bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) An Industrial Perspective on Electrochemistry and the Energy Transition
Authors: Endler Elizabeth , Stephens Ryan 
Published: September 2023

As wind and solar become an increasingly larger share of primary energy, the use of electrochemical storage and conversions is growing. Traditionally, carbon-based fuels such as oil, coal and natural gas have been globally traded and served as energy storage media for the power and transportation sectors. With the growth of lower-carbon energy technologies, particularly wind and solar power, effective use of renewable electrons requires high-performing, cost-effective solutions for storage and distribution services that are analogous to traditional fuels. Electrochemical energy storage technologies are increasingly used for a range of applications from kW to GW scales, with this deployment momentum built from improved performance and declining costs.
This talk will address where multiple types of storage exist in the historical & current energy system, their scales, and the roles of storage in the emerging energy transition from the perspective of an international energy company. Our energy storage and conversion research & development over the past decade will also be discussed, with a focus on current and emerging electrochemical systems designed for use in mobility, the power sector, and industry. Systems of active research include metal anodes used with high voltage cathodes and high energy density stationary batteries. This work has been driven by business challenges, with a range of modeling approaches used to generate insights that complement theory & experiment. Techniques include large-scale energy system modeling, modeling of power market operations, technoeconomic analyses to guide cost & performance targets of new technologies, and new ways to capture and predict physical phenomena that underpin device life and performance. Finally, commercial operation examples of energy storage operation will be provided, along with challenges still to be resolved through improved system understanding across scales.
(Invited) Selected Legacy of Dr. Ralph White’s Contributions – Relevance for Current and Next-Generation Batteries/Electrochemical Systems/Students/Researchers
Authors: Subramanian Venkat R. 
Published: September 2023

In this talk, a few selected contributions of Professor White will be briefly summarized. His contributions towards modeling and numerical simulation of batteries, and electrochemical systems will be reviewed. In addition, my personal perspective on the relevance of his contributions to the current and next-generation batteries/electrochemical-systems/students/researchers will be presented.
Selected examples of model-based BMS, mechano-electrochemical models, phase-field models, dendrite growth in 2D, and precise and efficient simulation of the same will be presented.
Numerical Modeling Unlocks Remarkable Ion Selectivity of Capacitive Deionization
Authors: Suss Matthew , Shocron Amit N. , Uwayid Rana 
Published: September 2023

Ion-selective water treatment is an important frontier in water research, as for many applications removing all ions indiscriminately leads to significant extra energy and downstream re-ionization costs. Capacitive deionization (CDI) is under intensive investigations for ion-selective treatment of polluted feedwaters [1]. CDI has the remarkable feature of being not only highly selective, but additionally dynamically tuneable to adjust, real-time, to varying feedwater composition and produced water targets [1]. However, we will show that to further develop CDI technologies to achieve desired separations, in feedwaters of several competing anions and cations, requires detailed numerical models. Such models couple ion transport theory to nanopore electrosorption, and often include pH dynamics. We here describe our recent work exploring the limits of ion-ion selectivity by capacitive deionization with inexpensive nanoporous carbon electrodes. We show how theory enabled us to achieve in the lab remarkable selectivity and a diverse set of separations, such as “perfect” divalent cation selectivity[2], monovalent ion selectivity[3], and removal of amphoteric pollutant species such as boric acid and nutrient species[4]. We show using strong-acid functionalized electrodes that the same two-electrode system can be used for either excellent divalent selectivity, or long-lasting monovalent ion selectivity, depending on cell operational parameters [2,3]. Our work furthers the argument that membraneless CDI, based on inexpensive and easily-scalable porous carbon electrodes, can address a wide variety of important applications in water treatment.
References:
[1] J.G. Gamaethiralalage, et al. “Recent advances in ion selectivity with capacitive deionization”, Energy &Environmental Science, 2021.
[2] R. Uwayid, E.N. Guyes, A.N. Shocron, J. Gilron, M. Elimelech, M.E. Suss. “Perfect divalent cation selectivity with capacitive deionization”, Water Research, 2022.
[3] E.N. Guyes, A. Shocron, Y. Chen, C. Diesendruck, M.E. Suss. “Long-lasting, monovalent selective capacitive deionization electrodes.” NPJ Clean Water, 2021.
[4] A.N. Shocron, E.N. Guyes, H.H. Rijnaarts, P.M. Biesheuvel, M.E. Suss, J.E. Dykstra, “Electrochemical removal of amphoteric ions”,
Proceedings of the National Academy of Sciences, 2021.

Figure 1

From Ref. 3. CDI concept for treatment of water for direct use towards irrigation. a) Schematic of a CDI cell fed with water containing excessive Na+ which must be removed for direct use in irrigation. The cell is charged at an applied cell voltage Vch at or above 1 V and for a time tch significantly shorter than the time to reach equilibrium, teq. b) The cathode nanopore is functionalized with strong-acid sulfonic groups, which enhances the preferential storage of monovalent Na+ over divalent Ca2+ at short charging times. c) The treated water has significantly reduced sodium absorption ratio (SAR) and ionic conductivity, rendering it

Figure 1
Modeling Charge Transport in Flowable Suspension Electrolytes
Authors: Majji Madhu V. , Brushett Fikile R. 
Published: September 2023

Abstract

Flowable suspension electrolytes (FSEs) consist of electrically conductive, redox-active, and/or energy-storing particles suspended in aqueous or non-aqueous electrolyte solutions (supporting salt + solvent). These particles, which can range in size from nanometers to micrometers, are subjected to Brownian forces, hydrodynamic forces, hydrophobic interactions, and van der Walls interactions among others. FSEs may enable electrochemical processes where solid reactants can be integrate with flow cells potentially unlocking new approaches to materials processing (e.g., synthesis, extraction/recovery). For example, FSEs has been demonstrated in redox flow batteries, facilitating higher energy densities without sacrificing independent power and energy scaling However, understanding and controlling charge transport through the deformable particle microstructures, especially under shear, is key to enable desirable current distributions and thus effective electrode utilization.
In this presentation, we investigate the impact of interparticle interactions, particle volume fractions, and applied shear rate on charge transport through FSEs. At sufficiently large volume fractions above the percolation threshold and stationary conditions, particle interactions in an FSE can drive the formation of networks that span the cell dimensions and provide electronic transport similar to stationary freestanding porous electrodes. However, under flowing conditions, shear forces can break these networks, hampering charge transport. Conversely, increasing attractive particle interactions or particle concentration can strengthen the particle networks and fortifying charge transport, albeit at the expense of fluid viscosity. To better understand these processes, we model the charge transport through these dynamic particle networks, using a combination of local charge transport models and discrete particle simulations, considering the Peclet number (ratio of shearing to Brownian forces) and Mason number (ratio of shearing to attractive forces). Our results contribute to the development of continuum models for charge transport in FSEs, which, in turn, can facilitate efficient and accurate system-level analysis.

Acknowledgments

This work was funded by the Skoltech – MIT Next Generation Program.
Dry Extrusion Process for Manufacturing of High-Energy Cathodes for Lithium-Ion Batteries
Authors: Sperling Tom , Hoffmann Alice , Wohlfahrt-Mehrens Margret 
Published: September 2023

For a sustainable production of lithium ion batteries, more environmentally friendly, energy saving and faster strategies are required. For cathode production NCM/NCA layered oxides are commonly used as active materials. Nevertheless, application of the very toxic and teratogenic solvent N-methylpyrrolidone (NMP) is still common for the industrial production of these cathodes. Besides the high toxicity, the NMP recovery after coating is very energy-, time- and cost-intensive.
As an alternative, to conventional NMP-based cathode production, we developed a dry extrusion process coupled with slot-die coating, to manufacture high-energy cathodes. The extrusion process offers continuous production, alongside a very good scalability to industrial demands and a significant reduction of mixing time. Since the process is NMP-free and the drying step is saved, it overcomes typical shortcomings of the wet coating as crack formation or binder migration occurring during solvent evaporation. In addition, producing high-energy electrodes leads to lower material costs and space savings, since less layers of Al/Cu foil and separator are required on cell level, compared to a battery of the same capacity and lower electrode mass loading.
Herein, we present the development of a dry cathode manufacturing process, a suitable recipe for dry processing, consisting of NCM622, PVdF, carbon black and a superplasticizer, as well as the optimization of the formulation in terms of processability and active material content. We also discuss the influence of process parameters such as temperature or rotation speed on the viscosity of the cathode paste. As a proof of concept, we processed powder mixtures, corresponding to our optimized formulation with about 90 % of NCM, in a pilot scale twin-screw extruder. By melt extrusion through a slot die, we create a thin film from the cathode composite that we directly apply on an Al current collector. We show a schematic representation of the process in the attracted graphic. By repositioning of the electrode coil, we also produce double-sided coatings. After calendaring, we characterize the dry processed electrodes electrochemically in half-cells. The electrochemical performance data is comparable to state of the art cathodes and results are promising that even higher active material contents can be reached. Therefore, the solvent free extrusion of cathodes is highly relevant for industrial applications.
Acknowledgement
The presented work was financially supported by BMBF within the project Tropex under the reference number 03XP0235C.

Figure 1
(Invited) Opening Twisted Molecular Chains of High Solid Content Screen Printable Ink for Screen-Printed Low-Tortuosity Electrodes
Authors: Wang Ying , Zhu Hongli 
Published: September 2023

Reducing the tortuosity of electrodes is an efficient technique for enhancing the charge transfer inside electrodes and boosting the fast-charging capabilities of lithium-ion batteries for electric vehicles. Compared to reported complex methods, screen printing is facile, economical, and printing pattern controllable. More importantly, the roll-to-roll screen printing equipment can be integrated into the existing electrode production system, allowing for the industrialization of low-tortuosity electrodes. However, the absence of screen-printable inks with a high solid content restricts the ink transfer volume per printing, lowering production efficiency and raising the price of screen-printed electrodes. By integrating rheological characteristics analysis, X-ray computed tomography characterization, and coarse-grained molecular dynamics (CGMD) simulation, we are able to recognize and illustrate the relevance of the molecular chain state in high-solid-content ink for screen printability. Additionally, we propose and develop a unique preparation procedure for producing high-solid-content screen-printable inks. In addition, the electrochemical performance of screen-printed electrodes was evaluated in order to enclose the importance of electrode micromorphology. This finding lays the door for the industrialization of screen-printable inks with high solid content and encourages additional research into screen-printed architectures with functional electrodes.
In this work, we demonstrated for the first time that the molecular chains within high-solid-content inks should be untangled to obtain outstanding screen printability. Specifically, the twisted molecular chains serve as extra networks that drag certain particles within the electrode ink onto the mesh, hence diminishing its screen printability. Therefore, we suggest a two-step approach for opening the twisted molecular chains of inks with a high solid content of 60%. Employing this type of ink, the mass loading per printing layer elevates to about 5 times greater than the existing cathode inks. After opening the twisted chains, the LiNi0.6Mn0.2Co0.2O2 cathode ink exhibited a lower viscosity, a faster thixotropic recovery, and superior screen printability than the ink containing twisted chains. Furthermore, due to the improved internal architectural integrity of screen-printed electrodes printed by the excellent screen-printability of ink, the electrode printed with optimized inks displayed a 33% larger charge capacity at 6C with a mass loading of 6.5 mg/cm2 than that produced with chains-twisted ink. In addition, based on the fundamental of the two-step approach, we present optimization approaches for altering screen-printable inks for a variety of circumstances. This idea could promote the coupling of screen printing with the production of functional electrodes and could be utilized for the production of screen-printable inks for all fields.
Mechanical Impacts from Cycling on Silicon Calendar Aging Measurements
Authors: McBrayer Josefine , Harrison Katharine L , Fenton Kyle , Minteer Shelley 
Published: September 2023

Much of the silicon anodes for lithium ion batteries literature concentrates on the volume expansion of silicon leading to poor cycle life. Recently, the poor calendar life of silicon has become more of a focus. Calendar aging is typically measured by long periods of open circuit voltage (OCV) that are intermittently interrupted with a reference performance test (RPT) to quantify performance and capacity fade. The United States Advanced Battery Consortium LLC protocol calls for an RPT once a month with daily voltage pulses to keep the state of charge the same during the rest. If the solid electrolyte interphase (SEI) is unstable and there is substantial volumetric changes during cycling, as is the case with silicon, the frequency and amount of cycling interruption may impact how calendar life is quantified. It was hypothesized that an SEI that equilibrates during a rest may be disrupted enough during RPT cycling that the SEI passivation is decreased and the start of the next rest will result in greater irreversible lithium inventory consumption to rebuild the SEI that was lost during cycling. To test this, a specially designed variable OCV-RPT protocol was applied to silicon – NMC622 full cells. It was found that for all rest durations, time since assembly, rather than cycling, dominated capacity fade, indicating that calendar aging is likely primarily governed by chemical SEI degradation during rest rather than mechanical SEI degradation during RPTs.
This research was supported by the U.S. Department of Energy’s Vehicle Technologies Office under the Silicon Consortium Project, directed by Brian Cunningham, and managed by Anthony Burrell. This work was conducted in part by the Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Sandia National Laboratories is a multimission Laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Spherical LiMn0.7Fe0.3PO4/C Cathode Materials for Lithium-Ion Batteries
Authors: Yamashita Hiroki , Shiozaki Mayu , Oikawa Mutsuki , Hirayama Yuko , Ogami Takaaki , Kanamura Kiyoshi 
Published: September 2023

Lithium manganese iron phosphates (LiMnxFe1-xPO4) [1] are attractive as next-generation cathode materials for lithium-ion batteries because they are safer than conventional lithium transition metal oxides (e.g. LiCoO2) [2] and are Co- and Ni-free. However, due to their low electronic conductivity [3], they can deliver much lower electrochemical properties than theoretically expected one. Therefore, many researchers have focused on chemical composition, reducing primary particle size, and carbon coating. On the other hand, granulation of LiMnxFe1-xPO4 primary nanoparticles is effective in improving poor handling of LiMnxFe1-xPO4 primary nanoparticles during cathode slurry preparation. However, electrochemical properties of granulated LiMnxFe1-xPO4 have not been well studied in previous reports. In this study, the electrochemical properties of the spherical LiMn0.7Fe0.3PO4/C composed of primary nanoparticles are reported. Spherical LiMn0.7Fe0.3PO4/C was synthesized by hydrothermal method followed by granulation and carbon coating. The synthesized spherical LiMn0.7Fe0.3PO4/C was characterized using X-ray diffraction (XRD) and scanning electron microscope (SEM). Electrochemical properties of spherical LiMn0.7Fe0.3PO4/C were examined using CR2032 coin-type cells. Fig. 1 (a) shows the SEM images of spherical LiMn0.7Fe0.3PO4/C. As shown in Fig. 1 (a), spherical particle 10 μm in diameter composed of homogeneously sized primary nanoparticles were observed. Fig. 1 (b) shows the galvanostatic charge-discharge curves for spherical LiMn0.7Fe0.3PO4/C at discharge current rates of 0.2, 1, 5, and 10 C in a voltage range of 1.5–4.5 V at 30 °C. Spherical LiMn0.7Fe0.3PO4/C delivered a 0.2 C discharge capacity of 153 mAh g−1. At the 10C rate, spherical LiMn0.7Fe0.3PO4/C also delivered a high discharge capacity of 137 mAh g−1, which was 89 % of the 0.2C discharge capacity. Detailed data of our study including blended cathode of LiNiaMnbCocO2 and spherical LiMn0.7Fe0.3PO4/C will be presented in the meeting.
References:

A.K. Padhi, J. Electrochem.Soc. 144 (1997) 1188.

C. Delmas et al., Nat.Mater. 7 (2008) 665.

A. Yamada et al., J. Electrochem. Soc. 148 (2001) A224.

Figure 1
(Invited) Bipolar Membrane Electrolysis for CO2 to Ethylene
Authors: Hatzell Marta , Song Hakhyeon 
Published: September 2023

Carbon dioxide conversion systems are important to drive down the cost of carbon capture through the creation of valuable products. However, how to integrate carbon capture with carbon conversion devices is not yet clear. Bipolar membrane electrolyzers have attracted significant interest as a device which is compatible with carbon capture, as these systems can operate with bicarbonate and carbonate-based solutions. In a bipolar membrane electrolyzer, carbonate is converted to carbon dioxide through a pH swing process driven by water dissociation within the bipolar membrane. However, balancing the rate of water dissociation, carbon dioxide production, and carbon dioxide electrocatalysis remains a critical challenge. Furthermore, steering carbon dioxide electrocatalysis toward a specific high value product such as ethylene is unclear.
Here, we set out to examine the activity of Cu, Ag and CuAg catalyst in a carbonate electrolysis system. Cu is a unique metal catalyst and has previously shown the capacity to generate multi-carbon products such as C2H4 and C2H5OH within gas phase anion exchange membrane electrochemical cell. Cu-based catalysts are however known to suffer sluggish C–C coupling kinetics which is a requirement for C2+ product formation. To overcome this challenge, bimetallic are used. For instance, through introducing a known CO-producing catalyst such as Au and Ag with Cu one can perform a cascade reaction. This tandem strategy can enhance performance of multi-carbon products by increasing the coverage of *CO intermediates, known as an important intermediate for C–C coupling, on the Cu surface. Thus, here we will detail a set of experiments aimed at discerning the selectivity of a bipolar-membrane electrode assembly cell which contains Cu, Ag, and Cu-Ag bimetallic electrocatalyst. We examine the impact of temperature, catalyst loading, and system operations. We also will briefly discuss technoeconomic considerations.
Effect of Cations on Electrocatalytic CO2-to-Methanol Conversion by Heterogenized Molecular Catalyst
Authors: Yu Sunmoon , Yamauchi Hiroki , Shao-Horn Yang 
Published: September 2023

Catalytic benefit and role of electrolyte cations for electrochemical CO2 reduction reaction have recently received significant research attention. It has been experimentally and theoretically demonstrated that cations can stabilize the key intermediate species, for example, *CO2
–, through mid- or short-range electrostatic interactions, facilitating the CO2 activation step.1-2 However, to date, these discussions are mostly limited to CO2-to-CO conversion (a two electron/proton transfer reaction) and electrostatic stabilization of reaction intermediate species.
In present work, we show that cations play a crucial role in further reducing CO2 to methanol. We found that cations engage as a promoter in the rate determining step of the CO2-to-methanol conversion, which involves a proton-coupled electron transfer, beyond the first CO2 activation step. For this study, heterogenized molecular catalyst with a cobalt single site (Co-N4) was employed, achieving ~25% methanol selectivity at –0.78 V vs. RHE. Through an isotope labeling experiment (13CO2 reduction reaction), we validated that methanol is produced by the CO2 reduction reaction. Furthermore, electrolytes with different cation species and concentrations were tested in a systematic manner to investigate the promoting effect of cations on methanol production. In addition, using deuterated electrolytes, we studied kinetic isotope effect, proposing a reaction pathway for CO2-to-methanol conversion on the cobalt single site. Our findings offer new insights into the beneficial effect of cations on electrochemical CO2 reduction reaction kinetics besides their widely acknowledged stabilizing effect. Our discovery also opens up new research directions where non-covalent interactions between electrolyte species and reaction intermediates are utilized to enhance electrocatalytic production of a desired product in CO2 reduction reaction beyond two-electron transfer products.
In this talk, I will discuss the promoting effect of cations on the electrochemical reduction of CO2 to methanol and conclude by proposing potential strategies to further improve the electrocatalytic CO2-to-methanol conversion.
References

Monteiro, M. C. O.; Dattila, F.; Hagedoorn, B.; García-Muelas, R.; López, N.; Koper, M. T. , Absence of CO2 electroreduction on copper, gold and silver electrodes without metal cations in solution. Nature Catalysis
2021,
4 (8), 654-662.

Resasco, J.; Chen, L. D.; Clark, E.; Tsai, C.; Hahn, C.; Jaramillo, T. F.; Chan, K.; Bell, A. T., Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide. Journal of the American Chemical Society
2017,
139 (32), 11277-11287.