Pt interatomic distances.
Here, we show results of electrocatalytic activity for oxygen reduction reaction of Fe-Pt alloy with a range of iron content (0 to 80%), the electrocatalytic activity of highly ordered array of Pt nanotubes for methanol oxidation and the effect of strained Pt on methanol oxidation. Structural and electrochemical data of the catalysts will be presented including rotating disk electrode (RDE) voltammetry and SEM images.
(Invited) Electrochemical Metallization For Semiconductor Applications
Authors: Ahmed Shafaat 
Published: November 2022

Initially after the invention of electroplating in 1805 it was mostly for used decorative applications and making printing press plates. But the introduction of copper as a replacement for aluminum as a CMOS interconnect material in 1997 by IBM (1) was a breakthrough in silicon chip manufacturing. The replacement of aluminum by copper not only has the benefit of lower interconnect resistance, but also has enabled improved interconnect reliability. Cu is expected to show better reliability because it has a high melting temperature and much lower grain boundary- and lattice diffusivity than aluminum (2). since electroplating is a low-cost and reliable technique, the method is being used for a wide variety of metal deposition applications in the semiconductor industry that includes interconnect & packaging metallization, and compound semiconductor fabrication for low-cost solar cells. Since the late 1990's, after IBM introduced copper interconnects, the development of the copper damascene process (1,3) and the implementation of the copper-based interconnect has had a considerable impact in the electrochemical society and semiconductor industries. Copper metallization technology has become critical for CMOS back-end interconnect, embedded multi-chip interconnect bridges, and interposers for 2.5D and 3D applications.
In this presentation, after a brief discussion of the history of metallization by electrochemistry for semiconductor applications, the development of Copper, Gallium, and Cobalt Metallization will be discussed with their application in the semiconductor technology. The discussion will focus on initial issues that arose and the various directions followed to properly address them. The presentation will then focus on the challenge of barrier and seed step coverage and their impact on defects in Cu damascene metallization. Topics of discussion will include the effect of additives, current density, bath aging, shelf life and their implication on product reliability.
References

R, Liu, C. Pai and E Martinez " Interconnect Technology Trend for Microelectronics", Solid state Electron. 43, 1003(1999)

S. Hau-Riege and C. V. Thomson, " Electromigration in copper interconnects with very different grain structures" Appl. Phys. Lett. 78, 3451 (2001)

K. Broadbent, E. J. McInerney, L. A. Gochberg, and R. L. Jackson, " Experimental and Analytical study of seed layer resistance for copper damascene electroplating" J Vac. Sci. Techonl. B17, 2584(1999)
(Invited) Mixed Redox-Active Molecules for High-Energy-Density and Stable Organic-Based Redox Flow Batteries
Authors: Amini Kiana , Jing Yan , Gao Jinxu , Aziz Michael 
Published: November 2022

The intermittency of wind and solar electricity limits their penetration into our energy mix. Safe, cost-effective, large-scale electrical energy storage could solve this problem. Redox flow batteries (RFBs) are emerging energy storage technologies that are expected to have an increasing market size due to their scalability, safety, and system flexibility. Aqueous organic-based RFBs have gained attention due to their potential low cost and the possibility of tailoring the redox properties by modifying the organic chemical structure. To date, significant progress has been made in improving the stability and consequently the lifetime of organic-based RFBs [1-4]. Increased energy density is also desirable but is constrained by limited organic solubility. In this work, we discuss strategies for enhancing the energy density of organic-based RFBs by utilizing mixtures of redox-active organic molecules. In particular, we demonstrate an anthraquinone-based flow battery in which utilization of multiple tailor-made anthraquinones yields a 40% increase in the volumetric capacity, from 26.8 Ah/L to 37.5 Ah/L, without sacrificing the capacity fade rate of the system. The required principles for designing a mixed redox-active organic-based RFB and the possible trade-offs and opportunities will be discussed. These findings provide a pathway for enhancing the competitiveness of RFBs for practical applications.
[1] Kwabi, David G., Yunlong Ji, and Michael J. Aziz. "Electrolyte lifetime in aqueous organic redox flow batteries: a critical review." Chemical Reviews 120, no. 14 (2020): 6467-6489.
[2] Jin, Shijian, Eric M. Fell, Lucia Vina‐Lopez, Yan Jing, P. Winston Michalak, Roy G. Gordon, and Michael J. Aziz. "Near neutral pH redox flow battery with low permeability and long‐lifetime phosphonated viologen active species." Advanced Energy Materials 10, no. 20 (2020): 2000100.
[3] Wu, Min, Yan Jing, Andrew A. Wong, Eric M. Fell, Shijian Jin, Zhijiang Tang, Roy G. Gordon, and Michael J. Aziz. "Extremely stable anthraquinone negolytes synthesized from common precursors." Chem 6, no. 6 (2020): 1432-1442.
[4] Wu, Min, Meisam Bahari, Yan Jing, Kiana Amini, Eric Fell, Thomas George, Roy Gordon, and Michael Aziz. "Highly Stable, Low Redox Potential Quinone for Aqueous Flow Batteries." Batteries and Supercaps (2022).