bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Reduced Order Modeling of Li-Ion Battery Systems - from Fundaments to Real-Life Applications
Authors: Coman Paul , White Ralph E. 
Published: December 2024

The development of efficient and safe battery packs is crucial for advancing energy storage technologies. This presentation offers a comprehensive overview of the transition from full-order physics-based modeling to reduced order modeling (ROM) in the context of single battery cells and battery packs, with a specific emphasis on managing and understanding thermal runaway. A detailed exploration of the methodologies used in full-order physics-based models, including ROM and multiphysics coupling, will provide a granular view of electrochemical, thermal, and electrical behaviors in battery systems.
To address these challenges, the presentation explores the development and application of reduced order models that approximate the behavior of these complex systems with significantly reduced computational demands. The focus is on simplifying the models while retaining essential dynamics, particularly in the context of thermal management to prevent thermal runaway.
The session will also cover how ROMs can accurately predict temperature and voltage within battery packs, enhancing predictive capabilities and operational safety. The electrical modeling of bus-plates and the electromagnetic modeling of cylindrical single cells will be discussed, highlighting their importance in the overall performance and safety of battery systems.
The discussion extends to the application of these ROMs in real-world scenarios, illustrating how they can be integrated into battery management systems to enhance performance and safety while ensuring efficiency. Case studies where ROMs have been successfully implemented to predict and mitigate thermal runaway in battery packs will be highlighted, showcasing the transition from fundamental research to practical applications.
Quantifying Volume Change in Porous Electrodes Via the Multi-Species, Multi-Reaction Model
Authors: Garrick Taylor R. , Fernandez Miguel , Verbrugge Mark , Labaza Christine , Mollah Rafid , Koch Brian , Jones Matthew , Gao Jing , Gao Xiujie , Irish Nicholas 
Published: December 2024

Automotive manufacturers are working to improve individual cell and overall pack design by increasing their performance, durability, and range, while reducing cost; and active material volume change1–7 is one of the more complex aspects that needs to be considered during this process. As the time from initial design to manufacture of electric vehicles is decreased, design work that used to rely solely on testing needs to be supplemented or replaced by virtual methods. As electrochemical engineers drive battery and system design using model-based methods8, the need for coupled electrochemical/mechanical9 models that take into account the active material change utilizing physics based or semi-empirical approaches is necessary. In this study, we illustrated the applicability of a mechano-electrochemical coupled modeling method considering the multi-species, multi-reaction model as popularized by Verbrugge10,11 and Baker. To do this, validation tests were conducted using a computer-controlled press apparatus that can control the press displacement and press force with precision. The coupled MSMR volume change model was developed and its applicability to graphite and NMC cells was illustrated. The increased accuracy of the model considering the coupled MSMR volume change approach shows in the importance of accounting for individual gallery volume change behavior on cell level predictions.
References:

T. R. Garrick et al., J. Electrochem. Soc., 164, E3592 (2017).

T. R. Garrick, X. Huang, V. Srinivasan, and J. W. Weidner, J. Electrochem. Soc., 164, E3552 (2017).

T. R. Garrick, K. Kanneganti, X. Huang, and J. W. Weidner, J. Electrochem. Soc., 161, E3297 (2014).

T. R. Garrick et al., J. Electrochem. Soc., 170, 060548 (2023).

D. J. Pereira, A. M. Aleman, J. W. Weidner, and T. R. Garrick, J. Electrochem. Soc., 169, 020577 (2022).

D. J. Pereira et al., J. Electrochem. Soc., 167, 080515 (2020).

D. J. Pereira, J. W. Weidner, and T. R. Garrick, J. Electrochem. Soc., 166, A1251 (2019).

T. R. Garrick, Y. Zeng, J. B. Siegel, and V. R. Subramanian, J. Electrochem. Soc., 170, 113502 (2023).

S. Pannala, H. Movahedi, T. R. Garrick, A. G. Stefanopoulou, and J. B. Siegel, J. Electrochem. Soc., 171, 010532 (2024).

M. Verbrugge, D. Baker, B. Koch, X. Xiao, and W. Gu, J. Electrochem. Soc., 164, E3243 (2017).

M. Verbrugge, D. Baker, and X. Xiao, J. Electrochem. Soc., 163, A262 (2015).
Inductive Behavior in Electrochemical Impedance Spectroscopy: Can We Discriminate between Adsorption and Non-Stationarity
Authors: Benbouzid Abdelmoheiman Zakaria , Turmine Mireille , Vivier Vincent 
Published: December 2024

Electrochemical impedance spectroscopy (EIS) is a widely used technique for studying electrochemical processes. EIS typically assumes a linear relationship between the applied signal (potential or current) and the measured response (current or potential). In other words, doubling the input perturbation must result in doubling the output, and the output signal must show no change in shape. However, by using “small input signals”, a linear response can be achieved. Similarly, stationarity is also a requirement for EIS measurements. In this case, several factors may be at the origin of the problem. For instance, as an electrochemical reaction progresses, the electrode surface and the surrounding electrolyte can change, affecting the resistance and capacitance, and consequently, the impedance. Temperature variations can also affect the conductivity and mobility of ions, leading to a shift in impedance as a function of the frequency. If a system is non-stationary during an impedance measurement, the measured value won't represent a single, fixed state. The impedance will depend on the time the measurement was taken. This can make it difficult to interpret the data and compare it with other measurements.
Conversely, reaction mechanism involving adsorbates may be misinterpreted. Indeed, adsorption processes can result in either capacitive or inductive time-constants, usually observed in the low frequency domain. Such a behavior has been reported in the literature for corrosion processes. In this presentation, we will show how non-stationarity can modify an impedance diagram. Particular attention will then be paid to the case of the response of an adsorbed intermediate, such as the corrosion of Mg, for which inductive feature can be observed. The importance of the Kramers-Kronig relationships will then be discussed.
Efficient Electrochemical Conversion of Ammonium Nitrate Solutions Using Novel Electrodes
Authors: Alvarez Pugliese Christian E , Haque Alamgir Mojibul , Ogonna Okoye Francis , Azuka Kingsley , Gutierrez-Carballo Alejandro , Babar Pravin , Botte Gerardine G 
Published: December 2024

ANSOL, a byproduct of the production of energetic materials, is a chemical waste composed mainly of ammonium nitrate. In this study, we investigate various electrochemical methods for converting ANSOL into hydrogen, nitrogen, and/or ammonia (Figure 1). To our knowledge, this is the first comprehensive examination in the literature of the electrocatalytic conversion of ≥ 1M ammonium nitrate solutions in alkaline media using Ni, Cu, Co, Pt, Ir, and combinations thereof. We employ different electrode synthesis techniques, including electrodeposition, nanoparticle synthesis via polyol methods, and thermal reduction.
Our approach is based in Botte's patented Ammonia GreenBox technology [1-3], which has demonstrated the conversion of ammonia into hydrogen and nitrogen at pilot scale in wastewater treatment, and most recently on the simultaneous removal of nitrates and ammonia [4]. Our findings reveal remarkable activity and selectivity in the electrochemical nitrate reduction and ammonia oxidation reactions, resulting in high ammonia and hydrogen yields with exceptional Faradaic efficiencies.

Figure 1
(Invited) ALD HfZrO2 Films from Ferroelectric to High-k Applications
Authors: Leonhardt Alessandra , Cimada Jessica , Ramachandran Ranjith , Surman Matthew , John Rohit , Mootheri Vivek koladi , Tang Fu , Schmotzer Michael , Givens Michael , Balseanu Mihaela , Illiberi Andrea 
Published: December 2024

HfO2 based ferroelectric (FE) materials have gained tremendous attention as a potential candidate for memory applications such as FeFET and FeRAM. Since its first demonstration as a FE material [1],
immense research has been done to circumvent the challenges such as scalability, increasing the
remnant polarization (Pr), and improving endurance. Among others, Zr-doped HfO2, HfZrO2 (HZO) is being intensively studied due to its compatibility with complementary metal oxide semiconductor (CMOS) processing and excellent scalability. ALD has been the technique of choice for the deposition of those films, due to the high conformality, high film quality and simplicity of tuning the composition. HZO has excelled in this field, with high polarization, high endurance and retention. Those properties were still further improved by the addition of dopants such as La, which resulted in the record high 2Pr for films fabricated by ASM and imec using metalorganic precursors [2].
In this presentation we take ALD HZO one step forward, and describe how, by tunning the processing parameters of these films , the ferroelectricity can be modulated in a broad range, and how this can be incorporated in applications where high dielectric constants are desired. We discuss significant learnings in this material system regarding phase composition and crystallization dynamics, and how these can be used to modulate HZO from a ferroelectric into a high-k material. The extreme adaptability of ALD HfZrO2 provides an opportunity for its insertion in different applications. This material can extend logic and memory roadmaps, providing high capacitance, low leakage and high 2Pr, all at ultra-scaled thicknesses.

References

S. Boscke et al, Appl. Phys. Lett. 99, 102903 (2011)

I. Popovici and J. Bizindavyi et al, IEDM 2022
ALD Synthesis of Transition Metal Phosphides
Authors: Zazpe Raul , Rodriguez Pereira Jhonatan , Charvot Jaroslav , Klikar Milan , Bures Filip , Macak Jan M. 
Published: December 2024

The ever-increasing global energy demand together with the environmental issue originated from the use of fossil fuel, has triggered an intense search for sustainable and clean energy alternatives, such us hydrogen energy, biomass and solar energy among others. In this context, a pivotal key to deliver sustainable and superior energy systems lies on the rational design and development of high-quality and cost-effective catalyst offering enhanced stability, activity and selectivity. Consequently, intense efforts have been devoted in the search and synthesis of new catalyst materials to replace the scarce and expensive traditional noble metals (e.g. Pt, Pd, Au and Ru) for energy conversion and energy storage applications.
Among the recently explored novel catalyst materials, metal phosphides (MPs) have emerged in recent years, attracting significant attention thanks to their intriguing properties [1]. In particular transition metal phosphides (TMPs) exhibit striking properties. The moderately strong M−P bonds lend outstanding mechanical properties, high thermal stability and outstanding chemical resistance to chemical attack and oxidation in acidic and alkaline solutions. Additionally, Co, Ni, Mo-based phosphides demonstrated excellent catalytic and bifunctional properties, in particular towards water splitting as both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) [2,3].
Herein, we present the synthesis of TMPs by thermal Atomic Layer Deposition (ALD) based on the use of different transition metal precursors and tris(trimethylsilyl)phosphine. The physical and chemical properties of the resulting TMPs thin films were extensively characterized by different methods, including atomic force microscopy, X-ray photoelectron spectroscopy and X-Ray diffraction. The presentation will introduce and describe the synthesis of the TMPs and the corresponding physical and electrochemical characterization toward electrocatalytic application.
[1] Z. Pu, T. Liu, I. S. Amiinu, R. Cheng, P. Wang, C. Zhang, P. Ji, W. Hu, J. Liu, S. Mu, Transition-metal phosphides: activity origin, energy–related electrocatalysis applications, and synthetic strategies, Adv. Funct. Mater., 2020, 30, 2004009.
[2] C.C. Weng, J.T. Ren, Z.Y. Yuan, Transition Metal Phosphide-Based Materials for Efficient Electrochemical Hydrogen Evolution: A Critical Review, ChemSusChem, 2020, 13, 3357-3375.
[3] C.-J. Huang, H.-M. Xu, T.-Y. Shuai, Q.-N. Zhan, Z.-J. Zhang, G.-R. Li, A review of modulation strategies for improving catalytic performance of transition metal phosphides for oxygen evolution reaction, Applied Catalysis B: Environmental, 2023, 325, 122313.
(Invited) Enhancing the Performance of Lithium-Ion Cathodes
Authors: Croy Jason R. , Chen Jiajun , Mallick Subhadip , Pathak Rajesh , Elam Jeffrey W. 
Published: December 2024

Significant attention has recently been given to increasing the energy density of commercial LiNi1-x-yMnxCoyO2 (NMC) lithium-ion cathodes with an added constraint of greatly mitigating the use of cobalt. These two goals can be achieved in a seemingly straightforward manner by simply increasing Ni contents, and several Ni-rich compositions have found commercial success. Nonetheless, the increasing demand for lithium-ion batteries has brought about the realization that a more diverse portfolio, with respect to cathode materials, will be critical to ensure supply chain security, lower costs, and wide-spread adoption of energy storage technologies. More specifically, substantially increasing the use of earth-abundant materials is now viewed as a necessary path forward to ensure sustainability. Earth-abundant elements are attractive options in terms of sustainable technological development as they have the potential for positive impact with respect to increasing the availability of raw materials, ultimately lowering costs, and increasing accessibility of dependent technologies such as electric vehicles.
Regardless of the class of cathode under consideration for a given application, a common theme among all lithium-ion cathode materials is their need for modification in order to meet the stringent demands of application. Of note, all cathode materials generally require surface stabilization to help enable acceptable performance in terms of metrics such as cycle-life and impedance. This is particularly true in the drive to develop solid-state batteries. In addition, small compositional changes in the way of bulk and surface dopants can also have a major impact on long-term performance.
This presentation will discuss work ongoing at Argonne National Laboratory related to the modification of lithium-ion cathodes. Commercially relevant materials, as well as novel materials currently in development at Argonne, will be explored. Atomic layer deposition will be highlighted as a unique tool to not only enable enhanced battery cell performance, but also as an opportunity to discover new materials in the rapidly expanding market of lithium batteries.
Ethylene Carbonate Oxidation Due to Reactive Oxygen Species Near the Cathode: Insights from High-Throughput DFT Calculations and Monte Carlo Simulations
Authors: Mohanakrishnan Rohith Srinivaas , Vijay Sudarshan , Spotte-Smith Evan Walter Clark , Rinkel Bernardine L. D. , McCloskey Bryan D. , Persson Kristin A. 
Published: December 2024

Understanding the intricate pathways of ethylene carbonate (EC) decomposition is pivotal for enhancing the stability and efficiency of electrolytes in various electrochemical applications. In this study, we delve into the decomposition mechanisms of EC in the presence of superoxide and peroxide species. The decomposition of EC-based electrolytes causes gas (carbon dioxide, carbon monoxide and hydrogen) evolution. Since this gas evolution is observed at potentials much lower than the oxidation potential of EC, it has been suggested that the mechanisms leading to decomposition are primarily chemical in nature (i.e., not related to the electrochemical oxidation of EC) and related to the reaction of reactive oxygen [singlet, superoxide, peroxide] with EC. [1,2,3]. Utilizing high-throughput Density Functional Theory (DFT) calculations, we meticulously explored the reaction networks of EC with superoxide and peroxide species across different cathode voltages. Our findings unveil compelling insights into the primary pathways dictating EC decomposition, which notably occur at potentials significantly lower than the oxidation potential of EC. Monte Carlo simulations were performed to understand the major products of the reaction network. Carbon dioxide is one of the major products in the reaction networks. Other major products include mono-carbonate, formaldehyde and organic products containing O-O in the fragments. We find that the products with O-O bond in the organic chain were also previously observed through mass spectroscopy experiments in [4]. Thus, using high-throughput data-driven approach, we are able to identify novel decomposition pathways of ethylene carbonate near the cathode.
Reference
[1] Freiberg, Anna TS, et al. “Singlet oxygen reactivity with carbonate solvents used for Li-ion
battery electrolytes.” The Journal of Physical Chemistry A 122.45 (2018): 8828-8839.
[2] Wandt, Johannes, et al. “Singlet oxygen evolution from layered transition metal oxide
cathode materials and its implications for lithium-ion batteries.” Materials Today 21.8 (2018):
825-833.
[3] Rinkel, Bernardine LD, et al. “Electrolyte oxidation pathways in lithium-ion
batteries.” Journal of the American Chemical Society 142.35 (2020): 15058-15074.
[4] Kaufman, et al. “Surface Lithium Carbonate Influences Electrolyte Degradation via Reactive Oxygen Attack in Lithium-Excess Cathode Materials” Journal of the American Chemical Society (2021): 4170–4176
(Invited) TFT Technologies from Commercial Displays to Emerging Immersive Displays
Authors: Kuo Yue , Nathan Arokia 
Published: December 2024

Thin film transistors (TFTs) are used in displays providing the function of controlling light transmission, such as LCDs, reflection, such as electrophoretic displays, or emission, such as LED or OLED displays, from individual pixels in a 2D array – named active matrix flat panel displays (AMFPDs). The advantages of using TFTs in displays include gray-scale, dynamic, crosstalk-free, and uniform images as well as low power consumption over a large area.
The first report on the functional TFT and the outline and demonstration of the TFT LCD triggered worldwide research and development activities on AMFPDs. The lack of commercial products on the market is due to the bottleneck in the manufacturing technology, i.e., availability of a large area, low temperature, and high throughput process. The invention of the a-Si: H TFT in 1979 solved the production problem [1]. TFT LCDs were quickly introduced to the market. The size of the commercial displays changed from 4” in the 1980s to 98” in 2023, as shown in Figure 1 [2]. Extremely low power consumption electrophoretic displays were also introduced to the market. The main drawback of the a-Si:H TFT is the low field effect mobility, e.g., £1 cm2/Vs, which limits applications in driver circuits as well as very high speed or high driving current displays. Poly-Si TFTs can have mobilities up to 2 orders of magnitude higher than that of a-Si:H TFT. However, due to the complicated process conditions, their applications have been limited to small-sized displays, such as 20-inch LCDs, OLEDs, and μ-LEDs. The driver circuits were successfully integrated into the display. The a-IGZO TFT has a field effect mobility between those of a-Si:H TFT and poly-Si TFT. The a-IGZO TFT array can be mass-produced at a low temperature on a large substrate. Therefore, since the first report of the a-IGZO TFT in 2004 [3], it was quickly accepted by the display industry. Commercial OLEDs and μ-LEDs based on a-IGZO TFTs have been manufactured. Driver circuits have also been demonstrated. However, due to the lack of the p-channel TFT, the CMOS circuit has to be made of the n-channel oxide TFT and the p-channel poly-Si TFT.
Recently, due to the advancement in semiconductor technology and software, immersive displays have emerged in areas of entertainment, industry, education, etc. Displays play an important role in this trend because the human interface with the data is critical to these functions [4]. There are some basic requirements on the display concerning image quality, power consumption, response to the environment, and the user’s physical condition. In many applications, the size, weight, and flexibility of the display are important. In this paper, the authors will discuss these issues based on the existing TFT technology and explore opportunities.

Kuo, ECS Interface, 22(1), 55-61, 2013.

A commercial TCL 98" LCD downloaded from Google.

Nomura, et al., Nature, 432, 488-492, 2004.

Kuo, IEEE J. Immersive Displays, 1, 28-40, 2024.

Figure 1
2-Dimensional Palladium Organometallic Framework Generated Via C-H Activation for Electrochemical Syngas Production from CO2
Authors: Jung Jong-Yeong , Kim Jaewook , Song Hyunjoon 
Published: December 2024

Noble metal catalysts have been recognized for their exceptional catalytic activity and efficiency, sparking extensive research efforts. Recently, there has been a notable shift towards utilizing noble metal catalysts supported on stable materials, particularly within the realm of heterogeneous catalysts. Metal-Organic Frameworks (MOFs) have emerged as promising candidates in this regard, offering versatile platforms that serve as porous substrates for dispersing external noble metal species. Various methodologies have been developed to fabricate MOF-based noble metal catalysts, including the introduction of metal nanoparticles, the anchorage of metalloligands, and the utilization of desired metal clusters within the framework. However, because MOFs require metals to form their structures, the introduction of metal nanoparticles and the use of metalloligands necessarily entails the use of undesired metals. Therefore, while it is attractive to synthesize MOFs composed only of desired noble metals, direct synthesis of noble metal-based MOFs has been rarely reported due to significant synthetic challenges arising from the self-assembly of noble metal nanoparticles during solvothermal reactions.
Considering the chemical softness of noble metals, expanding the range of metal–ligand bonds to include chemical soft bonds is crucial for diversifying linkages and incorporating metal atoms as low-valent metal ions and noble metals. Beyond traditional metal–oxygen and metal–nitrogen bonds with carboxylates and azolates, organometallic metal–carbon (M–C) bond connecting crystalline frameworks has gained attention. However, due to the scarcity of multivalent ligands for the M–C bond, generating organometallic frameworks with a single organic linker presents synthetic challenges.
Herein, we found a new synthetic strategy applying organometallic chemistry. We successfully synthesized a Pd organometallic framework, PdOF-1, with a terephthalic acid (H2bdc), one of the most common ligands used for MOFs. PdOF-1 crystals were obtained through a one-pot solvothermal reaction of Pd acetate and H2bdc in dimethyl sulfoxide. Via Pd-catalyzed ortho C–H activation directed by carboxylic acid, Pd–C bonds were formed which directly connected bdc and Pd atoms. The framework comprises atomically dispersed Pd atoms forming organometallic Pd–C bonds, constituting a 2D network with the C2/c space group. As a result, PdOF-1 showed electrochemical CO2 reduction to produce syngas (H2/CO = 0.98) at a low potential of −0.33 V vs. RHE. This work not only presents a rare Pd organometallic framework, but also suggests a synthetic strategy to synthesize noble metal networks with M–C bonds and atomically dispersed noble metals.