bluuebunny/crossref_metadata_2025_split huggingface dataset:
Surface-Limited Electrochemical Reactions for the Characterization of Mass Transport in Nanoporous Electrodes
Authors: Rondou Noah , Vereecken Philippe M. , Blom Martijn J.W. 
Published: December 2024

Minimizing transport losses in (nano)porous electrodes is essential to many electrochemical applications such as electrolyzers, fuel cells, high-power density batteries. Often diffusion is the dominating mechanism that limits mass transport in these electrodes with very large surface areas. Electrochemical methods that characterize diffusion in porous electrodes, such as electrochemical impedance spectroscopy and scanning electrochemical microscopy, are limited in their use due to complex data interpretation and/or stringent infrastructure requirements. We have developed a novel method that utilizes a surface-limited reaction in a rotating disk setup that allows for the fast and straightforward characterization of effective diffusion coefficients in nanoporous electrodes, as well as estimation of their roughness.
Surface-limited electrochemical reactions, such as underpotential deposition (UPD), are commonly used to characterize the electrochemical surface area of porous electrodes. However, it has been shown that in nanoporous electrodes these processes can run into mass transport limitations, taking minutes to reach completion1,2. We utilize this effect in a rotating disk electrode setup, where it results in a characteristic current transient (Fig. 1a). An analytical model was developed to describe these current transients and extract performance parameters. Different sections of the current transient can be utilized to gain information on the porous electrode as illustrated in Fig. 1a. Besides the effective diffusion coefficient, determining the roughness of the porous electrode, the uniformity of the external mass transport resistance, and the bulk diffusion coefficient are possible. The tortuosity can then be determined from the bulk diffusion coefficient, porosity, and the effective diffusion coefficient. Further analysis of the analytical model also shows the possibility of electrochemically mapping the distribution of active sites in porous electrodes.
The methodology was tested experimentally on a platinum nanomesh electrode3 utilizing Cu UPD. An SEM image of a cross-section of the electrode is given in Fig. 1b. The nanomesh electrode's intrinsic high volumetric surface area (~ 30 m²/cm³) leads for certain to mass transport limitations for the Cu UPD process even for Cu2+ concentrations up to 0.8 mol/L. This combined with the uniformity of the electrode thickness allows it to be the ideal model system to verify the analytical model. The methodology was validated for different reaction conditions by comparing the tortuosity which was found to remain constant. The applicability of our method to porous electrodes in general will be discussed.

References

Y. Liu, S. Bliznakov, and N. Dimitrov, J. Phys. Chem. C, 113, 12362–12372 (2009).

E. E. Levin et al., Nanomaterials, 13 (2023).

S. P. Zankowski and P. M. Vereecken, ACS applied materials & interfaces, 10, 44634–44644 (2018).

Figure 1
(Invited) Nano-Sized Metal Deposition on Doped Silicon: Electrodeposition and Characterization
Authors: Giurlani Walter , Pappaianni Giulio , Montanari Francesco , De Luca Antonio , Innocenti Massimo 
Published: December 2024

The electrodeposition of nanostructured materials onto silicon substrates offers a pathway to blend the advantageous traits of metals with silicon's exceptional electronic properties. This amalgamation facilitates the creation of integrated circuits, electrodes for batteries, supercapacitors, fuel cells, sensors, and photovoltaic cells [1]. This deposition method was selected for its cost-effectiveness, scalability, and rapid synthesis capability. It operates at room temperature and atmospheric pressure, utilizing aqueous solutions with adjustable properties.
In this study, we examined the feasibility of electrodeposited nanoparticles, ultra-thin films, and Under Potential Deposition (UPD) on n-doped silicon [2]. The initial metal selection for electroplating was based on Density Functional Theory (DFT) calculations, considering factors such as the Schottky barrier, metal-silicon interactions, and metal-metal formation energy. Voltammetric analyses were conducted using solutions containing Ni, Ru, Pd, Rh, Pt, Ag, Mn, Co, and Au. Charge-controlled depositions were executed, supplemented by tests on electroless deposition. Optimal deposition conditions were sought for the most promising metals. The resulting deposits were morphologically and compositionally characterized using Scanning Electron Microscope (SEM) techniques, complemented by analytical spectroscopy including Energy Dispersive X-ray Spectroscopy Analysis (EDS) and X-ray Photoelectron Spectroscopy (XPS).
Multiple charge-controlled deposition cycles were carried out to modulate the surface coverage, the average thickness, and the particle size distribution. The metal deposits thus obtained are under study to be used as promising templates to partially wet etching the underneath silicon and produce silicon nanowires (NWs). This procedure could create new opportunities for small-size and better-performing sensors [3].
Project funded under the National Recovery and Resilience Plan (NRRP), Mission 4 Component 2 Investment 1.3 - Call for tender No. 341 of 15 March 2023 of Italian Ministry of University and Research (MUR) funded by the European Union - NextGenerationEU - Project code PE_00000004, CUP B83C22004890007, Project title "3A-ITALY - Made-in-Italy circolare e sostenibile".
References
[1] Giurlani, Walter, et al. Nanomaterials 12.4 (2022): 610, 10.3390/nano12040610
[2] Sulka, Grzegorz Dariusz. Molecules 28.10 (2023): 4040, 10.3390/molecules28104040
[3] Leonardi, Antonio Alessio, et al. Journal of Materials Science: Materials in Electronics 31 (2020): 10-17, 10.1007/s10854-018-0417-y
Characterization and Functional Properties of Electroplated Silver and Silver Alloys from Cyanide Free Electrolytes
Authors: Orecchioni Quentin , Gigandet Marie-Pierre , Bedjou Walid , Tardelli Joffrey , Hihn Jean-Yves 
Published: December 2024

The reduction of tungstate ions in aqueous solution is often referred as induced codeposition. Those ions can only be reduced to a metallic state alongside another element which is mostly nickel. However, other metal such as cobalt and iron are reported in the literature. Various hypothesis have been made concerning the precise mechanism behind induced codeposition, but even if the exact role of the various chemical species isn’t fully understood, tungsten was successfully electrodeposited using more noble element such as copper and silver [1].
Silver electroplating is a widely used process in the connector industry. In fact, while silver coatings exhibit an extremely high thermal and electrical conductivity, they remain highly vulnerable to sulphuration and present poor mechanical properties both in hardness and wear resistances. For these reasons, electrodeposition of silver alloys has aroused a recent interest, relying on an alloying element addition that would compensate silver weaknesses. Alloy compounds inducing high mechanical and chemical resistances such as tungsten, are obvious candidates.
Moreover, limitations in free cyanide use in electroplating processes is an active research subject. While gold-cyanide complexes are stable enough to be used without any cyanide ions in solution, silver complexation in alkaline baths is highly dependent on high free cyanide concentrations. Processes using thiosulfate, nitrogen heterocyclic compounds or methane sulfonate were proposed as replacement solutions, but they are still under investigations [2].
The present study is part of the SILAHPERF project, led by IRT-M2P and UTINAM Institute, which try to investigate the codeposition mechanism of various silver-based alloys of interest with a particular focus on silver-tungsten while seeking for environmental-friendly solutions. A cyanide-free silver-tungsten plating bath is proposed and resulting coatings are characterized by various techniques (SEM, XRD, GDOES...). Resolutely intended for connector applications, functional properties such as hardness, wear resistance and electrical conductivity of the deposit were evaluated depending on bath composition and electrolysis parameters.
[1] A. Kola, X. Geng, and E. J. Podlaha, ‘Ag–W electrodeposits with high W content from thiourea–citrate electrolytes’, Journal of Electroanalytical Chemistry, vol. 761, pp. 125–130, Jan. 2016
[2] B. Satpathy, S. Jena, S. Das, and K. Das, ‘A comprehensive review of various non-cyanide electroplating baths for the production of silver and gold coatings’, International Materials Reviews, vol. 68, no. 7, pp. 825–861, Oct. 2023
Ternary Copper Vanadate Semiconductors and Alloys for Energy Applications
Authors: Rajeshwar Krishnan , Meletis Efstathios , Rawat Abhishek , Danladi Fahad , Hersam Mark C 
Published: December 2024

Alloys offer a promising avenue for enhancing materials performance, and many examples exist for how Group III-V and II-VI compound semiconductors have revolutionized human life quality, e.g., via devices including lasers, displays, night vision technology, solar cells etc. Unlike the well-studied and technologically advanced Group III-V and Group II-VI compound semiconductor alloys, alloys of ternary metal oxide semiconductors have only recently begun to receive widespread attention. Here, we describe the effect of alkaline earth metal substitution on the optical, electronic, and photoelectrochemical (PEC) properties of two families of copper vanadates (CuV2O6 and Cu2V2O7). As a host, the Cu-V-O structural framework presents a versatile platform to develop chemical (alloy) composition-property correlations. The influence of alkaline metal (e.g., Ca, Mg, Sr) incorporation was studied. Photoelectrochemical energy conversion/solar water splitting and wide bandgap oxide semiconductors and alloys for solar windows/displays and radiation detectors are the two targeted application areas here. Both synthetic aspects and chemical composition-property-performance correlations will be presented.
Acknowledgements. This work was primarily supported by the National Science Foundation UTA/NU Partnership for Research and Education in Materials (NSF DMR-2122128).
Design and Fabrication of an Economically Viable Open-Source Programmable Rasterable System for Electroplating
Authors: Anene Emmanuel Chikwado , Bruce David Robert 
Published: December 2024

The advent of an open-source programmable rasterable equipment that is economically viable represents a transformational change in three-dimensional (3D) electroplating technology, to allow researchers to design and construct their own system which is both cheaper and globally accessible.
In this research, we present the design of an open-source programmable rasterable electroplating system, whose working mechanism is based on both pulse width modulation (PWM) control of plating combined with geometric code (g-code) programming for automated movement. For the PWM control, a programmable current in the range of 0 – 20 mA and voltage 0 – 5 V is written as a computer code in an Arduino integrated development environment (IDE) as controlled by a Raspberry Pi microcomputer. The code is converted from a digital signal to an analog output signal by a printed circuit board potentiostat built from common components. Concurrently, the g-code, which is a numerical model, controls the movement of the anode during electroplating in order to electrodeposit/print a physical object corresponding to a 3D designed model. The codes can be modified freely to vary the potentials during electroplating and allow users define specific electrodeposition patterns.
Unlike traditional electroplating setups, our open-source programmable rasterable electroplating system was designed and constructed using globally available equipment: a Raspberry Pi 4 model B and an Arduino Uno, a printed circuit board potentiostat, and a modified Crealty Ender 3D printer. This system enables dynamic control over electrodeposition patterns and parameters. Moreover, it not only enhances efficiency and reproducibility but also democratizes access to advanced electrochemical techniques, paving the way for transformative discoveries in materials science, nanotechnology, and beyond.
A discussion of equipment limitations and tradeoffs between costs, availability and performance indicates opportunities for industrial application as well as for facilitating global teaching and learning.
Controlled Texture of Metal Electroforming through Pulse Electrodeposition
Authors: Mirabal Alex , Hooks Daniel E , Fensin Saryu Jindal , Stull Jamie A 
Published: December 2024

Impact physics provide equation of state information for material performance in extreme environments. There is some evidence that the underlying microsctructure impacts the response at some velocities1. One way to probe the microstructure is through controlled electrodeposition. Both pulse plating and chemical additives are known to modify the grain structure during electrodeposition. However, additives can be incorporated in the coating and influence the resulting properties such as hardness and mechanical properties. Therefore, we aim to control electroformed coatings through exclusively using square wave pulses.
There are some preliminary studies indicating control of grain size of electroplated coatings, however, process control has, so far, only been studied by post characterization analysis on often limited subsets2–5. A methodical approach leads to a deeper mechanistic understanding of isolating plating parameters to control the grain structure.
In this work, we explore the impact of current density, duty cycle, frequency and pulse widths/heights and their impacts on the grain structure. We show uniform grain structure through thick films (>3mm), and control over the texture and orientation of grains (Fig. 1).
(1) Escobedo, J. P.; Dennis-Koller, D.; Cerreta, E. K.; Patterson, B. M.; Bronkhorst, C. A.; Hansen, B. L.; Tonks, D.; Lebensohn, R. A. Effects of Grain Size and Boundary Structure on the Dynamic Tensile Response of Copper. J. Appl. Phys.
2011, 110 (3), 033513. https://doi.org/10.1063/1.3607294.
(2) Marro, J. B.; Darroudi, T.; Okoro, C. A.; Obeng, Y. S.; Richardson, K. C. The Influence of Pulse Plating Frequency and Duty Cycle on the Microstructure and Stress State of Electroplated Copper Films. Thin Solid Films
2017, 621, 91–97. https://doi.org/10.1016/j.tsf.2016.11.047.
(3) Chan, K. C.; Qu, N. S.; Zhu, D. Crystallographic Textures and Magnetic Properties of Electroformed Nickel. J. Appl. Electrochem.
1998, 28 (10), 1095–1099. https://doi.org/10.1023/A:1003452615814.
(4) Sivasakthi, P.; Sekar, R.; Bapu, G. N. K. R. Pulse Electrodeposited Nickel Using Sulphamate Electrolyte for Hardness and Corrosion Resistance. Mater. Res. Bull.
2015, 70, 832–839. https://doi.org/10.1016/j.materresbull.2015.06.019.
(5) El-Sherik, A. M.; Erb, U.; Page, J. Microstructural Evolution in Pulse Plated Nickel Electrodeposits. Surf. Coat. Technol.
1997, 88 (1), 70–78. https://doi.org/10.1016/S0257-8972(96)02928-3.

Figure 1
Effect of Fast-Charging and Cycling Window on Lithium-Ion Battery Performance and Aging
Authors: Venkatakrishnan Sankaranarayanan , Ramasamy Ramaraja 
Published: December 2024

Aggressive charging practices and extreme usage patterns of electric vehicle batteries pose safety risks, including fire hazards. Beyond fast charging, battery health is influenced by dynamic factors like temperature, state-of-charge (SoC) window of operation, and driving conditions relative to charging events1,2. Given that electric vehicles (EVs) rarely operate in their full SoC range (0–100%)3, understanding battery cell degradation across different SoC swing ranges and fast-charging effects becomes critical. This understanding not only optimizes battery usage and extends cell lifespan but also enhances lifetime economics and mitigates environmental consequences tied to raw material extraction and manufacturing2.
This study explores the impact of SoC swing ranges and fast charging on the performance and aging of commercially available 18650 cells equipped with graphite-NCA electrodes. Departing from the conventional constant-current constant-voltage (CC-CV) fast charging protocol, we adopted a scaled-down version of the 150-kW real-world battery electric vehicle (BEV) fast charging profile. Unlike the broader SoC range of high current charging typical in CC-CV protocol, the real-world BEV fast-charging profile charges the battery at peak power or peak current only in a narrow SoC range between 10% and 40% SoC and then tapers down. Cycling experiments were conducted for two sets of SoC ranges: 0%-50% and 0%-100%. Both cycling experiments exhibited similar trends in overall capacity fade, yet the underlying causes differed. The DV-IC analysis revealed that the loss of active negative electrode material (LAMNE) was pivotal in capacity fade for both cycling experiments. Notably, during 0%-100% SoC cycling, loss of positive electrode material was observed alongside LAMNE. Additionally, variations in the homogeneity of lithium distribution within the negative electrode and kinetic rate degradation of the negative electrode were evident.
This research underscores the critical role of SoC swing ranges and fast charging protocols in battery degradation, with differential voltage and incremental capacity analysis revealing distinct degradation pathways. It highlights the need for optimized battery usage strategies to extend cell lifespan, enhance lifetime economics, and mitigate environmental impact, thereby contributing to the sustainable growth of the EV market.
References:

C. R. Birkl, M. R. Roberts, E. McTurk, P. G. Bruce, and D. A. Howey, Journal of Power Sources, 341, 373–386 (2017).

J. S. Edge et al., Physical Chemistry Chemical Physics, 23, 8200–8221 (2021).

G. Luo, Y. Zhang, and A. Tang, Energies, 16, 4232 (2023).
(Invited) Probing the Functionality of Lithium Carbonate in Lithium Metal Interphases through Model and Native SEI
Authors: Gallant Betar M. 
Published: December 2024

The lithium (Li) metal anode promises significantly higher capacity than graphite and is central to strategies to develop advanced Li-ion batteries with improved energy, lifetime and performance. Yet, the Coulombic efficiency (CE) of Li anodes in liquid electrolytes still falls well below the >99.9% targeted for electric vehicles. Efficiency and capacity loss arise from uncontrolled reactivity at the solid electrolyte interphase (SEI) and its resulting physicochemical, ionic and electronic properties, which couple to inhomogeneous plating/stripping, SEI breakage, electrolyte infiltration and additional consumption, and ultimately to loss of active Li inventory as stranded Li0 or SEI Li+. Despite empirical insights into electrolyte design guidelines, quantitative understanding of SEI functionality is underdeveloped, hindering attempts to control and improve its properties through tailoring of its materials chemistry.
This talk will discuss ongoing efforts to improve understanding of phase-specific functionality in the SEI, with an objective of identifying compositional design principles to minimize active Li inventory loss. We developed approaches to isolate and synthesize SEI-relevant ionic and organic phases, including lithium fluoride (LiF)1, lithium oxide (Li2O),2and recently lithium carbonate (Li2CO3), at representative nanometer-scale thicknesses directly on Li metal. These interfaces are interrogated via targeted electrochemical techniques to reveal their Li+ conductivity, providing a framework to assess which phases bolster, or hinder, ion transport in the SEI. Here we examine in detail the role of Li2CO3, a pervasive yet metastable SEI component that has long been asserted to improve CE in conventional carbonate electrolytes.3-5 By synthesizing model Li2CO3 interphases, we measure the ionic conductivity, probe reaction pathways in contact with specific electrolyte constituents, and interpret its properties against other key ionic SEI phases. We further examine the role of carbonate on the native SEI through re-examination of CO2 gas as a cell additive in a wider range of electrolytes—including modern formulations like ethers and localized high-concentration electrolytes (LHCEs)—than those studied previously. In combination with titration methods,6,7 we finally reveal how Li2CO3 relates to capacity loss at the anode and conditions in which enhancing Li2CO3 translates into improved CE.

He, R. Guo, G. Hobold, H. Gao and B.M. Gallant, PNAS 2020, 117, 73-79.

Guo and B.M. Gallant, Chemistry of Materials 2020, 32, 13, 5525-5533.

Plichta, S. Slane, M. Uchiyama, M. Salomon, D. Chua, W. B. Ebner and H. W. Lin, J. Electrochem. Soc. 1989, 136, 1865.

Aurbach, Y. Gofer, M. Ben-Zion and P. Aped, J. Electroanal. Chem 1992, 339, 451.

D. Aurbach, I. Weissman, A. Zaban and O. Chusid, Electrochimica Acta 1994, 39, 51.

Fang, J. Li, M. Zhang et al., Nature 2019,572, 511–515.

M. Hobold and B. M. Gallant, ACS Energy Letters 2022, 7, 3458-3466.
(Invited) Metallization for Advanced Semiconductor Technology Nodes: Wet-Chemical Deposition and Etching, Characterization, and (Semi) Damascene Approaches
Authors: Philipsen Harold 
Published: December 2024

To ensure semiconductor technology scaling to continue for the decades to come, the industry focuses on identifying alternative metals (elemental or alloys), that can replace copper in the back end of line (BEOL) integration scheme, for which the metal is used as main conductor for most of the metallization levels. Recently, the semi-damascene process is being developed, in which the interconnect metal is first deposited and then patterned using a dry etching process (‘direct metal etch’), in a fashion closely resembling the traditional Al metallization. One of the advantages is that any metal that can be deposited as a blanket thin film (either by physical vapor deposition (PVD), electrochemical deposition (ECD), electroless deposition (ELD), chemical vapour deposition (CVD), or atomic layer deposition (ALD)) can subsequently be patterned, provided that the critical requirement for dry etching of ‘volatilization’ of the metal is fulfilled. Furthermore, it allows the integration of materials for which no ECD, ELD, CVD or ALD process is available to fill damascene trenches.
In this contribution, intrinsic material properties (bulk resistivity, electromigration, ...) and composition (surface versus bulk composition as well as surface oxide) of a wide range of metals and alloys of interest to the BEOL will be compared. An overview of wet-chemical deposition approaches of a few selected metals (Cu and Rh) will be given. For ELD, the focus will be on discussing the mechanistic understanding of the intrinsically complex process, for which the stability and reactivity of the reducing agent is affected by solution pH and composition as well as the presence of oxygen. For ECD, results will be discussed for Rh and Ni, for which an electrochemical quartz crystal microbalance (EQCM) was used to quantify the amount of material deposited and interpret the various features detected in cyclic voltammograms. Metal ion solution speciation as well as stability, of importance for both deposition methods, has been studied using UV-vis spectroscopy and electrochemical characterization (linear sweep and cyclic voltammetry). Deposits were analysed morphologically using transmission electron microscopy and the chemical composition was assessed by elemental mapping.
During process integration, the surface-chemical composition of metals / alloys needs to be carefully controlled, as this can, for instance, critically impact metal line resistance or result in wet etching or corrosion. A few example cases in which this is relevant will be presented, e.g. the reversible surface oxidation and reduction of Cu was studied using EQCM, the surface chemistry of NiAl was characterized using electrochemical measurements, and the reversible surface nitridation of a model metal (Mo) is demonstrated as a method to protect against unwanted metal dissolution.