bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Nucleation and Growth: A Multimicroscopy Approach at the Same Scale
Authors: Torres Daniel , Bernal Lopez Miguel , Ustarroz Jon 
Published: February 2024

Electrodeposition is a critical electrochemical reaction with broad applications in technology. This demands a comprehensive understanding of the electrochemical nucleation and growth process (EN&G), and the different factors driving the formation of a new phase on a given substrate. Our understanding of the role of the substrate and the real nature of active sites still remains elusive due to the challenge of probing specific sites and bringing a statistical interpretation of the nucleation process. Moreover, conventional macroscopic approaches often record electrochemical magnitudes over large areas (cm2) which are then correlated with surface characterizations obtained from a vastly different scale (~μm2), correlations, which are not necessarily representative of the macroscopic surface. In order to establish meaningful and unambiguous correlations, it becomes necessary to employ techniques capable of surveying the surface with a high spatial-temporal resolution, such as scanning probe techniques, capable of recovering information in a scale closer to the growth of the new phase, i.e., local scale1. To address these challenges, we employed Scanning Electrochemical Cell Microscopy (SECCM), to study the EN&G of Cu on a glassy carbon substrate at a scale closer to the initial stages of the electrodeposition2. SECCM can be combined with other imaging methods such as scanning electron microscopy (SEM) to recover information from the deposited nanostructures at the same scale as the electrochemical response3. This so-called multimicroscopy approach allows us establishing direct correlations between the EN&G and the morphological, structural, and compositional features of the substrate and deposit. As a result, new insights that are not available with conventional macro-electrochemical analysis can be gained, such as the time-, potential-, and site-dependent nature of the EN&G process with a statistical perspective. This approach provides a new avenue for developing novel analysis strategies to understand the real nature of active sites for nucleation.
References

M. Bernal, D. Torres, S. S. Parapari, M. Čeh, K. Ž. Rožman, S. Šturm, and J. Ustarroz, Electrochim. Acta, 445, 142023 (2023).

D. Torres, M. Bernal, A. Demaude, S. Hussain, L. Bar, P. Losada-Pérez, F. Reniers, and J. Ustarroz, J. Electrochem. Soc., 169, 102513 (2022).

D. Torres, M. Bernal Lopez, and J. Ustarroz, Electrochemical nucleation and growth: A multimicroscopy Approach at the same scale, In preparation. (2023).

Figure 1
Electrodeposited Ni-Based Catalysts for the Oxygen Evolution Reaction
Authors: Deo Yashwardhan , Thissen Niklas , Mechler Anna K. 
Published: February 2024

Alkaline water electrolysis is one of the most mature technologies for producing green hydrogen. However, there still are possibilities to enhance this process by using better electrocatalysts for the kinetically limited oxygen evolution reaction (OER). While there are several existing methods for catalyst synthesis, such as spray coating, coprecipitation and hydrothermal synthesis, they face challenges of either versatility or scalability.[1,2] In this regard, electrodeposition is a promising catalyst synthesis method, due to its excellent process control and ease of scalability.
In this work, electrodeposition is used to prepare nickel-based catalysts as a benchmark system. These catalysts are deposited on expanded Ni-mesh supports. Initially, the deposition parameters are optimized to obtain uniform Ni deposits, which provide reproducible activity measurements. Herein, we observe that the deposited Ni catalysts exhibit better OER activities than the Ni mesh support, most likely due to the evolution of a pyramidal morphology with an increased surface area (Fig. 1). The optimized deposition parameters are further used to deposit different Ni-based alloys such as Ni-Fe and Ni-Co, by adding the respective ionized metal species to the Ni electrolyte. The microstructure and composition of these catalysts is analyzed using material characterization techniques like scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). Finally, the OER activity and long-term stability of the deposited catalysts is evaluated in an in-house developed electrochemical beaker cell at elevated concentration, temperature, and current densities (30 wt.% KOH, 80 °C, up to 1 A/cm2). The results obtained for the different catalysts are compared to understand the correlation of the catalyst structure and composition with their electrochemical OER performance under industrial conditions.

Bibliography

[1] Lu Xunyu et al.; Nature Communications; DOI: 10.1038/ncomms7616
[2] Zuraya Angeles-Olvera et al.; Energies; DOI: 10.3390/en15051609

Figure 1
Electrodeposition of Zn-Cr Alloys: A Comparison with Pure Zinc
Authors: Galeotti Francesca , Lissandrello Federico , Magagnin Luca 
Published: February 2024

The electrodeposition of zinc coatings is one of the most common surface treatments for providing corrosion resistance to metallic components. From the thermodynamic point of view, zinc is located in a sweet spot, with its reduction potential being lower than most other common metals, while at the same time being not too susceptible to atmospheric corrosion; overall these features make zinc the ideal candidate for the electroplating of sacrificial coatings for corrosion protection. Owing it to its low cost and scalability, zinc electroplating has cemented itself as a cornerstone process in a variety of industrial sectors in the last decades. [1]
While zinc coatings corrosion resistance has proved to be satisfactory in most cases, it could still be improved to operate even in more aggressive environments. For this purpose, electrodeposition of zinc alloys with transition metals from the iron group (Ni, Co, Fe) has proven to be a successful method to enhance zinc coatings corrosion resistance. In particular, zinc-nickel alloys have found the greater success among them, due to improved corrosion resistance and mechanical properties. [2]
Zinc-chromium alloys also present a good opportunity to improve coatings performance, thanks to the passivating effect of Cr. In fact, electrodeposited ZnCr alloys with a Cr content up to 10.4% were found to exhibit a corrosion potential shifted by up 150 mV in the anodic direction with respect to the pure zinc counterpart. [3] This shift led to a significant decrease in the coating dissolution rate but was sufficiently small that the layers could still preserve their sacrificial nature towards the underlying steel.
In this work, ZnCr coatings are deposited on low carbon steel from an acidic sulfate formulation containing Cr(III) ions at various concentrations. The properties of ZnCr coatings are explored by varying the most common parameters such as current density, composition, and pH. Furthermore, the resulting coatings are characterized through conventional surface analysis techniques such as SEM, EDS, XRD and XRF. Finally, the corrosion resistance performance of the ZnCr coatings is compared to pure Zn coatings to highlight the benefits of the alloy.
Bibliography
[1] R. Winand, “Electrodeposition of Zinc and Zinc Alloys,” Mod. Electroplat. Fifth Ed., pp. 285–307, Feb. 2011.
[2] N. Lotfi, M. Aliofkhazraei, H. Rahmani, and G. B. Darband, “Zinc–Nickel Alloy Electrodeposition: Characterization, Properties, Multilayers and Composites,” Prot. Met. Phys. Chem. Surfaces, vol. 54, no. 6, pp. 1102–1140, Nov. 2018.
[3] V. Chakarova, T. Boiadjieva-Scherzer, D. Kovacheva, H. Kronberger, and M. Monev, “Corrosion behaviour of electrodeposited Zn-Cr alloy coatings,” Corros. Sci., vol. 140, pp. 73–78, Aug. 2018.
Silver-Rich Clusters Reveal the Initial Size of Nanoscale Network during Dealloying Via Kinetic Monte Carlo Simulation
Authors: Li Yong , Markmann Jürgen , Weissmuller Jorg 
Published: February 2024

As residues of the master alloy that survived corrosion, the silver-rich clusters of nanoporous gold (NPG) fabricated by dealloying affect the functional properties of the material. Also, they are representative of the initial nanoscale network established at the beginning of dealloying. The evolution of silver-rich clusters during dealloying at different potentials is investigated via kinetic Monte Carlo simulations [1]. Our simulations show that the dealloying consists of two characteristic processes: (i) the primary process produces an initial three-dimensional bicontinuous network with silver-rich clusters embedded in the ligaments and pure gold covered on ligaments' surface. See Fig.1(a). (ii) the secondary process coarsens the ligaments and further dissolves silver from the ligaments. See Fig.1(b). The size of silver-rich clusters, L
Ag, scales with that of ligaments, L
lig, during primary dealloying for all studied potentials (Fig.1(c)). Both sizes decrease with increasing dealloying potential. The trends in size and potential are consistent with a Gibbs-Thompson-type relation (dash-dotted line in Fig.1(c)). Yet, the size of silver clusters remains invariant when the ligament size increases during secondary dealloying. Our simulations reveal that the survived clusters provided a way to measure the initial ligament size.
Fig.1. Renderings of slicing the NPG structure at different dealloying time (a-b) and the size evolution during primary dealloying (c) (Ref.[1]): (a) the primary dealloying establishes the initial 3D nanoscale network, (b) the secondary dealloying dissolves Ag clusters and coarsens ligaments, (c) inverse of Ag cluster size, L
Ag and of ligament size, L
lig, during primary dealloying as a function of dealloying potential, Φ.
Reference:
[1] Y. Li, B.-N. D. Ngô, J. Markmann, J. Weissmüller. Evolution of length scales and of chemical heterogeneity during primary and secondary dealloying, Acta Materialia, (2021) 117424.

Figure 1
Reactive Aerosol Jet Printing of 2D and 3D Ag Patterns
Authors: Gibertini Eugenio , Magagnin Luca 
Published: February 2024

Printed electronics is a rapidly growing field that involves the use of printing technologies to create electronic devices such as sensors, displays, and solar cells 1. Unlike traditional electronics, which rely on rigid and bulky components, printed electronics can be obtained on flexible and lightweight substrates such as plastic and paper, allowing the development of novel applications such as wearable electronics, smart packaging, and medical sensors. Printing technologies uniquely feature miniaturization and patterning capability at low-cost and high-throughput production. Among them, screen-printing, inkjet printing (IJP) and aerosol jet printing (AJP) are the most employed to fabricate conductive metallic patterns of Ag, Au, Cu and other metal nanoparticles (NPs). These printing techniques typically requires concentrated ink of metal NPs. However, specially in the case of IJP and AJP the synthesis of very small NPs (d < 100 nm) as well as proper ink formulation and long-time stability are major limitations to printing conductive metallic patterns 2.
In this work, we propose an innovative method to produce 2D and 3D patterns and structures of Ag NPs by reactive Aerosol Jet Printing (r-AJP) on different substrates, using a custom-built aerosol jet printer. Ag NPs were in-situ reduced coupling two aerosol streams carrying the Ag precursor and a reducing agent, respectively. The process is fast, scalable and cheap. The electrical properties, in terms of both linear and areal electrical conductivity, of the r-AJP silver structures metallization patterns were investigated. Furthermore, the effect of both process parameters and precursor solution physical properties on printed Ag structure and morphology was assessed by x-ray diffraction (XRD) and scanning electron microscopy (SEM) in order to define the optimized condition for high definition 2d and 3D patterns by r-AJP.

Bibliography

P. Martins et al., Advanced Functional Materials, 33, 2213744 (2023).

Y. Sui and C. A. Zorman, J. Electrochem.
Soc., 167, 037571 (2020).
Ni-P Electroless Plating of Polyethylene Terephthalate Fibers with Various Twist Number Utilizing Supercritical CO2-Assisted Catalyzation
Authors: Kondo Hikaru , Kurioka Tomoyuki , Chiu Wan-Ting , Chen Chun-Yi , Chang Tso-Fu Mark , Ueno Roka , Jinno Arisa , Kurosu Hiromiti , Sone Masato 
Published: February 2024

Weavable devices are multifunctional fabric-based devices prepared by weaving various functional fibers into a single piece of fabric. Metalized polymer fibers are promising electrical conductors for such weavable devices because of the decnet electrical conductivity derived from the metal coating and flexibility arising from the polymer fiber. However, ensuring both sufficient electrical conductivity and stability in these metalized polymer fibers for practical device application remains challenging because of the insufficent adhesion between the metal coating and polymer fiber. An electroless plating with the catalyzation step performed in supercritical carbon dioxide (sc-CO2)1 is developed to produce metallized polymers possessing high electrical conductivity and good adhesive properties between the metal coating and polymer fiber. In application, fibers are often twisted to enhance a specific property, such as the mechanical property, and the twist number (twist per meter, T/m) is expected to affect the electroless plating performance.
In this presentation, Ni-P electroless plating of polyethylene terephthalate (PET) fibers with a different twist number (twist per meter, T/m) is reported. The sc-CO2-assisted catalyzation was utilized to achieve electroless plating of Ni-P coatings on the PET fibers. The electrical resistance of the Ni-P/PET fibers was decreased following an increase in the twist number as listed in Table 1. Elemental analyses revealed that the Ni content in the Ni-P coating was higher for the PET fibers with a larger twist number. This tendency corresponded well the the electrical resistance results since Ni-P with a higher Ni content is expected to have a lower electrical resistance. Results obtained in this study indicate that PET fibers with a larger twist number is beneficial for the electroless Ni-P plating by decreasing of the electrical resistance in the fabricated Ni-P/PET fibers.

Reference

T.-F.M. Chang et al., Microelectron. Eng.
2020, 223, 111233.

Figure 1
Differences in the Ti4+/Ti3+ Redox Reactions between Li4Ti5O12 and LiTi2(PO4)3 Observed By Soft X-Ray Spectroscopy
Authors: Asakura Daisuke , Kitaura Hirokazu , Kiuchi Hisao , Miyawaki Jun , Harada Yoshihisa , Kobayashi Masaki , Amemiya Kenta , Yoshioka Satoru , Kobayashi Eiichi , Miseki Yugo , Hosono Eiji 
Published: February 2024

Clarification of the redox reaction in electrode materials for Li-ion batteries is essential to obtain strategies to improve the performances such as charge-discharge capacity, voltage and cyclability. We focus on the difference in voltage, i.e., redox potential between Li4Ti5O12 (LTO) and LiTi2(PO4)3 (LTP). Spinel-type LTO with a redox potential around 1.5 V vs Li/Li+ is one of the anode materials [1], while the main redox potential of LTP (NASICON-type structure) is around 2.4 V vs Li/Li+ [2]. Although the difference in redox potential is as large as ~0.9 V, it has been thought to be that Ti4+/Ti3+ redox couple is identical for both LTO and LTP. Here, we demonstrate the electronic-structure analysis of LTO and LTP by using soft X-ray absorption spectroscopy (XAS) and soft X-ray photoemission spectroscopy (XPS). Operando Ti L
2,3-edge XAS by use of an all-solid-state cell [3,4] successfully revealed reversible Ti4+/Ti3+ redox reactions by discharge/charge for both materials, but the XAS line shapes were different. By analyzing the spectra using multiplet calculation [5], differences in the crystal-field splitting for the TiO6 octahedron and O 2p -> Ti 3d charge-transfer (CT) effect were found. The different CT effect was also confirmed by Ti 2p-3d resonant XPS measurements for the initial-state LTO and LTP samples. Moreover, the difference in redox potential is mostly explained by the energy levels of the pre-edge structures in the O K-edge XAS calibrated with the O 1s XPS spectra. In the presentation, the understandings of the spectroscopic results will be discussed in detail.

References

[1] K. M. Colbow et al., J. Power Sources
26 (1989) 397-402.
[2] C. Delmas et al., Solid State Ionics
28-30 (1988) 419-423.
[3] K. Akada et al., Sci. Rep.
9 (2019) 12452.
[4] K. Akada et al., J. Electron Spectrosc. Relat. Phenom.
233 (2019) 64-68.
[5] E. Stavitski and F. M. F. de Groot, Micron
41 (2010) 687-694.
(Invited) Electrodeposition of In and Ga from Non-Aqueous Electrolytes
Authors: Fransaer Jan , Monnens Wouter 
Published: February 2024

Indium and gallium are metals whose applications have increased during the last decades. Both metals are primarily used in the form of binary, tertiary or quaternary (semi)conductor compounds in integrated circuits, photovoltaics, liquid crystal display devices, lasers and light-emitting diodes.
In the past, the electrodeposition of indium and gallium has been investigated from both aqueous and non-aqueous electrolytes. Due to the negative standard reduction potentials of the two metals (E°In(III)/In(0) = −0.34 V and E°Ga(III)/Ga(0) = −0.53 V), their electrodeposition from aqueous electrolytes is hampered. This is especially true for gallium. In this talk, the electrodeposition of indium and gallium was investigated from several organic solvents. The investigated electrolytes are 1,2-dimethoxyethane (DME), polyethylene glycol (PEG), dimethyl sulfoxide (DMSO), and acetonitrile, containing chloride, bistriflimide, or methanesulfonate-based indium or gallium precursors.
The electrochemistry and the electrodeposition of indium and gallium was studied using various electrochemical methods in combination with quartz crystal microbalance (QCM) and rotating (ring) disk electrodes. DMSO-based electrolytes enabled the electrodeposition of indium at room temperature and above its melting point (159.6 °C), while DME electrolytes gave rise to gallium electrodeposits composed of small liquid gallium spheres (Fig 1). In all the investigated electrolytes, the formation of intermediate monovalent indium(I) or gallium(I) species during reduction and oxidation was demonstrated. These species are unstable and react away via disproportionation reactions. Yet, it was found that the extent of their formation and their stability depends on the nature of the electrolyte. In addition, the electrodeposition of indium antimonide (InSb) films and eutectic gallium indium (EGaIn) liquid metal lines and patterns will be discussed, as well as the electrochemical synthesis of spherical indium nanoparticles.
Influence of Cyclic Alkyl Carbonate Ring-Opening Processes on Electrode/Electrolyte Interphase Formation in Li-Ion Batteries
Authors: Gogoi Neeha , Berg Erik J. 
Published: February 2024

Cyclic alkyl carbonates, such as ethylene and vinylene carbonate (EC and VC), form solid electrolyte interphases (SEI) suppressing continuous solvent reduction at the graphite anode. There is a consensus that the choice of carbonate clearly affects SEI performance. VC has been observed to polymerize, forming poly(VC), but also to release major amounts of CO2,1,2 which are two seemingly contradictory processes. In this work, we present a detailed study of reaction pathways of EC and VC in typical Li-ion battery electrolytes. The rate of the decomposition reactions of these carbonates in presence of hydroxide is monitored using an injection cell coupled mass spectrometer at varying temperatures ranging from 30°C to 60°C. The activation energies from the Arrhenius relationship between the CO2 evolution rate and the cell temperature confirms that VC hydrolysis is autocatalytic rather than stoichiometric. Direct quantifications and comparisons of the solubilized reaction products will be done over varying times and temperatures with the help of in-situ nuclear magnetic resonance (NMR) and Raman spectroscopy that will help in clarifying the individual steps in the reaction process. The kinetic studies of EC and VC hydrolysis in model systems like this is an important step towards improving our understanding towards carbonates as there is always some trace amounts of hydroxides present in the cells. The complex interconversions and equilibria of these organic alkyl carbonates and oxides investigated herein, will add to the knowledge of interphase formation processes, and support the tailoring of electrolyte formulations in order to enhance performance of future Li-ion batteries.
References:
(1) Sasaki, T.; Abe, T.; Iriyama, Y.; Inaba, M.; Ogumi, Z. Formation Mechanism of Alkyl Dicarbonates in Li-Ion Cells. J. Power Sources
2005, 150 (1–2), 208–215. https://doi.org/10.1016/j.jpowsour.2005.02.021.
(2) Ota, H.; Sakata, Y.; Inoue, A.; Yamaguchi, S. Analysis of Vinylene Carbonate Derived SEI Layers on Graphite Anode. J. Electrochem. Soc.
2004, 151 (10), A1659. https://doi.org/10.1149/1.1785795.

Figure 1
Pushing the Energy-Lifetime Frontier of Li-Ion Batteries with Optimized Ni-Rich, Co-Free NMA-W Cathodes
Authors: Hamam Ines , Omessi Roee , Dahn Jeff R. 
Published: February 2024

Especially in the electric vehicle industry where both high energy density and long lifetime batteries are sought, Ni-based cathode materials such as LiNi1−x−yMnxCoyO2 (NMC) and LiNi1−x−yCoxAlyO2 (NCA) provide a fitting compromise in capacity and cyclability. In recent years, the high cost of cobalt in addition to the problematic geopolitics surrounding cobalt mining have motivated research efforts toward cobalt-free cathode materials.1 However, Ni-rich materials are subject to inevitable failure mechanisms such as microcracking and parasitic reactions with the electrolyte which are further aggravated with an increase in Ni-content and in the absence of Co.2 Many strategies have been proposed to overcome these challenges such as doping and/or coating the cathode particles,3 but there remains a need to further increase energy density with minimal compromise to lifetime.
In this work we present a cathode active material system designed to push Ni-rich and Co-free materials to the limit of their performance. This is done by choosing optimal polycrystalline particle size, a balance of Mn and Al content, and a sufficient amount of high-valence doping. Additionally, appropriate synthesis conditions are needed to obtain the desired morphology and infuse the intergranular boundaries with the W dopant. It is then important to choose an appropriate upper cutoff voltage during cycling to maximize energy while avoiding drastic crystal changes.4 This optimized NMA-W material system delivers specific capacity above 200 mAh/g while retaining 95% of its capacity without relying on any amount of Co.
The series of NMA-W materials presented in this work were characterized and tested. Scanning electron microscopy (SEM) images were used to observe morphology and crystallite growth after synthesis. X-ray diffraction (XRD) analysis was conducted to monitor the crystal parameters and accelerated rate calorimetry (ARC) was used to assess the thermal stability and safety of the material. Compression tests were also conducted to study the strength of the particles and their propensity to crack under stress.

Choi, J. U., Voronina, N., Sun, Y. K. & Myung, S. T. Recent Progress and Perspective of Advanced High-Energy Co-Less Ni-Rich Cathodes for Li-Ion Batteries: Yesterday, Today, and Tomorrow. Adv. Energy Mater.
10, 1–31 (2020).

Li, H. et al. An Unavoidable Challenge for Ni-Rich Positive Electrode Materials for Lithium-Ion Batteries. (2019) doi:10.1021/acs.chemmater.9b02372.

Yan, W., Yang, S., Huang, Y., Yang, Y. & Guohui Yuan. A review on doping/coating of nickel-rich cathode materials for lithium-ion batteries. J. Alloys Compd.
819, 153048 (2020).

Nam, G. W. et al. Capacity Fading of Ni-Rich NCA Cathodes: Effect of Microcracking Extent. ACS Energy Lett.
4, 2995–3001 (2019).