bluuebunny/crossref_metadata_2025_split huggingface dataset:
Deep Metal-Assisted Chemical Etching Using a Porous Monolithic AgAu Layer to Develop Neutral-Colored Transparent Silicon Photovoltaics
Authors: Shin HyeonOh , Kwon Tae_Hyuk 
Published: December 2024

Neutral-colored transparent crystalline silicon photovoltaics (c-Si TPV) was reported as remarkable building-integrated photovoltaics (BIPV) due to its high efficiency with excellent transmittance. Deep reactive ion etching (DRIE) is required to fabricate this photovoltaics where the microhole-shaped light transmission windows were placed on bare crystalline silicon (c-Si, ca. 200 μm thickness) to transmit all visible wavelengths, which causes both high fabrication cost and the plasma damage on Si surface. A prominent replaceable method is metal-assisted chemical etching (MACE) which occurs through the redox reaction at the Si/metal catalyst/etchant solution interfaces because it features simplicity, versatility, and cost-effectiveness. However, the metal catalysts that grow via electroless deposition are deposited as particle-form, which act individually during MACE and induce the uneven MACE, thus yielding a lot of defects on the resultant Si.
Here, we report deep MACE using a porous monolithic AgAu layer on c-Si for fabricating c-Si TPV. To prevent the uneven etching of c-Si by Ag particles, the porous monolithic Ag layer is developed by introducing acetonitrile (AN) to enhance the interaction between the c-Si surface and Ag precursor. This results in cooperative motion during MACE, as confirmed by microscopic observation, surface area measurement, and computational simulations. The durability of this Ag catalyst can be further improved by passivation with Au via galvanic replacement (i.e., the porous monolithic AgAu layer), thereby preventing indiscriminate defect generation. Thus, the fabricated c-Si TPV using MACE and a porous monolithic AgAu layer exhibits high performance of 13.0% with 20% neutral-colored transparency, representing results superior to those obtained with samples fabricated by DRIE (11.5%).

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Implementation of Electrolytic Phosphating for Steel Wire Drawing as an Alternative to Conversion Coatings
Authors: Lissandrello Federico , Corti Nicola , Mazzeo Gabriele , Magagnin Luca 
Published: December 2024

Wire drawing is a cold deformation process in which a steel wire is pulled through several dies of decreasing size, in order to reduce its diameter. To ensure smooth operations and to maximize the lifetime of the expensive dies, lubrication of the wire is mandatory prior to the drawing step. More importantly, the lubricating layer is required to remain adherent to the steel surface for multiple deformation steps, while also maintaining its performance throughout the entire process. For this application, zinc phosphate conversion coatings are widely utilized in combination with an aqueous lubricant based on stearate salts. In fact, phosphate coatings can easily deform under the compressive load of the drawing step, while their porous nature maximizes the amount of lubricant that can be applied to the wire surface. [1]
Despite the good performance offered by conversion phosphating, there is an active interest in replacing this technology as it generates a significant amount of waste byproduct, the so called “phosphate sludge”. At the same time, finding an alternative conversion formulation that ensures the same performance is not a trivial task, especially when price is also factored in. In this context, electrolytic phosphating could offer an elegant, yet effective solution: the process allows the formation of coatings with the same chemical composition and morphology as conversion phosphating but prevents the formation of the sludge byproduct. With the application of an external voltage, it is in fact possible to trigger the local increase in pH responsible for phosphate formation without having to rely on the dissolution of the substrate. [2]
In this talk we will present the implementation of electrolytic phosphating in what is arguably its most relevant industrial application. In particular, by designing the phosphating tank around the symmetry of the steel wire, it is possible to ensure uniform distribution of the current density on the substrate, effectively avoiding the main drawback of the electrolytic process. Furthermore, the higher deposition rate obtained with the electrolytic setup allows the implementation of a continuous operation process, with a higher throughput than traditional batch conversion phosphating. The presentation will showcase results coming from laboratory-scale experiments as well as data resulting from real case-studies at the industrial level.

References

[1] A. Dubois, L. Lazzarotto, L. Dubar, J. Oudin, A multi-step lubricant evaluation strategy for wire drawing–extrusion–cold heading sequence, Wear 249 (2001) 951–961. https://doi.org/10.1016/S0043-1648(01)00830-4.
[2] F. Lissandrello, N. Lecis, L. Magagnin, Investigating the effect of current density in ultra-fast electrolytic zinc phosphate deposition, Electrochim Acta 478 (2024) 143840. https://doi.org/10.1016/J.ELECTACTA.2024.143840.
Understanding the Role of the Black Anodic Film in Copper Electrodeposition in Sulfuric Acid Medium: Organic Additives Free Electrolytes
Authors: Dematos Jean , Gigandet Marie-Pierre , Hihn Jean-Yves 
Published: December 2024

In the process of copper electroplating from a sulfuric acid bath it is well known that the copper anodes must contain a small quantity of phosphorous (CuP) (0.04 to 0.06 %). In the other hand, the electrolyte must contain a small amount of chloride ions (50 to 100 mg/L). The result is the formation on an anodic black film. The latter is essential in the proper functioning of the copper electroplating process. The presence of this black film prevents the formation of anodic sludge which compromises the quality of the copper deposits. The anodic behavior of copper is of great interest not only from the theoretical point of view but also as an important practical problem. The anodic sludge is formed by one of the following mechanisms [1], [2], Eq. (1) which is the disproportionation reaction of the cuprous ions, mechanism 1:
2 Cu+ ↔ Cu2+ + Cu (1)
Eq. (1) is responsible for the formation of anodic sludges. The mechanism 2 is the preferential dissolution along the intergrain boundaries and the consequent detachment of complete crystal grains from the crystalline structure. The addition of phosphorus as an alloying element during the manufacture of the anodes and the presence of chloride ions in the plating bath result in the formation of the anodic black film which eliminates the possibility of copper anode grains detachment and the alteration of the anodic dissolution mechanism. Copper anode dissolution proceeds under a two steps mechanism described by Eq. (2) and (3):
Cu ↔ Cu+ + e- (2)
Cu+ -> Cu2+ + e- (3)
Both of these reactions take place in the anodic film. In order to move from a bath with additives to a bath without additives, it is essential to answer the following questions: What is the effect of organic additives on the anodic side? What is the optimal concentration range for chloride ions? What is the influence of the grain size of Copper-Phosphorus anodes?
The present work deals with a extended characterization of the black anodic film and relevant insights about its formation mechanisms.
[1] : ST. RASHKOV and L. VUCHKOV, The Kinetics and Mechanism of The Anodic Dissolution of Phosphorus-Containing Copper in Bright Copper Plating Electrolytes, Surface Technology, 14 (1981) 309 – 321.
[2] : G. S. Frankel, A. G. Schrott, H. S. lsaacs, J. Horkans, and P. C. Andricacos, Behavior of CuP and OFHC Cu Anodes under EIectrodeposition Conditions, United States. Department of Energy, Brookhaven National Lab., Upton, NY (United States), 1992.

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Understanding Electrochemical Measurements of Lithium Diffusion in Porous LiNiO2 Cathodes
Authors: Vettori Kilian , Henss Anja , Janek Jürgen 
Published: December 2024

The chemical diffusion coefficient of lithium in cathode active materials is one of the key parameters determining battery performance. Fast diffusion allows fast charging and access to higher capacities before the potential limits of typical cycling routines are reached. Understanding the measurement of this crucial parameter through simple, non-invasive, in-situ electrochemical methods facilitates the investigation and optimization of cathode active materials for lithium-ion batteries. In this presentation, these electrochemical procedures are applied to LiNiO2 cathodes as a model system of the Ni-rich cathode active materials in liquid electrolyte cells.
These measurement routines have a history of almost 5 decades and have been adapted and modified since then. Recently they have received renewed interest for the reasons mentioned above. The presented electrochemical methods, including variations of galvanostatic and potentiostatic intermittent titration techniques (GITT and PITT), electrochemical impedance spectroscopy (EIS) and newer adaptations such as the Atlung method for intercalant diffusion (AMID) and Intermittent current interruption (ICI), are compared and reviewed with respect to underlying physical concepts of solid state diffusion and their application in typical porous cathodes for liquid electrolyte lithium ion batteries. Figure 1 gives a schematic view of lithium concentration in a cathode particle during delithiation and its relation to the electrode potential and the diffusion process.
The aim of this presentation is to enable more researchers to include diffusion measurements into their experiments and to facilitate the choice of method by comparing different techniques. By revisiting the fundamentals of solid state diffusion, it allows a deeper understanding of the chemical lithium diffusion coefficient and its measurement.

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Optimization and Electrochemical Testing of 3-Electrode Pouch Cell for Insights into Battery Prototyping
Authors: Roberts Alexander John , Greszta Agata , Somyanonthanakun Wuttichai 
Published: December 2024

When promising new materials are discovered and assessed for their electrochemical performance in batteries or other energy storage devices, their testing is typically performed initially in small coin cells, progressing to the single layer pouch cell (SLP) and on to commercially relevant prototype devices in various cell formats. As this development process moves from laboratory to commercial reality, the findings at coin cell level and SLP are typically used at an early stage to inform on expected performance. It is often the case that some device performance metrics obtained at SLP scale to those of a final prototype or commercial device, with other metrics from the same cell not giving a true indication.
In this work, we initially look to answer the question ‘what size does my test cell have to be to inform on final device performance?’ This is done through variation of design and size of Li-ion pouch cells, from coin to SLP, through multilayer pouch (MLP) cells of varied numbers of electrodes, and consideration of the relationship of cell parameters such as capacity, rate, resistance, and lifetime relative to those of final MLP prototype device.
A further challenge in the assessment and development of new materials performance and properties as we move from lab to commercially relevant prototype lies in understanding the potentials that individual electrodes experience in larger cell formats. Whilst this is relatively straightforward at the small scale with various methods of constructing coin/ Swagelok test cells with a reference electrode (3-electrode cells), as we move to SLP and MLP, this becomes significantly more challenging. Through the monitoring of individual electrode potentials in the larger format cell, invaluable information can be obtained, for example, for tailoring cell balance for application, helping to develop new algorithms for fast charging and understanding the effects of rate on lifetime.
Having considered the necessary cell size to inform on performance of final prototype device, this information has been used in the development of a 3-electrode cell, with the effect of reference electrode size and position, on anode and cathode potential measurement along with cell performance.
Interplay of Thermal Gradients and C-Rate on Lithium Plating
Authors: Ishtiaque Md Mahdi Ul , Ramamurthy Jayanth , Pint Cary L. , Kingston Todd A. 
Published: December 2024

Extreme fast charging (XFC) of lithium-ion batteries is crucial for solving range anxiety and rapid adoption of electric vehicles by significantly reducing charging time [1]. However, one of the key challenges in achieving this goal is lithium plating at the anode during the charging process [2]. Moreover, XFC will induce spatial temperature variations within the battery pack which will translate into thermal gradients inside a cell [3]. Interelectrode thermal gradients were previously found to induce accelerated lithium plating, degrading the battery life drastically [4], [5]. Therefore, it is critical to understand the complex interplay between C-rate and thermal gradients on lithium plating and its governing mechanisms. In this work, we investigate lithium plating under various thermal gradients and C-rates in single-layer NMC/graphite instrumented pouch cells. Thermistors were placed inside the cell at each electrode to precisely measure the magnitude of the thermal gradient conditions being applied. Galvanostatic cycling was performed at different C-rates and interelectrode thermal gradients. A comprehensive analysis was performed, including incremental capacity analysis. Three-electrode cells were utilized to isolate graphite-specific electrochemical processes and decipher the governing mechanisms. Post-mortem analysis was also performed to corroborate the electrochemical behavior.

Acknowledgments

The authors thank Dr. Michele Anderson (Office of Naval Research, grant N00014-22-1-2411) for financial support of this work. The authors also acknowledge Dr. Rachel Carter (U.S. Naval Research Laboratory) for technical discussion of this work.
References
[1] X. G. Yang, T. Liu, Y. Gao, S. Ge, Y. Leng, D. Wang, and C.Y. Wang , “Asymmetric Temperature Modulation for Extreme Fast Charging of Lithium-Ion Batteries,” Joule, vol. 3, no. 12, pp. 3002–3019, 2019, doi: 10.1016/j.joule.2019.09.021.
[2] C. Fear, M. Parmananda, V. Kabra, R. Carter, C. T. Love, and P. P. Mukherjee, “Mechanistic underpinnings of thermal gradient induced inhomogeneity in lithium plating,” Energy Storage Mater., vol. 35, no. July 2020, pp. 500–511, 2021, doi: 10.1016/j.ensm.2020.11.029.
[3] I. A. Hunt, Y. Zhao, Y. Patel, and J. Offer, “Surface Cooling Causes Accelerated Degradation Compared to Tab Cooling for Lithium-Ion Pouch Cells,” J. Electrochem. Soc., vol. 163, no. 9, pp. A1846–A1852, 2016, doi: 10.1149/2.0361609jes.
[4] R. Carter, T.A. Kingston, R.W. Atkinson, M. Parmananda, M. Dubarry, C. Fear, P.P. Mukherjee, and C.T. Love “Directionality of thermal gradients in lithium-ion batteries dictates diverging degradation modes,” Cell Reports Phys. Sci., vol. 2, no. 3, p. 100351, 2021, doi: 10.1016/j.xcrp.2021.100351.
[5] R. Carter and C. T. Love, “Modulation of Lithium Plating in Li-Ion Batteries with External Thermal Gradient,” ACS Appl. Mater. Interfaces, vol. 10, no. 31, pp. 26328–26334, 2018, doi: 10.1021/acsami.8b09131.
Aging and Power Characterization of Graphite-NMC Cells Containing Coal-Derived Graphites
Authors: Wolfe Kody D , Paul Abigail , Magee Regan , Wilczewski Warren , Wichert Nathan , Lowe Jeffrey , Trembly Jason , Staser John A. , Garrick Taylor R. 
Published: December 2024

Virtual scale-up of battery cell and pack designs requires detailed information about the thermodynamics and kinetics of lithium storage and transport in the active materials. To investigate lithium transport and kinetics in coal-derived graphites, pouch cells containing three coal-derived anode materials and one control synthetic graphite were prepared and tested with a reference performance test (RPT) followed by hybrid pulse power characterization (HPPC) every 50th cycle. The RPT, performed at a slow rate (C/50) yields pseudo-open circuit voltage behavior that is used to study changes in active material storage mechanisms by comparing to the initial behavior through the lens of the multi-species, multi-reaction (MSMR) model.1,2 HPPC testing at various state-of-charge (SOC) measures the transient resistance and is used to extract kinetic and diffusion parameters.
A comparative study between the three developed coal-derived anode materials will be presented with emphasis on enabling virtual scale-up and studying potential degradation pathways. The overarching goal of this work is to develop a workflow for validating alternative graphite materials to address graphite supply chain issues for applications in electric vehicles and grid storage.
References
1. M. Verbrugge, D. Baker, B. Koch, X. Xiao, and W. Gu, J. Electrochem. Soc., 164, E3243 (2017).
2. A. Paul et al., Journal of The Electrochemical Society, 171, 039001 (2024).
The Dopamine Assisted Synthesis of Integrated MoO3/Carbon Electrodes with Enhanced Charge Storage Properties for Aqueous Zinc-Ion Batteries
Authors: Pomerantseva Ekaterina 
Published: December 2024

Molybdenum trioxide (MoO3) emerged as a promising cathode materials for aqueous zinc-ion storage. In our investigation, we explored dopamine assisted synthesis routes to enhance the charge storage properties of MoO3 electrodes in electrochemical cells with aqueous electrolytes containing Zn2+ ions.
We developed a synthesis approach, in which dopamine hydrochloride (Dopa·HCl) was introduced into a hydrogen-peroxide initiated sol-gel reaction, yielding a powder precursor (Dopa)xMoOy, which underwent hydrothermal treatment (HT). Detailed characterization of the HT product revealed crystallization of the MoO3 phase combined with the dopamine carbonization. Therefore, this product was designated as HT-MoO3/C. The light-blue color of HT-MoO3/C, as opposed to the white color of MoO3, suggested presence of oxygen vacancies, however, their presence was not confirmed. The increased specific capacitance delivered by the HT-MoO3/C electrode as compared to the reference MoO3 electrode in 5M ZnCl2 electrolyte can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Building on the developed synthesis method, ethanol was introduced into reacting mixture during HT with the aim to reduce Mo in the forming HT-MoO3/C product. The dark-blue color of the produced powder, indicative of oxygen deficiency in MoO3 structure, was in agreement with XPS, TGA, Raman spectroscopy and XRD analyses confirming the presence of oxygen vacancies in the forming HT-MoO3-δ/C. Compared to the MoO3, four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon. Cyclic voltammetry-based charge storage mechanism analyses of the cells containing HT-MoO3-δ/C cathode, Zn anode and 30m ZnCl2 water-in-salt electrolyte revealed increases in ion transport kinetics attributed to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. With our synthesis method, oxygen vacancy formation can be easily controlled by changing the amount of ethanol during HT step of the synthesis route. Our work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.
Determination of Flash Point in Gel-Polymer Electrolytes for Their Use in Safe Quasi-Solid Batteries
Authors: St-Antoine Caroline , Michaud Paradis Marie-Chloe , Gonnel Pauline , Foran Gabrielle , Prébé Arnaud , Aymé-Perrot David , Dolle Mickael 
Published: December 2024

Gel polymer materials have recently gained significant attention for their use as electrolytes in quasi-solid batteries. A gel polymer electrolyte consists of a polymeric matrix in which a solvent is trapped. This composition offers a compromise between high ionic conductivity (facilitated by the solvent) and enhanced safety (provided by the polymeric matrix), making them a promising technology for short-term high-performance batteries. It is widely accepted that the polymeric matrix plays an important role in improving the overall safety of the electrolyte, notably by increasing its mechanical strength.1,2 However, there is a lack of systematic research on the effect of the polymeric matrix on the overall flammability. In the field of battery research, there is no standardized test to define and quantify the flammability of a gel polymer electrolyte.
This work focuses on the development of a flammability test that is adapted for the analysis of gel polymer electrolytes. The flash point temperature represents the lowest temperature at which there is enough vapor to produce a flame with a source of ignition. Flash point measurement is a standardized test extensively studied for liquid chemicals. In our previous work, flash point measurement was adapted for the analysis of gel polymer electrolytes by coupling the flash point instrument with a thermal imaging camera.3 This novel methodology and the subsequent data processing were automated and treated through computer vision to accurately identify the flash point temperature, eliminating potential errors associated with human interpretation on whether the flame is seen or not. The employed deep learning algorithms exhibit high accuracy in detecting the presence of the flash point with a small amount of solvent (15 L), making then suitable for the analysis of gel-polymer electrolytes. Moreover, the effect of intermolecular interactions between the solvent and the salt and between the solvent and the polymeric matrix have been studied by FT-IR and were shown to increase the flash point temperature.
References

Castillo, A. Santiago, X. Judez, I. Garbayo, J. A. C. Clemente, M. C. Morant-Minana, A. Villaverde, J. A. Gonzalez-Marcos, H. Zhang, M. Armand and C. M. Li, Chem Mater, 2021, 33, 8812-8821. 23.

Li, J. Chen, L. Fan, X. Kong and Y. Lu, Green Energy & Environment, 2016, 1, 18-42.

St-Antoine,C., et al., Journal of Materials Chemistry A, 2023. 11(20): p. 10984-10992.

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