bluuebunny/crossref_metadata_2025_split huggingface dataset:
Carbon Back Electrode Added SnO2 Nanoparticle for Scalable Multiporous-Layered-Electrode Perovskite Solar Cells
Authors: Shioki Takaya , Oishi Kouta , Matsumura Taiki , Tsuji Ryuki , Ito Seigo 
Published: December 2024

Fully printable carbon-based multiporous-layered-electrode perovskite solar cells (MPLE-PSCs) has long-term stability, because the thick carbon layer (~15 μm) can be protected the perovskite light absorption crystals from ambient water and oxygen [1-5]. This allows MPLE-PSCs to be manufactured in air, and scale-up is possible when used in conjunction with printing technologies. However, the power conversion efficiency (PCE) is lower than that of general thin-film type perovskite solar cells. To solve this problem, we need to introduce high-quality perovskite light-absorbing crystals inside the porous layer by controlling the permeation and crystallization process of the perovskite precursor solution. In this study, it was found that by mixing SnO2 in the mesoporous carbon electrode, the SnO2 acts as an inorganic binder and helps the perovskite precursor solution to penetrate. MPLE-PSCs with a sub-module size of 15.17 cm2 active area were also fabricated using this SnO2-mixed carbon electrode.
In order to fabricate MPLE-PSCs, a hole blocking layer (compact-TiO2) layer was deposited on the FTO (fluorine-doped SnO2) glass substrate by the spray pyrolysis method. Then, electron transport layer (mesoporous TiO2), insulation layer (mesoporous ZrO2) and hole transport layer/back contact electrode (mesoporous carbon) were coated by screen printing method. Finally, the perovskite precursor solution ((HOOC(CH2)4NH3)0.05(CH3NH3)0.95PbI3, 1.2 mol/L in γ-butyrolactone) was dropped and annealed to complete the MPLE-PSCs [1].
Analysis of the pore size distribution of the carbon electrode, contact angle, and elemental distribution in the cross-section of the MPLE-PSCs showed that mixing SnO2 changed the morphology of the carbon electrode and allowed the perovskite precursor solution to penetrate throughout the mesoporous electrode. The PCE of MPLE-PSCs mixed with SnO2 was found to be 11.02 % at the optimum ratio (15 wt% SnO2 to carbon powder). Furthermore, the PCE of a sub-module fabricated with the same material achieved 9.03 %. This value represents a significant improvement by 22.9 % compared to the pristine-carbon case.
[1] A. Mei, et al., Science
345, 295 (2014).
[2] R. Tsuji, et al., Electrochemistry
88, 418 (2020).
[3] R. Tsuji, et al., Photonics
7, 133 (2020).
[4] D. Bogachuk, et al., Carbon
178, 10 (2021).
[5] E. Kobayashi, et al., Cell Rep. Phys. Sci.
2, 100648 (2021).
On Identifying Crossover Induced Self-Discharge of Non-Aqueous Redox-Flow Batteries and Ketazin Based Redox-Active Species
Authors: Fricke Sebastian , Krämer Susanna , Sowa Karin , Winter Martin , Gruenebaum Mariano 
Published: December 2024

Redox flow batteries (RFB) are a promising technology for storing electrical energy in the grid because of their high scalability, design flexibility, long-term efficiency and durability. Hence, great efforts have been invested in this area of research. Especially in regards of organic redox-active species (RAS) a wide variety of different molecular design approaches have been examined. While many of these RAS are convincing due to their simple synthesis and cheap raw materials (cheap production) as well as high redox potentials (high cell voltage), high redox reversibility and low crossover tendency (high long-time stability), or high solubilities (high capacity), only a few can combine all these requirements for an optimal RAS.
In this work, we therefore present the functional group of ketazines (see Figure 1) as basis for organic RAS potentially exceeding previous organic RAS in RFB performance. With its simple two-step synthesis, easy variation of functionalization and low-cost raw material, this functional group offers not only high variability but also adaptability to specific NARFB (non- aqueous RFB) needs. This functional ketazine group is exemplary shown by the molecule AMAP here (see Figure 2).
In addition, we present a simple experimental procedure that can be used to analyse crossover rates of an RFB system (i.e. RFB cell structure, electrolyte composition and separator / membrane). To this end, we have developed a crossover mass transport concept that allows qualitative and quantitative crossover investigations. Using this experimental route, it is shown how different operating parameters within a specific RFB setup (e.g. RAS concentration, RAS structure, type of separator / membrane, ...) can influence the crossover behaviour of the RAS, and thus the resulting capacity loss. In this way, the comparability of different RFB systems can be improved and the best combination of RFB cell structure, electrolyte composition and separator/membrane for most efficient long-term charge-discharge cycling can be selected.

Figure 1
Diameter and Morphology of Colloidal-Silica-Abrasives Depending on Surfactant Concentration with Amine-Functional Group
Authors: Park Jea-Gun , Jeon Min-Uk , Kim Pil-su , Kim Ju-Yeon , Jin Hyeong-Ju , Ahn Ho-Jun , Park Jin-Hyung 
Published: December 2024

As the design rule of logic semiconductors has been scaled down to 5, 3, 2.1, 1.5, and 1.0 nm, the line width of Cu film used as interconnect lines in logic semiconductors has also been rapidly reduced to 36, 32, 24, 20, and 16 nm. The CMP (Chemical Mechanical Planarization) of these Cu lines is a crucial fabrication process, posing challenges in achieving E.O.E (Edge Over Erosion), as well as minimizing dishing and erosion during the CMP of Cu films. Specifically, the E.O.E in the CMP of Cu films is primarily influenced by the diameter and morphology of colloidal silica abrasives in the CMP slurry. In a conventional synthesis method synthesis of colloidal-silica-abrasives, the diameter of colloidal-silica-abrasives could be obtained by adjusting the precursor concentrations such as TEOS, alcohol, and alkali catalyst. It has been reported that the effect of precursor concentration and the presence of a carboxylic acid-functionalized surfactant, specifically ethylene-diamine-tetraacetic acid (EDTA), on the morphology of colloidal silica abrasives.
Therefore, in our study, we designed a novel synthesis method for colloidal silica abrasives by incorporating a charged functional group surfactant into the conventional synthesis process of colloidal silica abrasives. The effect of the surfactant having the positive charged amine functional group (i.e. Triethanolamine: Tri-ETA, Ethylenediamine: EDA, Diethylenetriamine: DETA, Triethylenetetramine: TETA) were estimated as function of the number of amine functional group in the surfactant, as shown in Fig. 1. When the number of positive charged amine functional groups increased 0 to 4, the diameter of colloidal-silica-abrasives increased from 67.2 to 143.86 nm and the solid loading of colloidal-silica-abrasives increased from 2.0 to 2.2 wt%. In addition, the synthesis with positive charged amine functional group was transformed from cocoon shape to spherical shape. We will present the changes in colloidal silica abrasive morphology as the concentration of amine functional groups, as well as the distinctions between amine and carboxyl funtuonal group. Moreover, we intend to provide a thorough investigation into the mechanisms underlying each synthesis.

Acknowledgement

This research was supported by the MOTIE(Ministry of Trade, Industry & Energy (1415180388) and KSRC(Korea Semiconductor Research Consortium) (20019474) support program for the development of the future semiconductor device, and by the Brain Korea 21 PLUS Program and the Samsung Electronics’ University R&D program.

Figure 1
Influences of the Aqueous Electrolyte Composition and the Deposition Parameters on the Electrodeposition of Nickel-Rhenium Alloy
Authors: Omar Nurul Amanina Binti , Dombrowe Scott , Koester Frank , Lampke Thomas 
Published: December 2024

Rhenium is used as an alloying element for many special materials in high-temperature applications, such as turbine blades, catalytic converter, and thermocouples. These applications require a high melting temperature of the materials, which can be achieved by a small amount of rhenium in the alloy. Rhenium has the second highest melting temperature after tungsten at 3186 °C [Naor et al., 2009]. Furthermore, at high temperatures, rhenium has a good resistance to creep and fatigue as well as to chemical reactions that occur in this temperature range. Due to its scarcity on earth and the resulting high prices, a broad application of rhenium using conventional manufacturing processes such as primary shaping like casting is not economical. [Naor et al., 2010]
A resource-conserving and economical process, on the other hand, is galvanic deposition, in which the required application-dependent properties can be produced in the form of a thin layer on inexpensive components. Rhenium can be electroplated from aqueous solutions, but only with poor current yields of around 10 %. With the aid of co-deposition of nickel, the current yield can be increased to approx. 90 % in laboratory scale. With the nickel-rhenium alloys depositions, rhenium deposition rates of up to 70 wt% could be realized. Furthermore, the layer properties can be influenced by the electrolyte composition and the process parameters.
The deposited Ni-Re layers were characterized using scanning electron microscopy-EDX, laser scanning microscopy and Vickers microhardness testing.
Kinetics and Stability of Sustainable Indium Alkaline Electrodeposition
Authors: Carrea Davide , Piccinni Marco , Friedman Gary , Colombara Diego 
Published: December 2024

Indium is widely utilised for the fabrication of CuIn1-xGaxSe2 (CIGS) based solar cells1,2. Such devices are constituted by thin layers of various materials stacked on top of each other, one of which is the CuIn1-xGaxSe2 absorber layer itself. Cu-In-Ga alloys as absorber precursors can be obtained using cathodic electrodeposition of each separate elemental layer from three distinct galvanic baths containing Cu2+, In3+, and Ga3+ ions, respectively.
State-of-the-art indium galvanic baths display low faradaic efficiency. Being mostly acidic or neutral, these baths are affected by the hydrogen evolution reaction under highly cathodic potentials. The most known alternative to enhance faradaic efficiency is to employ non-aqueous media 3–5.
In this study, we present a sustainable alkaline galvanic bath yielding smooth In electrodeposits. Alkaline conditions naturally hinder hydrogen evolution, but favour strong precipitation of In2O3 and In(OH)3. Here, we solved this conundrum by identifying competitive organic compounds capable of complexing In3+, thus avoiding the formation of such precipitates. Moreover, we carried out potentiometric titration experiments to identify the stoichiometry of the coordination compounds.
This galvanic bath was formulated, characterized and stabilized for alkaline pH. The faradaic efficiency was assessed and the deposition kinetics explored using coulometric techniques on rotating disk electrodes (RDEs). We are currently investigating the deposition mechanism in detail and plan to leverage the acquired knowledge to further optimize the deposition process.

Acknowledgements

This work was supported in part by the Italian Ministry of Foreign Affairs and International Cooperation”, grant number US23GR17. REMAP6 has received funding from the European Commission PathFinder open programme under grant agreement No. 101046909. Funded by the European Union. Views and opinions expressed are however those of the author(s) only and do not necessarily reflect those of the European Union or European Innovation Council and SME Executive Agency (EISMEA). Neither the European Union nor the granting authority can be held responsible for them.

References

J. Zhou and C. Li, in E3S Web of Conferences,, vol. 267, EDP Sciences (2021).

L. Thouin, S. Massaccesi, S. Sanchez, and J. Vedel, Formation of copper indium diselenide by electrodeposition, p. 81–88, (1994).

W. Monnens, C. Deferm, K. Binnemans, and J. Fransaer, Physical Chemistry Chemical Physics, 22, 24526–24534 (2020).

R. Piercy and N. A. Hampson, The electrochemistry of indium, p. 1–15, (1975).

S. Zein El Abedin et al., Electrochim Acta, 52, 2746–2754 (2007).

https://re-map.eu/
Mitigating Anodic Reactions in Water-in-Salt Electrolytes for Refractory Metal Electrodeposition
Authors: McBride Michael , Rutledge Amanda , Hooks Daniel E 
Published: December 2024

The use of water-in-salt electrolytes has been a transformational advancement in electrochemistry. Water-in-salt electrolytes rely on a super high concentration of salts in aqueous electrolytes to lower the activity of water. The water is occupied in the solvation of the salts, leaving minimal ‘free water’ in the system. In the context of electrodeposition, this results in a widened cathodic window as the limited quantity of protons suppresses the hydrogen evolution reaction (HER).
Seldom discussed is the impact on anodic reactions that are also limited by the transport of water for the oxygen evolution reaction (OER). Lithium chloride (LiCl) has been used as a cost effective and readily available support salt in water-in-salt electrolytes. However, in this system OER competes with chlorine evolution. At low pH chlorine evolution is more thermodynamically and kinetically favorable. This reaction depletes the system of chlorine atoms required to solvate excess water and saturates the electrolyte with dissolved chlorine. As a result, the electrolyte has a limited lifetime.
One solution to this problem is the use of proton exchange membranes to separate the anode from the cathode. The use of these membranes will be discussed focused on our interest in rhenium (Re) electrodeposition. Rhenium has traditionally been difficult to deposit by electrolysis from aqueous solutions due to the over potential for hydrogen evolution and complex electrochemical reactions. Further, many intermediate rhenium oxides catalyze HER, so maintaining a stable water-in-salt electrolyte is crucial.
Herein, we present systematic studies investigating various proton exchange membranes in an H-cell confirmation on the electrodeposition of rhenium. Perfluorosulfonic acid and hydrocarbon polymer backbones are explored, both with sulfonic acid functional groups. As these membranes are semipermeable, membrane thickness is also explored. Both volume changes in the two H-cell components and pH are monitored as a function of time. The impact on the morphology and electrodeposition kinetics of rhenium will be presented as a function of membrane properties.
Anomalous Electrodeposition of Palladium – Antimony Alloys
Authors: Freydina Evgeniya , Monroe Jeffrey C. , Hilty Robert D. 
Published: December 2024

Electrodeposition of Pd-Sb alloy was studied in tartrate – ammoniacal electrolytes. Unlike any other known binary plating system, the resulting alloy was typically obtained with anomalously constant composition of about 30 wt.% antimony in a large process window. Factors like concentrations of Pd and Sb in solution, current density, temperature and agitation only slightly affected the Sb content in the deposit.
The alloy exhibits several practical properties. As plated, it has a nanocrystalline structure and a moderate compressive stress of about 13 ksi (90 MPa). It is harder than pure palladium with typical Vickers microhardness of 550-650 HV10 and has good wear durability and corrosion resistance.
The plating process produces unexpectedly uniform composition and properties on the substrates with the most intricate shapes. Meanwhile, plating thickness tracks with local current density fluctuations we expect on a complex shaped part.
Cyclic voltammetry provides some insight into the unusual co-deposition of palladium and antimony. Additional data on the structure of the electrolyte and the deposit are presented.
Figure 1. A part coated with Pd-Sb alloy. The Sb content (wt.%) is uniform around the surface of the part.

Figure 1
Adsorption of Organic Molecules at Solid-Electrolyte Interface – the Effect of the Electrolyte and Electrode Structure
Authors: Pikma Piret , Ers Heigo , Siinor Liis 
Published: December 2024

Understanding processes at the molecular level at the solid-liquid interface is essential to improving and developing novel technologies in electrochemistry, molecular electronics, catalysis, corrosion inhibition, electrodeposition of metals, formation of composite layers, and energy storage devices. Self-assembled monolayers (SAMs) play a significant role in many of those applications and their improvements [1-2]. At the same time, the characteristics of SAMs depend on many aspects, like the characteristics of individual molecules forming the monolayer, the interactions between these molecules, SAM interactions with the electrolyte, the crystalline surface of the substrate, etc.
The adsorption of bipyridines resulting in the formation of various nanostructures at the electrode surface has been studied in both aqueous electrolytes [2-5] and, more recently, in IL medium [6-8]. The adsorption of bipyridines is of interest as it offers insight into the interactions which drive the formation of self-assembled monolayers. This is due to aromatic nitrogen-containing heterocycles, which facilitate the possibility of interacting with the surface or other molecules through nitrogen lone electron pair, π-π stacking or hydrogen bonds.
To this day, the universal understanding that the adsorption of organic molecules results in the formation of an ordered monolayer is based on the phenomenon observed in mainly aqueous solutions. However, the conception might not be straightforwardly transferrable to the organic additive + ionic liquid | electrode interface. For example, the existence of an interfacial multilayer structure of pure IL ions in contrast with an aqueous electrolyte has been previously shown in both experimental and computational studies. Furthermore, it has been shown that in ILs, if the ions form rigid layers on the electrode, it is necessary to apply an overpotential for interfacial restructuring.
This work compares the adsorption of 4,4′-BP and 2,2′-BP at the interfaces between various metal single crystal electrodes (Sb, Bi, Au, Cd) and aqueous or ionic liquid electrolytes. The adsorption process has been studied by applying scanning tunnelling microscopy, electrochemical impedance spectroscopy and cyclic voltammetry methods. Based on the comparison, similarities and differences between aqueous and ionic liquid as electrolytes will be pointed out. Additionally, the influence of the physical and chemical properties of the various metal single crystal electrodes will be discussed.
[1] D. R. MacFarlane, et al., Energy Environ. Sci. 7, 232–250 (2014)
[2] N.V. Plechkova et al., Chem. Soc. Rev. 37, 123–150 (2008)
[3] Pikma et al., Electrochem. Commun. 2015, 61 (Supplement C), 61–65.
[4] H. Ers et al., Electrochim. Acta 2022, 421, 140468.
[5] H. Ers et al., J. Electroanal. Chem. 2021, 903, 115826.
[6] L. Siinor et al., Electrochem. Commun. 2013, 35, 5–7.
[7] L. Siinor et al., J. Electroanal. Chem. 2014, 719, 133–137.
Advancements in Analyzing Organic Additives in Electroplating Baths: A Focus on Electrochemical Impedance Spectroscopy (EIS) Coupled with Distribution of Relaxation Times (DRT)
Authors: Giurlani Walter , Verrucchi Margherita , Bonechi Marco , Zangari Giovanni , Innocenti Massimo 
Published: December 2024

Organic additives play a crucial role in upholding the quality of metallic coatings within commercial electroplating baths. However, their effectiveness diminishes over time due to degradation and drag-out. Continuous monitoring and precise dosing are imperative to uphold optimal concentration levels, preserving both technical integrity and aesthetic appeal. Traditional chromatographic techniques are impractical for routine industrial analysis due to the complex formulation and synergistic effects of various additives. Electrochemical methods, such as the Hull cell test and Cyclic Voltammetric Stripping (CVS) measurements, are commonly employed to adjust additive concentrations based on their impact on the electrodeposition process. Although widely utilized, the Hull cell test relies on trial and error and operator experience, providing only qualitative assessments. CVS, which measures changes in the rate of copper deposition to reflect additive concentration, may not be universally suitable for all electroplating baths due to their varying complexities.
Prior Electrochemical Impedance Spectroscopy (EIS) investigations on copper plating baths have qualitatively linked impedance changes with aging [1]. Our objective was to quantify additives using EIS. To achieve this, experimental data were analyzed in terms of resistive and capacitive components to calculate the distribution of relaxation times (DRT) via Lasso regression [2]. The resulting data were subjected to multivariate analysis to address this challenge.
The promising outcomes [3] render this method highly appealing in both industrial and academic contexts. Its application in the galvanic field is particularly advantageous for gaining insights into the function of individual additives, their interactions, and the aging process of plating baths.
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] C. Gabrielli et al., J. Appl. Electrochem. 2008, 38, 457–468.
[2] A. Piccioni et al., J. Phys. Chem. C 2023, 127, 7957–7964.
[3] M. Verrucchi et al., J. Electroanal. Chem. 2024, 954, 118045.
Electroplating Zirconium from Low Temperature Deep Eutectic Solvents
Authors: Stull Jamie A , De Silva Umanga , Janusz Jordyn , Jones Ben 
Published: December 2024

High temperature coatings such as zirconium are highly desirable in several applications due to their high melting point, corrosion resistance, and low neutron cross section. As such these materials are commonly used in nuclear reactors and the chemical processing industry. Due to the reduction potential of zirconium typical aqueous electroplating methods are not feasible. Physical deposition methods are possible but are limited to thin coatings (1-5 mm) and difficult for complex geometries and through holes. To achieve thicker conformal coatings molten salt electroplating is commonly employed. This method requires high temperatures (600-700°C) and complex experimental set-up that can accommodate the high temperatures and exclude water and oxygen.
Our team is developing low temperature (80-100°C) electroplating solvents based off deep eutectic chemistry. These solvents are low cost and low hazard. We have explored different deep eutectic solvents (DES) using choline chloride as the hydrogen bond acceptor. The hydrogen bond donor has been varied, ethylene glycol and urea are examples that have been explored. We have completed electrochemical (cyclic voltammetry) and solubility studies of multiple supporting electrolytes (LiF, LiCl, etc.) and zirconium metal salt. Preliminary electroplating results will also be presented.