bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemically Modulated Separation of Olefin-Paraffin Gas Mixtures in Membrane Electrode Assemblies
Authors: Akashige Toshihiro , Katzenberg Adlai , Frey Daniel , Merkhaji Debdyuti , Urbina-Blanco Cesar , Chen Brian , Okamoto Yoshiyuki , Modestino Miguel A 
Published: September 2023

Olefin-Paraffin separations are ubiquitous chemical processes used in purifying monomers for the manufacture of a large variety of polymers and chemical intermediates. Some of the highly demanded olefin-made products include polyethylene, ethylene oxide, vinyl acetate, polypropylene, acrylonitrile, propylene oxide, and acrylic acid. Olefin-paraffin mixtures are relatively difficult to separate because of the similarity in physical properties of each component. Currently, olefins are typically purified via cryogenic distillations, a highly energy-intensive process that liquifies the hydrocarbon gas mixture and re-vaporizes them repeatedly, requiring approximately 3.6 MJ per kg of olefin purified. Because of the large energy-intensive of the process, olefin separations are responsible for approximately 0.3% of the global energy consumption, to produce 200 and 130 million metric tons per year of ethylene and propylene respectively (2020).
Alternative non-thermal olefin-paraffin separation methods have the potential to increase the efficiency of this separation, and thus increase its sustainability. In this presentation we will discuss an alternative separation method based on an electrochemically modulated swing absorption system. In this system, Nickel(II) maleonitriledithiolate, an electrochemically active organometallic complex, is dispersed in an ionogel and integrated in a membrane electrode assembly (MEA). The oxidation state of Nickel(II) maleonitriledithiolate can be electrochemically modulated based on potential. At its oxidized state [i.e., Ni (IV)], the complex has a strong affinity towards the olefin’s pi-bond, while at its reduced state [i.e., Ni (II)] the complex loses this affinity. Our results show that when exposed to propylene-propane gas mixtures, propylene was selectively captured by the organometallic species during oxidative phase, and then released or decoupled during reductive phase. Its paraffin counterpart, propane, behaved as spectator molecules throughout the whole process, demonstrating consistent olefin separation through this selective capture-and-release mechanism. I will discuss how varying the composition of the MEA exposed potential mass transport limitations that play an important role in the separation efficiency and throughput. Experiments conducted under varying potentials exhibited operational robustness of the MEA in gas separations if electric potentials are carefully tuned between 1-3V in the oxidative cycle, and at approximately -2V in the reductive cycle. This proof-of-concept demonstration represents an important step towards achieving high-performing electrochemically-modulated olefin-paraffin separations that can integrate renewable electricity sources directly and help decarbonize the chemical manufacturing industry.

Figure 1
Synthesis and Morphological Control of Fe Metal Particles By Controlling the Metal Complex Condition in Basic Solution
Authors: Takahashi Hideyuki , Yokoyama Koji , Araya Yuma , Asakura Tomokazu , Kumon Shoichi , Sato Kimitaka , Yokoyama Shun 
Published: September 2023

Coronavirus outbreaks have recently necessitated rapid virus recovery and vaccine developments. Magnetic beads are essential components to recover virus in an immunoprecipitation process. Pure iron particles with a diameter of 1 µm can be used as core materials of high-performance magnetic beads.
Thus, the development of effective and green synthesis method of Fe nanoparticles is important. However, Fe nanoparticles were synthesized only in acidic solution by using strong reducing reagent, such as NaBH4, while it cannot be achieved in the basic solution since iron hydroxide, which is easily formed in this condition, cannot be reduced into metals. However, former is not suitable for commercial synthesis method because of its intense reducing process. Thus, the reducing rout of Fe species under basic condition should be developed.
Here, until now, we tried to synthesis the various metal/alloy nanoparticles, such as Pd20Te7 nanoparticles and uniform Cu-In (CI) alloy nanoparticles, by utilizing the restrict metallic complexes controlling method in an aqueous solution under room temperature. In this method, reduction potential of the metal species can be controlled under the room temperature, consequently metal/alloy nanomaterials with uniform and well crystallized structure can be successfully synthesized.
So, in this study, we proposed the synthesis method of iron particles under basic conditions, and morphological conditions control of iron particles by utilizing the “gel-sol” method using gel networks, which is a safe and simple approach to suppress the chain crystallization.
Calculation results indicated that Fe complex can be restricted into one species as the function of pH, complexing reagent species and/also concentration. For example, Fe complex can be restricted into single complex in the basic condition (for example 8<pH<11).
By using this homogeneous condition, metal Fe nanoparticles were successfully synthesized. The addition of gel networks into the synthesis system can effectively suppress the chain crystallization of iron particles. Furthermore, in order to obtain iron particles with organic-free surface, we proposed a novel method to decompose and remove the gel networks.
Other results will present in our presentation. This work was supported by JSPS KAKENHI Grant Number 21H03628 and DOWA holdings.
[1] H. Takahashi et.,al, Applied Catalysis A: General 392 (2011) 80–85
Combinatorial Screening of Nb1-x-YTixWyOz Materials for Li-Ion Battery Anodes
Authors: Sieffert James Michael , Lang Christopher , Rehman Sarish , McCalla Eric 
Published: September 2023

While much attention in recent years has been given to high performance Li-ion batteries for electrical vehicles, other applications require properties that demand a different set of material considerations such as long lifetimes and extremely high safety and reliability. Anodes for such batteries must be carefully selected to properly achieve these goals. The most commonly industrially utilized anode material, graphite, is not ideal for such applications due to particle fracture and Li dendrite growth at high rates. The current state of the art for high power anode materials is Li4Ti5O12 (LTO) where energy density is sacrificed (theoretical capacity of about 170 mAh/g) in order to operate at potentials where the electrolytes are highly stable.
Nb-based oxides have been of interest recently in this regard, with materials such as Nb2TiO7 being considered as industrially relevant for applications where LTO currently dominates. To date in the literature, only 3 compositions have been considered.[1-2] Herein, a wide array of Nb based materials are explored for use as anodes by way of high-throughput experimentation. Over 128 different compositions in the Nb-Ti-W-O pseudoternary space are prepared and characterized with both X-ray diffraction and cyclic voltammetry. Of note, this system features a number of promising solid-solutions that extend well into the ternary system. These compositions derive from crystal structures that are found on both the Nb2O5-WO3 and Nb2O5-TiO2 pseudobinaries, but wide substitutions of the third metal are found to be feasible. This dramatically increases the candidate list for potential anodes. Importantly, the electrochemical performance varies dramatically across the solid solutions. Some ternary compositions feature high discharge capacities of up to 300 mAh/g and high reversibility with 98% capacity retention after 10 cycles. It should be noted that the pseudobinaries have been previously studied in our group with a far lower capacity retention than those found here for some pseudoternary compositions. The rate performance is also found to be outstanding.
The improved specific capacity at a comparable potential as LTO makes Nb-W-Ti-O materials highly promising for applications where high rates and safety are paramount. Results presented here will guide further exploration of the rich chemistry available for Nb-based anodes.
References:

K. J. Griffith, K. M. Wiaderek, G. Cibin, L. E. Marbella and C. P. Grey, Nature, 559, 556–563 (2018)

H. Ding, Z. Song, H. Zhang and X. Li, Mater. Today Nano, 11, 100082 (2020).
Titration Techniques for the Determination of Surface Species on Cathode Active Materials
Authors: Schuer Annika Regitta , Kuenzel Matthias , Yang Shuo , Mueller Franziska , Kosfeld Malte , Passerini Stefano , Bresser Dominic 
Published: September 2023

Lithium ion batteries (LIBs) are the most important energy storage technology of our time. The number of LIBs has been constantly growing during the last years as well as the range of applications where LIBs are used, increasing the need for high energy density LIBs.
One of the main cathode materials for high energy density LIBs is Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811).1 Unfortunately, due to the high Ni content this material is extremely sensitive towards water which poses a particular challenge for more sustainable aqueous processing. Contact with even traces of moisture from the air causes immediate formation of surface species such as LiOH and Li2CO3.2,3 The presence of these surface species not only leads to Li leaching from the structure and subsequent capacity loss but also facilitates side reactions with the electrolyte resulting in gas evolution and ultimately early failure of the battery.4

Developing reliable methods for the quantification of these harmful surface species can provide a link between the amount of surface species and the detrimental impact on the cell performance. Here we employed different measurement techniques to quantify the amount of LiOH and Li2CO3 on the NCM811 material surface.5 Warder titration6 and Winkler titration7 are two methods that have been long known for the determination of hydroxides and carbonates. We optimized these techniques for the determination of very small quantities of surface carbonate or hydroxide by testing the sensitivity for small lab size quantities of material and removing the possibility of additional CO2 uptake through the air. Titration as a way to quantify the amount of LiOH and Li2CO3 is a valuable measurement technique that can help to predict performance issues of the battery and can serve as a tool for quality control of cathode active materials.

References

(1) Armand, M.; Axmann, P.; Bresser, D.; Copley, M.; Edström, K.; Ekberg, C.; Guyomard, D.; Lestriez, B.; Novák, P.; Petranikova, M.; Porcher, W.; Trabesinger, S.; Wohlfahrt-Mehrens, M.; Zhang, H. J. Power Sources
2020, 479, 228708.
(2) Hofmann, M.; Kapuschinski, M.; Guntow, U.; Giffin, G. A. J. Electrochem. Soc.
2020,
(3) Jung, R.; Morasch, R.; Karayaylali, P.; Phillips, K.; Maglia, F.; Stinner, C.; Shao-Horn, Y.; Gasteiger, H. A. J. Electrochem. Soc.
2018, 165 (2), A132–A141.
(4) Kim, Y. J. Mater. Sci.
2013, 48 (24), 8547–8551.
(5) Schuer, A. R.; Kuenzel, M.; Yang, S.; Kosfeld, M.; Mueller, F.; Passerini, S.; Bresser, D. J. Power Sources
2022, 525 (231111).
(6) Benedetti-Pichler, A. A.; Cefola, M.; Waldman, B. Ind. Eng. Chem. - Anal. Ed.
1939, 11 (6), 327–332.
(7) Winkler, C. Praktische Übungen in Der Maßanalyse, 5. Auflage.; Verlag von A.Felix: Leipzig, 1920.
(John B. Goodenough Award of The Electrochemical Society) Oxide Revolution in Energy Storage
Authors: Manthiram Arumugam 
Published: September 2023

Lithium-ion batteries have become an integral part of our daily life. The triumph of lithium-ion batteries is due to their much higher energy density compared to the other rechargeable battery systems. The high energy density along with superior cycling stability became possible because of the use of oxide cathodes in lithium-ion cells. There are only three families of cathodes for practical lithium-ion cells, and all the three of them are oxides: layered, spinel, and polyanion oxide cathodes.
As we move forward with vehicle electrification and renewable energy storage, multiple parameters, such as cost, energy density, power density, cycle life, safety, and environmental impact, need to be balanced. Among them, cost along with sustainability and supply chain issues is at the forefront. Cathode is the most expensive component in the cell. The oxide cathodes will still dominate the field, but with fierce efforts to reduce or eliminate less abundant and expensive metals in the cathode. This presentation will focus on eliminating the most expensive cobalt from layered oxide cathodes, then reducing the next expensive nickel in oxide cathodes, and finally replacing/eliminating lithium with sodium in oxide cathodes.
Reducing or eliminating cobalt in layered oxide cathodes by increasing the nickel content helps to increase the energy density and reduce the cost, but cathodes with high nickel contents are plagued with cycle, thermal, and air instabilities along with severe scale-up challenges. This presentation will focus on overcoming these challenges with controlled compositional and synthesis designs along with a profound understanding of the intricacies involved with the aid of advanced characterization methodologies. Particularly, issues, such as what different dopants really do, which dopant does what, and which is critical between surface reactivity and crack, in stabilizing high-nickel cathodes will be discussed. The dependence of surface reorganization/degradation pathways on electrolytes and the importance of electrolyte composition and high-voltage stability in stabilizing the cathode-electrolyte interphase will be presented with both graphite and lithium-metal anodes.
Finally, elimination of both cobalt and lithium while reducing the nickel content much further down will be described with sodium batteries based on layered oxide cathodes. Tailored electrolyte designs that provide long-life sodium cells with suppressed dendrites and enhanced safety will be presented.
Understanding the Effects of Uniform Stack Pressure in Extreme Fast Charging Lithium-Ion Batteries Via Operando X-Ray Diffraction
Authors: Allan-Cole Elizabeth , Garman Rachel , Hartin Sarah , Roberts Lacey , Narasimhan Swati , Toney Michael F 
Published: September 2023

Enabling fast charging in lithium-ion batteries (LIBs) is critical for electric vehicle development, the U.S. goal being to charge to 80% of full capacity in 15 minutes [1]. This is a challenge due to significant capacity fade occurring at charge rates of 6C (charge in 60/6 = 10 minutes) and above. Fast charge rates induce irreversible lithium (Li) plating that adversely impacts battery performance and safety. External stack pressure can improve electrical contact and minimize delamination; further, an understanding of the impact of pressure on capacity fade can provide insight into the degradation mechanisms [2,3]. In this work, we investigate the extreme fast charging (XFC) regime, focusing on cell degradation and parasitic Li plating using single-layer pouch cells with graphite anodes, LiNi0.5Mn0.3Co0.2O2 (NMC532) cathodes, and 1.2 M LiPF6 in 3:7 weight % ethylene carbonate and diethyl carbonate (Gen2 electrolyte). To study the effect of pressure, electrode thickness and material capacity were varied. Cells were cycled under set uniform stack pressure configurations at 6C up to 140 times and tested between 10 – 150 psi. We have characterized fast charging cells under uniform pressure with spatially resolved operando X-ray diffraction (XRD) from high energy, high flux synchrotron radiation to study Li plating, parasitic reactions, and Li intercalation into graphite. Through spatially resolved operando XRD, we have mapped the intensity of LixC6 and Li metal peaks across the electrode to correlate peak intensity as a function of pressure and electrode thickness. This was complemented with ex situ X-ray photoelectron spectroscopy to study the composition of parasitic reaction products, corrosion and to correlate heterogeneity and local Li plating. Our results show an improvement in battery performance with increased uniform pressure. A reduction in Li plating was observed at elevated uniform pressures and Li plating appears more prevalent on the thicker electrodes. We believe that at increased pressure the reduced capacity fade arises from improved wettability, where the electrolyte acts as a lubricant increasing active sights, and a reduction in polarization across the thickness of the electrode leading to more homogenous reaction conditions. We emphasize the importance of electrode stack pressure in XFC batteries by quantifying the degradation mechanisms that cause capacity fade to enable better battery engineering.
References

USABC Goals – Lithium Electrode Based Cell and Manufacturing for Automotive Traction Applications, USABC (United States Advanced Battery Consortium), http://www.uscar.org/guest/article_view.php?articles_id=85

C. Cao et al. J. Electrochem. Soc. 129, 040540 (2022).

J. Cannarella and C. B. Arnold, J. Power Source, 245, 745-751 (2014).
(Digital Presentation) Mathematical Modeling of Thermal Events for Electrification Applications: Challenges and Opportunities
Authors: Zeng Yangbing , Yadav Anil , Lananna Scott , Garrick Taylor R. 
Published: September 2023

In support of GM’s traction battery efforts, we have derived and implemented a method to link the heat generation due to chemical and electrochemical sources during a thermal event to the thermal runaway and thermal propagation of a battery module and a battery pack. Mathematical modeling of thermal runaway and propagation provides critical design insights and has become an important part of the electric vehicle (EV) development process. This talk covers multiple modeling methods with various levels of details to drive battery back and battery module design, as well as battery cell selection from a coarse to fine level. At a cell level, thermal runaway and propagation kinetics can be simulated and linked to characteristics of the battery cell design, from molecular, electrode, and jellyroll packaging level.
At the module, pack, and vehicle level, a Conjugated Heat Transfer (CHT) method alongside with the Computational Fluid Dynamics (CFD) can be used to describe flow and heat transfer conditions inside and outside of the vehicle. Integrating all of these analysis in the design and development process provides a powerful way to optimize key thermal runaway mitigation components for electric vehicles.
(Keynote) Learning Electrochemical Models from Images
Authors: Bazant Martin Z. 
Published: September 2023

As illustrated by the work of Ralph White, traditional methods of electrochemical engineering are based on human intelligence: Mathematical models encoding physical hypotheses are proposed, tested against experimental data and refined by fitting adjustable parameters. Artificial intelligence is beginning to challenge this paradigm, since predictions can be made directly from data without the need for models, but such knowledge is often not transferrable to new situations. This talk will present a hybrid approach of solving PDE-constrained inverse problems to derive new multiscale models, in the context of Li-ion batteries. Examples include learning models of reaction kinetics and surface heterogeneities from x-ray adsorption images of phase separation in lithium iron phosphate nanoparticles [1], x-ray diffraction spectra for fictitious phase separation in nickel-rich oxide porous electrodes [2], and optical videos of lithium plating on graphite particles [3].
[1] H. Zhao, H. D. Deng, A. E. Cohen, J. Lim, Y. Li, D. Fraggedakis, B. Jiang, B. D. Storey, W. C. Chueh, R. D. Braatz, and M. Z. Bazant, Learning heterogeneous reaction kinetics from X-ray movies pixel-by-pixel, preprint, https://www.researchsquare.com/article/rs-2320040/v1
[2] J. Park, H. Zhao, S. D. Kang, K. Lim, C.-C. Chen, Y.-S. Yu, R. D. Braatz, D. A. Shapiro, J. Hong, M. F. Toney, M. Z. Bazant, and W. C. Chueh, Fictitious Phase Separation in Li Layered Oxides Driven by Electro-Autocatalysis, Nature Materials 20, 991-999 (2021).
[3] T. Gao, Y. Han, D. Fraggedakis, S. Das, T. Zhou, C.-N. Yeh, S. Xu, W. C. Chueh, J. Li, M. Z. Bazant, Interplay of lithium intercalation and plating on a single graphite particle, Joule 5, 1-22 (2021).
(Invited) Modeling Two-Phase Transport in the Cathode Catalyst Layer of a PEM Fuel Cell with a Focus on the Ionomer Phase Structure and Its Effect on Oxygen Transport
Authors: Nguyen Trung Van 
Published: September 2023

A hydrophobic treatment was developed to reduce the liquid water saturation level and increase its removal rate from the cathode catalyst layer (CL) of a PEM fuel cell. If this was achieved, the transport rate of oxygen to the reactive sites would be expected to increase and the fuel cell performance would be improved, especially in the high current-density mass-transport controlled region. The performance of the fuel cells with the hydrophobically treated cathode CLs tested with humidified air at 70oC shows significant improvement (> 200% increase in peak power).[1,2] The polarization curves obtained show improvements over the entire curve from the kinetic-controlled region to the mass-transport affected and mass-transport limited regions instead of only the mass-transport limited region as originally expected. A mathematical model was developed to provide insight into the causes for the observed responses with a focus on the oxygen-water two-phase transport phenomena in the catalyst layer. It suggests the hydrophobic treatment affects the CL in two ways. First, the interface of the ionomer layer exposed to the gas pores becomes more hydrophobic and facilitates less coverage and faster water drainage from the CL resulting in better performance at high current densities. Second, it reduces the hydration level in the ionomer phase which results in higher oxygen concentration in the ionomer phase on top and in the catalyst agglomerates leading to higher performance over the whole polarization curve. This presentation will discuss the major features of the new model and the findings obtained in this study.[3] These efforts show that the modeling work is not just a simulation of the experimental results using established theories and equations. It requires researching, finding, and understanding the mechanisms and phenomena that govern the physical processes in the fuel cell and result in the measured fuel cell performance. The modeling work provides insights that could not be gained from fuel cell testing.
References

Regis P. Dowd Jr., Cynthia S. Day, and Trung Van Nguyen, “Engineering the Ionic Polymer Phase Surface Properties of a PEM Fuel Cell Catalyst Layer,” J. Electrochem. Soc., 164 (14), F138-F146 (2017). 10.1149/2.1081702jes

Regis P. Dowd, Yuanchao Li, and Trung Van Nguyen, “Controlling the Ionic Polymer/Gas Interface Property of a PEM Fuel Cell Catalyst Layer During Membrane Electrode Assembly Fabrication,” J. Appl. Electrochem., 50 (10) 993-1006 (2020). 10.1007/s10800-020-01453-w

Yuanchao Li and Trung Van Nguyen, “A One-Dimensional Model of the Cathode Catalyst Layer of a PEM Fuel cell Hydrophobically Treated for Water Management,” J. Electrochem. Soc., 169 114505 (2022). 10.1149/1945-7111/ac9bdf