bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Reduced Order Modeling Approach to Capture Transport within a Three-Electrode System Towards Fast Charge Applications
Authors: Mollah Rafid , Garrick Taylor R. , Gao Jing , Zeng Yangbing , Koch Brian 
Published: December 2024

In support of GM's traction battery efforts, we derive and implement a reduced order modeling method to describe the electrochemical performance of a battery cell through the combination of a modified Newman Pseudo-2-Dimensional model and a three-electrode experimental apparatus. To assess the capability of the method, we compare the modeling results with experimental data for a lithiated graphite electrode and a lithiated nickel rich electrode system. The model is applied to simulate the electrochemical and transport processes within the battery cell to predict the negative electrode potential and positive electrode potential with respect to a lithium iron phosphate reference electrode, as well as the terminal voltage.
The manufacture and set up of the three-electrode system, model development and reduction approaches, as well as a discussion of applicability to fast charge considerations to avoid lithium plating at the anode during a charging event will be presented.
References:

T. R. Garrick, J. Gao, X. Yang, and B. J. Koch. 2021. J. Electrochem. Soc. 168 010530

T. R. Garrick, J. Gao, X. Yang, and B. Koch. 2021, Meet. Abstr. MA2021-02 485

T. R. Garrick, J. Gao, and B. J. Koch. 2022. Meet. Abstr. MA2022-02 1077

T. R. Garrick, Y. Zeng, J. B. Siegel, and V. R. Subramanian, J. Electrochem. Soc., 170, 113502 (2023)
Three-Dimensional Microstructure Modeling of Lithium Deposition and Dendrite Formation during Automotive Relevant Cycling
Authors: Teel Hunter , Garrick Taylor R. , Lopata Joseph Steven , Shimpalee Sirivatch 
Published: December 2024

Dendrites generally form during rapid charging of lithium-ion batteries when lithium plating is favored over intercalation. If not removed during discharging cycles, the potential exists for dendrites to grow through the separator and short between the anode and cathode. One metric for diagnosing lithium plating conditions in a computational model is the minimum local potential at the anode, where lithium plating is seen to be thermodynamically favorable below 0.0 V with respect to Li metal. [1-2] Three-dimensional (3D) microstructure model can provide insight to predict the possibility of local lithium plating as well as the possible formation of dendrites. This model can also be used as a tool to detect possible global lithium plating onset. The moving boundary technique with mesh movement can be employed to separate the electrolyte region into a liquid phase and a solid phase.[3]
This approach is applied in our 3D microstructure model of a lithium-ion battery[4] to observe the growth of lithium plating as well as dendrites at the anode during rapid charging cycles. Under beginning conditions at the solid/electrolyte interface (SEI), the solid metal phase is deposited at the SEI. Upon growth, the overall electrolyte resistance at the tip of the metal phase is reduced, leading to dendrite growth. The 3D microstructure model provides valuable insight into various conditions that may cause plating, if dendrites are formed due to plating, and whether the dendrites formed may proceed through the separator.

References

T. R. Garrick, J. Gao, X. Yang and B. J. Koch, J Electrochem Soc, 168, 010530 (2021).

U. Janakiraman, T. R. Garrick and M. E. Fortier, J Electrochem Soc, 167, 160552 (2020).

T. Jang, L. Mishra, S. A. Roberts, B. Planden, A. Subramaniam, M. Uppaluri, D. Linder, M. P. Gururajan, J.-G. Zhang and V. R. Subramanian, J Electrochem Soc, 169, 080516 (2022).

J. Lopata, T. R. Garrick, F. Wang, H. Zhang, Y. Zeng, S. Shimpalee, Journal of The Electrochemical Society, 170, 020530 (2023).
(Invited) (Digital Presentation) Development of Temperature-Dependent Degradation Models for Large-Format Lithium-Ion Batteries
Authors: Mishra Lubhani , Subramaniam Akshay , Garrick Taylor R. , Subramanian Venkat R. 
Published: December 2024

Advancing electric transportation technologies is critically dependent on maximizing the performance and lifetime of Electric Vehicle (EV) batteries, which is directly related to the economic case for EVs. Large-format cells are achieving increasing popularity for EVs to maximize volumetric and gravimetric energy densities. However, due to the large format size cells that are currently used for applications within the electrification portfolio, challenges have arisen that are tied to thermal management. Spatial variations in current density and temperature negatively affect overall cell utilization and lifetime. Identifying these temperature-dependent degradation mechanisms often relies on post-mortem analysis of cells, while model systems may be required to characterize spatial non-uniformities in degradation adequately. These challenges, along with the need for a comprehensive understanding of the degradation mechanisms, have led to the development of rigorous electrochemical models for battery degradation. These physics-based models serve as a powerful complementary tool in obtaining a better understanding of such phenomena. Simulating performance scenarios can lead to significant improvements in cell design and experimentation while also reducing time and cost commitments for the same.
The primary goal of this work is the development and validation of a physicochemical degradation model for automotive lithium-ion batteries to predict the degradation in the large-format cell in the presence of temperature gradients using the given set of cell parameters with temperature dependence. It was realized that the degradation trajectories are a result of a combination of both LLI (loss of lithium inventory) and LAM (loss of active material) fade mechanisms at both anode and cathode. The state-of-the-art electrochemical models for lithium-ion cells (p2D models) were implemented in both in-house codes and equation-based formulation in COMSOL Multiphysics with weak form implementation. The codes were validated against experimental cycling data at different operating temperatures at each stage of the model development. The validated codes possess the ability to estimate local degradation rates and consequent impact on cycling performance for EV batteries at a range of operating conditions. Thus, the model is a means of identifying dominant degradation mechanisms in practically relevant operating conditions, helping improve overall lifetime, and enhancing value by helping identify improvements in battery operations. The errors between the model and data can provide information on the suitability of a given model and the relative prevalence of a given degradation mechanism, with useful, practical benefits.
On the Proper Use of a Warburg Impedance
Authors: Orazem Mark E. , Ülgüt Burak 
Published: December 2024

Recent battery papers commonly employ interpretation models for which diffusion impedances are in series with interfacial impedance. The models are fundamentally flawed because the diffusion impedance is inherently part of the interfacial impedance.
This presentation is based on a recent publication [1]. A derivation for faradaic impedance is presented which shows how the charge-transfer resistance and diffusion resistance are functions of the concentration of reacting species at the electrode surface, and the resulting impedance model incorporates diffusion impedances as part of the interfacial impedance. Conditions are identified under which the two model formulations yield the same results. These conditions do not apply for batteries.

Mark E. Orazem and Burak Ulgut, J. Electrochem. Soc., 171 (2024), 040526
Innovative Methods for Crafting Hierarchically Structured, High-Performance Self-Supporting Flexible Bifunctional Electrocatalysts in Rechargeable Zinc-Air Batteries
Authors: Chen Yingjie , Meng Xiangyu , Dong Lifeng 
Published: December 2024

Efficient bifunctional electrocatalysts are pivotal for enhancing the performance of rechargeable zinc-air batteries, particularly in facilitating the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Recent strides in electrostatic spinning technology have yielded notable progress in polymer-zinc-air battery systems. This study introduces two innovative methodologies for synthesizing self-supporting flexible bifunctional electrocatalysts featuring hierarchical structures and high catalytic activity through meticulous adjustment of electrostatic spinning parameters.
The first approach integrates metal-organic frameworks with electrospinning technology to fabricate FeCoNi nanoparticle-decorated N-doped carbon hierarchical networks. These nanoparticles, originating from Fe3+/Co2+/Ni2+ ions within the electrospun fibers, catalyze the pyrolysis of ZIF-67 on the fiber surface, thereby generating reticulated carbon microfibers.
The second approach capitalizes on the characteristics of organic salts in polymer solutions via electrospinning to produce FeCoNi flexible carbon nanofibers. These catalysts undergo secondary growth of FeCoNi- and N-doped carbon nanotubes on fiber surfaces, yielding numerous metal-nitrogen-carbon (M-N-C) ORR active sites and FeCoNi alloy-based OER active sites.
Both methodologies yield bifunctional electrocatalysts exhibiting outstanding ORR and OER activity, surpassing conventional Pt/C and RuO2 catalysts. Rechargeable zinc-air batteries employing these catalysts demonstrate high peak power density and remarkable cycling stability, positioning them as promising contenders for next-generation energy storage solutions.
Development of Large-Sized CO2 Electrolyzer Producing CO for Industrial Applications
Authors: Kofuji Yusuke , Fujiwara Naoya , Yonetsu Maki , Kiyota Yasuhiro , Kudo Yuki , Mikoshiba Satoshi , Yanagi Kosuke , Kikuchi Isamu , Kimura Shunsuke , Kitagawa Ryota 
Published: December 2024

Utilization of carbon dioxide (CO2) as a feedstock of valuable chemicals is necessary to achieve carbon neutrality. CO2 electrolysis producing valuable organic molecules such as carbon monoxide (CO) is one of the most promising methods. To implement this technology in society, a large-sized electrolyzer that can convert a huge amount of CO2 are required. Toshiba is developing a low-temperature zero-gap type CO2 electrolysis cell/stacks with 400 cm2 electrodes to produce CO [1,2], which can be converted into chemicals and fuels by catalytic reactions with hydrogen. With properly designed gas flow plates and optimal operation conditions, CO faradaic efficiency of the 400cm2 single cell were comparable to that of a smaller cell with 4 cm2 electrode [3]. Another problem to be solved is low durability of the electrolyzer. During continuous operation of the electrolyzer, several failure modes such as cathode flooding, salt precipitation, diaphragm degradation, corrosion of flow plates, and catalyst dissolution often occur. By resolving each of these failure modes, stable performance over 500 h was achieved. Additionally, in this presentation, we report the results of electrolysis tests using CO2 gas containing impurities that are expected to be contaminated in an actual environment, and the results of electrolysis tests to confirm effects of a ripple current generated from AC/DC converter on the efficiency of CO2 electrolyzer.
Part of this work is commissioned by Ministry of the Environment, Government of Japan.
[1] Y. Kofuji, A. Ono, Y. Sugano, A. Motoshige, Y. Kudo, M. Yamagiwa, J. Tamura, S. Mikoshiba, and
R. Kitagawa, Chem. Lett., 50, 482-484 (2021).
[2] Y. Kiyota, Y. Kofuji, A. Ono, S. Mikoshiba, and R. Kitagawa, 242nd ECS Meeting, I05, 1942,
(2022).
[3] Naoya Fujiwara, Yusuke Kofuji, Satoshi Mikoshiba, Ryota Kitagawa, Atsushi Matsunaga, Isamu
Kikuchi, Soichiro Shimotori, 244th ECS Meeting, I05, 2328, (2023).
Insights from the Systems Scale to Design Practical CO2 Electrolyzers
Authors: da Cunha Shashwati C , Resasco Joaquin 
Published: December 2024

Electrochemical CO2 reduction (CO2R) can convert captured CO2 into chemical feedstocks and fuels using renewable electricity and water, but scaleup has been limited. To guide targets that set the direction of research in the field, we connect a systems-level perspective on CO2R with electrolyzer design. A physics-informed technoeconomic assessment can highlight the sensitivity of overall process cost towards improvements at the electrolyzer scale, identifying the most impactful opportunities to improve performance. The assessment confirms the importance of better materials (membranes, catalysts), which has been the focus of the field, and that electricity prices are currently too high for economical CO2R. However, we find a critical and overlooked need for improved reactor design to make CO2R economically viable. Analyzing the separations needed for state-of-the-art CO2R electrolyzers shows that maximizing single-pass conversion comes at the cost of product composition and process energy. This is because electrolyzers increase conversion by restricting feed flow rate or by using strongly acidic electrolytes. Both these conditions promote the HER side reaction, wasting expensive electricity on making byproducts.
Our work has shown the tradeoff between single-pass conversion and selectivity for CO2 electrolyzers, a limitation that arises directly from current reactor design. Due to selectivity loss, we show that increasing single-pass conversion beyond ~10% increases process cost for current electrolyzer designs and process costs. Since the relationship between selectivity and single-pass conversion comes from the plug-flow channel design, we call on the field to investigate reactor designs that modify this crucial handle on CO2R cost by improving the availability of CO2 to the catalyst surface. On the other hand, we show that mitigating the “carbonate problem” leads to relatively small improvements in cost for relevant electrolytes. Moreover, operation at high current density (>1 A/cm2)has been repeatedly proposed as a target for the field. Such high currents lead to a tradeoff between capex and utility cost at a much lower current density than has been proposed. At current electricity prices, the optimal total current density is <300 mA/cm2. Therefore, high operating currents will worsen process costs, unless accompanied by much lower electricity costs or considerable improvement in the full-cell polarization curve for CO2R in membrane electrode assemblies.
Exploring the Role of Natural Convection in 2-Stage Electrochemical CO2 Separation
Authors: Ripley Katelyn M. , Clarke Lauren E. , Caruso Isabella , Brushett Fikile R. 
Published: December 2024

Current state-of-the-art carbon dioxide (CO2) capture systems are often implemented at large scale thermal power plants and industrial facilities due to their capital-intensive designs.1 However, there are many smaller scale applications for CO2 separation, such as from commercial buildings, airplanes, and/or submarines, that could benefit from scalable technologies with lower energy requirements. Consequently, 2-stage electrochemical CO2 separators have been proposed as systems with the potential to achieve high energy efficiencies and to operate at the compact sizes required for space-constrained applications.2 While electrochemical capture systems most similar to thermochemical capture systems employ separation units such as absorption columns and flash tanks in addition to the electrochemical reactor, the envisioned 2-stage process combines the activation step with CO2 absorption and the deactivation step with CO2 desorption, all within a single unit. Unfortunately, experimental studies have thus far shown these devices cannot support high current densities and exhibit considerable losses. Understanding and mitigating these losses is key to improving the performance of these separators.
Here, we develop a two-dimensional cell model to simulate the capture and release of CO2 from a 2-stage electrochemical separator with freely-solubilized, redox-active capture molecules. We first discuss the governing equations within the model and, using representative redox couples, we experimentally validate that the model can adequately predict voltage–current relationships. Through this validation, we observe that electrode reactions generate concentration gradients that induce natural convection within the device, enabling higher than expected current densities. To maximize the benefits of natural convection, we then explore the impacts of capture species and electrolyte properties, cell design, and operating conditions on performance by experimentally and computationally varying redox species concentrations, cell orientation, and electrode dimensions. Finally, we incorporate the CO2 binding/release reactions to predict the effect of natural convection on CO2 capture and release. We find that density gradients within the cell also impact the CO2 back-flux from the higher concentration anode to the lower concentration cathode, affecting the separation flux and minimum work. We anticipate that this model will support electrochemical reactor design campaigns leading to higher-performing devices for a range of CO2 separation applications.

References

M. Wang, A. Lawal, P. Stephenson, J. Sidders, and C. Ramshaw, Chem Eng Res Des, 89, 1609–1624 (2011).

L. E. Clarke, M. E. Leonard, T. A. Hatton, and F. R. Brushett, Ind Eng Chem Res, 61, 10531–10546 (2022).
Ligand-Functionalized Membranes for Lithium-Selective Electrodialysis Separations
Authors: Abels Kristen , Barbosa Botelho Amilton , Chen Xi , Tarpeh William Abraham 
Published: December 2024

Selective electrodialysis requires further development of ion-selective membranes to enable the selective recovery of target ions from aqueous streams. In this work, we evaluated a library of commercial membranes to assess their potential for ion-ion separations and to elucidate the fundamental mechanisms of ion permselectivity in these materials. This screening of commercial membranes confirmed the limitations of size and electrostatic selectivity mechanisms in the separation of ions of similar size and/or charge. We then synthesized a library of novel ligand-functionalized membranes to study the impact of additional ion-specific coordinative interactions on lithium permselectivity under diffusive transport and selective electrodialysis. The complete characterization of the library of novel, ligand-functionalized membranes provides additional experimental data on the effect of not only ligand-cation interaction free energies, but also the effect of ligand grafting densities on ion permeabilities and permselectivities. For example, variation of membrane pyridine content from 0-50 mol% in a subset of the membrane library was found to have substantial impact on lithium/nickel permselectivities, including 3-4 times higher than the permselectivities measured with the commercial membranes. In the future, these experimental results could support further development of ion transport theory in ligand-functionalized membranes with ligand grafting densities included as model parameters. This work could also lead to future grafting density optimization studies with the goal of maximizing ion permeability and/or permselectivity. Membranes were also tested in four-chamber electrodialysis reactors to characterize performance during electrolysis; selectivity was still observed during operation.
Note: This presentation reflects research funded by an ECS/Toyota Young Investigator Fellowship.
Fundamentals Studies of Sludge Electrolysis Using Bovine Serum Albumin (BSA) as a Model Compound
Authors: Abbasi Ehsan , Alvarez Pugliese Christian E , Botte Gerardine G 
Published: December 2024

The Haber-Bosch process is the main industrial practice for producing ammonia, known for its energy intensity. Current ammonia production is unsustainable, and the overuse of synthetic fertilizer has led to significant environmental impact in air, water, and soil. Organic waste, such as sewage sludge from domestic wastewater treatment plants represents a valuable resource for nitrogen recovery, containing approximately 6% nitrogen content (1) in dry basis.
Electrolysis of waste activated sludge (WAS) has the potential to recover nitrogen from this slurry waste (2-3), where nitrogen is mainly present in the form of proteins constituting 30-40% of the total solids in sludge (4). Developing efficient electrochemical processes to valorize organic waste such as WAS is critical to achieving sustainability goals, protecting the environment, and enabling economic development and growth (5). While efforts have been made to employ sludge electrolysis at high to moderate voltages to mineralize the organic matter completely or partially, the optimal scenario for electrolysis would involve the selective transformation of sludge components into valuable products like ammonia and other nutrients that can be further separated as a fertilizer (4). However, the complexity of sludge components, such as proteins, their solubility, denaturation, and structural variability, presents one of the main challenges that needs to be addressed in the process.
Given the complexity of real sludge, it is reasonable to begin with a model compound such as a protein to understand the fundamental behavior of the system. Bovine Serum Albumin (BSA) is a globular protein that contains approximately 15-17 percent nitrogen by weight. This protein is relatively inexpensive, readily available, and possesses appropriate structural complexity for fundamental studies. In this presentation, the most recent results for the electrochemical oxidation of BSA will be discussed, aiming to provide a better understanding of the mechanism of reaction of complex organic nitrogen compounds.
Reference:

D. Bolzonella, C. Cavinato, F. Fatone, P. Pavan and F. Cecchi, Waste Management, 32, 1196 (2012).

M. Jafari and G. G. Botte, Frontiers in Chemistry, 10, 974223 (2022).

M. Jafari and G. G. Botte, Journal of Applied Electrochemistry, 51, 119 (2021).

K. Xiao and Y. Zhou, Journal of Cleaner Production, 249, 119373 (2020).

C. Alvarez-Pugliese, D. Donneys-Victoria, W. J. Cardona-Velez and G. G. Botte, Current Opinion in Electrochemistry, 46, 101508 (2024)