bluuebunny/crossref_metadata_2025 huggingface dataset:
Multiscale Safety Evaluation of Sodium-Ion: Safer Than Lithium-Ion?
Authors: Bates Alex Martin , Torres-Castro Loraine , Langendorf Jill , Johnson Nathan Brenner , Kustas Jessica , Rodriguez Mark , Rich Chaz
Published: December 2024

Sodium-ion technology is a promising alternative to lithium-ion cells due to lower materials cost and similar performance characteristics. The transition to commercialization of room temperature, rechargeable sodium-ion batteries is ramping up, with several products already on the market. However, the safety characteristics of sodium-ion cells are not well known. This talk will address the gap by presenting findings from safety testing conducted on commercially available 18650 sodium-ion cells composed of a NaNiMnFeO cathode and a hard carbon anode.

Safety testing included a range of temperature, mechanical, and electrical abuse conditions, including nail penetration, crush test, external short circuit, overcharging, and overtemperature. Furthermore, the heat flows associated with materials-level degradation and subsequent reactions were characterized through techniques including differential scanning calorimetry and thermogravimetric analysis. The thermal characterization was used to delineate the underlying reaction pathways and support explanations of the, sometimes, dramatic outcomes observed in 18650 safety testing.

Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Effects of Friction Stir Welding on the Structure and Protectiveness of Rust Layers Grown on Low-Alloyed Steels Under Cyclic Wet/Dry Corrosion Condition
Authors: Tsuchiya Hiroaki , Kobayashi Yuichiro , Kawakubo Takumi , Ushioda Kohsaku , Fujii Hidetoshi , Yamashita Masato , Fujimoto Shinji
Published: December 2024

Due to superior mechanical properties and low cost of steels, they are widely used as structural materials for infrastructure. However, steels are prone to corrode in atmospheric environments. Therefore, several alloying elements are added into carbon steel to improve atmospheric corrosion resistance. Arc welding has been widely used as a joining process for steel infrastructure, but segregation of solute elements occurs, leading to weld cracking and decreased corrosion resistance. Therefore, countermeasures have been desired. Friction stir welding, so-called FSW process is a solid-state joining technique that can prevent the segregation. In the present work, the effects of friction stir welding on the structure and protectiveness of rust layers on low-alloyed steel were examined.
Green Corrosion Inhibitor Based on Triazoles for Steel Reinforcement in Concrete Elements
Authors: Troconis de Rincon Oladis Marici , Escribano Jorge , Dacio Loreto , Alvarez Leonardo X. , Rincon Troconis Brendy Carolina
Published: December 2024

Reinforced concrete plays a crucial role in the construction of structures around the world. But these structures are frequently subject to corrosive conditions, which can affect their structural performance, shorten their useful life and cause failures with catastrophic consequences. The high pH of concrete stabilizes the formation of a passive oxide layer on the rebar. However, this protective film can be compromised if the threshold chloride concentration on the surface of the steel bar is reached, which can occur as the structure ages while exposed to chloride-containing environments. Considering the growing environmental concerns about the effectiveness of existing corrosion control methods, this study investigates the potential of 1-benzyl-4-phenyl-1H-1,2,3-triazole (BPT), an organic compound synthesized with an ecological and sustainable method, as a corrosion inhibitor for steel reinforcement in concrete.

The objective of this work is to evaluate the corrosion inhibition of BPT to protect reinforcing steel in simulated marine environments. BPT was initially evaluated in synthetic pore solution (SPS/8.33 g/L NaOH + 23.3 g/L KOH + 2.0 g/L Ca(OH)2, pH: 13.6) in presence of chlorides to determine its optimal concentration. Electrochemical techniques were used following the ASTM G180 standard and include: electrochemical impedance spectroscopy (EIS), linear polarization resistance, and cyclic anodic potentiodynamic polarization. Then BPT-containing mortar specimens were tested under accelerated exposure by simulated seawater spray (modified ISO 11474) using electrochemical techniques. Likewise, the physical-mechanical properties of the mortar were evaluated. The results demonstrate that BPT provides different mechanisms to inhibit rebar corrosion, including adsorption to steel (EIS results) and reduced mortar permeability (resistivity and capillary sorption tests). In addition, BPT increases the compressive strength of concrete.

This work highlights the effectiveness of a green corrosion control technology to extend the life of critical reinforced concrete structures, supporting a sustainable future.
Comparative Study of the Influence of Al & Mg Content on the Microstructure and Electrochemical Behaviour of Hdg Zn-Al-Mg Coatings
Authors: Malla Amar , Sullivan James , Penney David , Britton Daniel
Published: December 2024

Systematic investigations into the individual effects of increasing alloy additions of Mg and Al on the corrosion mechanisms of ZMA coating have demonstrated that microstructural phases and their surface distribution determine the anodic and cathodic behaviour of the coating. Increasing Al and Mg from 1 to 3 wt.% leads to an improved corrosion performance of the coating yet the improvement was greater for Al compared to Mg. Simultaneously increasing both Al and Mg to 3 wt.% again increased the corrosion performance. However, it was greater than 3 wt. % Mg but was lower the 3 wt.% Al.
Coupling of Offshore & Offgrid Wind Power & PtX-Processes, Supported by a MWh-Scale Battery for Safety, Stand-By Energy & PtX-Process Support
Authors: Peters Willi , Mariappan Sakthivel , Drillet Jean-Francois
Published: December 2024

A promising path for long-term energy storage is the production of e-fuels via Power-to-X processes (PtX). “Green” hydrogen is generated via water electrolysis and serves as a basic feedstock for the synthesis of chemicals and fuels such as methane, ammonia, methanol and other synthetic hydrocarbons. These fuels offer the advantage of an existing storage infrastructure and furthermore allow for the coupling of all energy sectors, e.g. transportation, industry, heating etc., to wind and solar power.

Within the German flagship project
H2Mare
the consortium
PtX-Wind
is developing experimental, research and production offshore & off-grid PtX platforms that are directly coupled to wind power. In case of wind calm, storm, maintenance and system failures, a CO2-free, electrochemical storage unit should provide enough energy for stand-by & emergency operation of electrolysis & PtX plants as well as for vital platform instruments. Furthermore, the battery should, if economically viable, support the PtX-plant operation due to wind power variability.

Together with industrial & academic partners the main task at the DFI focuses on dimensioning a battery storage system for a research PtX platform, comprising a 5 MW electrolysis unit & a 1.7 MW PtX-platform. Therefore, suitable battery technologies such as PbAc, PbGel, LFP, NMC and supercapacitors are being tested to verify battery properties provided by the manufacturer. The performance of some pre-selected candidates at module level (0.5 kWh, PbAc, PbGel, LFP) will be presented. Combined with a year-round wind farm power profile, the battery properties were implemented into the software “System Advisor Model (SAM)”1 and a minimal battery size (0.52 MWh) for the stand-by/emergency operation (0.47 MW) was determined, based on the 1C rate capability of state-of-the-art LFP batteries. Economic considerations on stand-by battery size will be presented, as well as a battery size for the improvement of PtX-plant productivity.

Literature: [1] Open source software website: https://sam.nrel.gov/download.html;
Biobased Proton Exchange Membrane Using an Anionic Nanocellulose System
Authors: Brito dos Santos Fernanda , Whitbeck Alex , Jalaee Adel , Gyenge Elod L. , Foster Johan
Published: December 2024

As integral parts of fuel cells, polymer electrolyte membranes (PEM) facilitate the conversion of hydrogen’s chemical energy into electricity and water. Such energy-conversion devices require stability, high ionic conductivity, and good water uptake and mechanical properties, while being cost-effective and sustainable. Nanocellulose membranes, which are promising materials for PEMs, present all the requirements except high ionic conductivity. The introduction of negative charges or other components such as nanoparticles or conductive polymers in the nanocellulose membranes structures is a promising solution to increase ionic conductivity in these bio-based materials. Here, our target is to understand how we can improve the ionic conductivity of nanocellulose materials while retaining thermal and mechanical properties. We produced negatively charged nanocellulose fibril (CNF) membranes (TEMPO-CNF and sulfonated-CNF) that present different functional groups and acidity (pKa COO-: ~3-4 and pka SO3-: ~7) which leads to differing ionic conductivities. We also studied the synthesis of these two nanocelluloses in a mixed membrane containing 1:1 TEMPO-CNF: sulfonated-CNF and how the membrane structure (porosity and thickness) impacts the ionic conductivity. All bio-based PEMs exhibited an impressive thermal stability up to 190 °C and high mechanical properties with a maximum Young’s modulus of around 1.15GPa, tensile strength of 0.18GPa, and storage modulus over 13GPa, as well as a high hydrophilicity with a water uptake as high as 6334%. These results are comparable to bio-based membranes mentioned in the literature and to commercially available membranes. Utilizing modified CNFs as a bio-based template for a commercial PEM would reduce costs, improve sustainability, and valorize cellulose through a new, high value application. The intrinsic renewability and tunability of cellulose-derived materials makes them promising candidates to meet the demands of novel sustainable energy solutions, and these bio-based membranes hold the potential for further enhancement through optimizing support structure materials, blend compositions, and production techniques.

Figure 1
Laser Molecular Beam Deposition of Halide Perovskite Solar Cell Materials: The Correlation between Preparation Conditions and Film Properties
Authors: Matsuki Nobuyuki , Sato Tomomasa
Published: December 2024

Halide perovskite solar cells (PSCs) have now developed to achieve conversion efficiencies of more than 26% [1], and the durability time for which PSCs do not suffer a loss in conversion efficiency has reached over 2300 hours [2]. The conversion efficiency of PSCs based on tin (Sn), which is lead-free, has also exceeded 14% and is improving further [3]. It is possible to find the key to improving various physical properties of PSCs by artificially controlling the atomic-level microscopic construction of the crystal structure and interfaces. From this perspective, we have applied laser molecular beam deposition (LMBD), which enables deposition control of organic and inorganic materials at the atomic level, to develop PSCs-related materials [4]. In this study, we investigate the correlation between the laser conditions and the physical properties of the films deposited by continuous infrared (IR) or ultraviolet (UV) pulsed laser deposition of PCSs-related materials.

LMBD of PCSs-related materials were conducted using the following process: on a synthetic quartz substrate placed in an ultra-high vacuum chamber a halide perovskite film was formed at room temperature or ~150 ºC by irradiating a semiconductor continuous infrared laser (wavelength: 808 nm) or an Nd:YAG Q-Switch quadruple wavelength UV pulsed laser (wavelength: 266 nm, 10 Hz) onto PbI2 and MAI, or CsPbBr3 material targets. The optical, crystalline, and electrical properties of the films were then characterized by UV-visible spectroscopy, X-ray diffraction (XRD), and I-V measurements, respectively.

Figure 1 shows the dependence of deposition rate on laser power density P
D for LMBD of CsPbBr3. Interestingly, the deposition rate reaches a maximum at approximately 5 W/cm2 with increasing P
D, before decreasing rapidly above this value. This suggests that the effective deposition rate is reduced due to the etching of the deposited surface by the ion bombardment of the laser ablation. Figure 2 illustrates the results of XRD peak intensity normalized by film thickness (red circle) and crystallite diameter (open diamond) estimated from the diffraction peak of CsPbBr3 (220) plotted as a function of P
D. This indicates that the orientation of CsPbBr3 (220) becomes more aligned with increasing P
D.

In this presentation, we will report details of the correlation between LMBD conditions and various properties of PCSs-related materials.

References

[1] H. Chen et al., Nature
613, 676 (2023).

[2] L. Xu et al., Small
19, 2207226 (2023).

[3] J. Zhao et al., Adv. Ener. Mater.
13, 2204233 (2023).

[4] K. Kawashima et al., Sci. Technol. Adv. Mater.
18, 307 (2017).

Figure 1
Exploration of New Lead-Free Organic-Inorganic Metal Halides for Photovoltaic Applications
Authors: Hirano Yuri , Klee Pia , Cordes David Bradford , Slawin Alexandra Martha Zoya , Payne Julia Louise
Published: December 2024

Organic-inorganic metal halides exhibit excellent compositional flexibility. When an ideal perovskite structure is adopted, they have the general formula ABX3, where A+
can be an organic or inorganic cation, B
2+ is an inorganic cation and X-
is a halide anion. By changing the A, B, and X sites, the crystal structure, electronic structure and band gap can be tuned for a variety of optoelectronic applications, such as solar cells, light-emitting diodes, and photodetectors. However, the toxicity of lead in these materials is undesirable for practical applications. Thus, lead-free organic-inorganic metal halides are being extensively explored.

In this study, we explored organic-inorganic metal halides based on the meta-xylylenediammonium (MXD) cation and a variety of trivalent metals. MXD contains an aromatic ring and is expected to improve stability in ambient conditions [1]. We succeeded in synthesising single crystals via a solution-based approach [2][3]. Based on single crystal X-ray diffraction, the structures were found to consist of isolated octahedra (or groups of octahedra) and are commonly referred to as zero-dimensional materials. We also investigated the tunability of the band gap due to halide substitution. As shown in Fig.1, the colours of samples change depending on the halogen content. Also, diffuse reflectance UV-visible spectroscopy clearly shows that the optical band gap is tunable. Here, we show the results of single crystal and powder diffraction, photoluminescence, scanning electron microscopy and ambient pressure photoemission spectroscopy to link the structure and optical properties of these new materials.

References

[1] I. Smith, E. Hoke, D. Solis-Ibarra, M. McGehee and H. Karunadasa, Angew. Chem. Int. Edi., 2014, 53, 11232-11235

[2] P. S. Klee, Y. Hirano, D. B. Cordes, A. M. Z. Slawin and J. L. Payne., Cryst. Growth. Des. 2022, 22, 6, 3815–3823

[3] Y. Hirano and J. L. Payne, in preparation, 2024

Figure 1
(Invited) Perovskite-Based Tandems: Perovskite/Si 2J and Beyond
Authors: Kim Jin Young
Published: December 2024

Perovskite/Si double-junction (2J) tandem solar cells are attracting interest due to their rapidly increasing efficiency. Their certified record efficiency (33.9%) has surpassed the theoretical limit efficiency of single-junction (1J) solar cells. In this presentation, recent research progresses in the high-efficiency and stable perovskite/Si 2J tandem researches done in our lab will be briefly introduced,[Kim et al., Science 368, 155 (2020); Ji et al., Joule 6, 2390 (2022)] and novel approaches to develop perovskite tandems beyond the perovskite/Si 2J tandems with record-high efficiencies, such as the perovskite/perovskite/Si triple-junction (3J) tandems,[Choi et al., ACS Energy Lett., 8, 3141 (2023)] perovskite/CZTSSe 2J tandems,[Hwang et al., Energy Environ. Mater., 7, e12489 (2024)] and perovskite/CIGS 2J tandems will be discussed.
(Invited) Advanced Electrodes and Carrier Transport Layers for Flexible/ Foldable Photovoltaic Devices and Modules
Authors: Choy Wallace C.H.
Published: December 2024

While the power conversion efficiency (PCE) of single-junction perovskite solar cells (PSCs) has increased to over 26%, there are some challenges to achieving flexible large-area PSCs with good long-term stability for practical applications. In this work, we demonstrate a self-assembled gradient Ti3C2Tx MXene incorporated PEDOT:PSS HTL for promoting flexible large-area PSCs by establishing half-caramelization-based glucose-induced MXene redistribution. Through this process, the Ti3C2Tx MXene nanosheets are spontaneously dispersed and redistributed at the top region of HTL to form the unique gradient distribution structure composed of MXene:Glucose:PEDOT:PSS (MG-PEDOT). Our results show that the MG-PEDOT HTL not only offers favorable energy level alignment and efficient charge extraction, but also improves the film quality of the perovskite layer featuring enlarged grain size, lower trap density, and longer carrier lifetime. Consequently, the power conversion efficiency (PCE) of the flexible device based on MG-PEDOT HTL is increased by 36% compared to that of pristine PEDOT:PSS HTL. Meanwhile, the flexible perovskite solar minimodule (15 cm2 area) using MG-PEDOT HTL achieves a PCE of 17.06%. The encapsulated modules show remarkable long-term storage stability at 85degC in ambient air (~90% efficiency retention after 1200 hours) and enhanced operational lifetime (~90% efficiency retention after 200 hours) [1]. With the adoption of the flexible transparent electrodes [2-5] and the introduction of a new modification on the perovskite active layer, the power-per-weight of our flexible PSCs reaches about 8 W/g while the power-per-weight of PEN/ITO-based control about 1-1.5 W/g. The work contributes to the development of flexible PSCs for practical applications.

[1] R. Zhang, W.C.H. Choy*, et al, Adv. Funct. Mater., 33, 2210063, 2023.

[2] J. Kim, W.C.H. Choy*, et al, Adv. Energy Mater., 10, 1903919, 2020.

[3] X. He, W. C. H. Choy*, et al, Adv. Funct. Mater, 2010764, 2021.

[4] J. Zheng, W.C.H. Choy*, et al, Energy & Environ. Sci., 16, 3770 2023.

[5] J.J. Kim, W.C.H. Choy*, et al, Nature Comm. DOI:10.1038/s41467-024-46243-6.
Improving Stability and Efficiency of Perovskite Solar Cells with Creatine-Based Passivation Methods
Authors: Min Jihyun , Park Taiho
Published: December 2024

Defects within perovskite structures can induce trap-assisted non-radiative recombination, leading to hastened degradation and a notable decline in device efficiency and stability. Consequently, mitigating these traps becomes pivotal for enhancing both efficiency and stability. In this investigation, we introduced (α-methylguanido)acetic acid, also known as creatine, employing two distinct approaches: (1) employing additive engineering for bulk perovskite passivation, and (2) implementing perovskite surface passivation via a capping layer atop the 3D perovskite. Intriguingly, in the surface passivation method, the formation of the 2D perovskite layer exhibited distinct characteristics compared to additive engineering. The formation of the 2D capping layer displayed a lower activation energy, feasibly facilitated by the preceding formation of the 3D perovskite layer. This 2D capping layer not only effectively transformed unstable defects on the perovskite surface into more stable 2D perovskite but also fine-tuned energy levels to enhance hole extraction capabilities. Consequently, the perovskite solar cell equipped with the creatine-based 2D capping layer showcased a remarkable power conversion efficiency (PCE) of 22.6% and sustained nearly 80% of its initial PCE over 250 hours under N2 conditions at room temperature. Furthermore, it retained 66% of its initial efficiency over 120 hours under N2 conditions at a thermal condition of 80 °C.
(Invited) Plasma-Tailored Nanocarbons As Advanced Electrodes for High-Frequency Supercapacitors
Authors: Marath Santhosh Neelakandan , Cvelbar Uros
Published: December 2024

Increasing demand for miniatured electronic devices with high power efficiencies and energy densities led to the exponential growth of electrochemical capacitors. Currently, the available electrochemical capacitors deliver the highest performance at direct current (DC), mainly in the low-frequency regions (less than 1 Hz) due to their electrode architecture and configurations. Therefore, using electrochemical supercapacitors in commercial applications is still in the initial phase. The use of such systems in large-scale electricity applications is also limited due to the insufficient response in the alternating current (AC). Considering that energy storage devices mostly deliver high performance at DC, it is crucial to design a device that responds to AC power sources which can sufficiently convert AC to DC for consumer needs. Therefore, the research interest in line-filtering supercapacitors is gaining attention nowadays. Such supercapacitors have been highly influenced by the design and architecture of the electrode material employed. Electrical conductivity of the electrode material, minimum contact resistance between the active material and current collector, thickness between 1-10 μm and microstructure design are critical for designing high-performing line filtering supercapacitors. Directly depositing the active material on the current collector without using polymeric binders is crucial for designing electrodes with such features. Among different deposition techniques, plasma-enhanced chemical vapour deposition stands out due to its advantages for designing nanostructures directly on substrates with different morphology, orientation, dimensions and thicknesses. This paper presents the advantage of plasma for the structure-controlled designing and tailoring of carbon nanostructures as advanced electrodes in supercapacitors for AC to DC line filtering applications. The plasma-deposited vertical carbon nanostructure electrodes achieved a capacitance of 430 μF in the high-frequency range (100 Hz) and displayed a phase angle of ∼ -80°. Besides, a prismatic prototype was designed to investigate the stability and filtering efficiency of the electrodes to convert AC to DC, which displayed a capacitance of 12 mF at 100 Hz with long-term filtering stability (above 3 h). The excellent filtering efficiency of supercapacitors made of plasma-designed carbon nanostructures opened up new paradigms to replace conventional aluminium electrolytic capacitors for high-frequency performances.
(Invited) Opportunities and Challenges in Fe-Based Layered Oxide Cathodes for Sodium-Ion Batteries
Authors: Lee Eungje , Park Jehee , Gim Jihyeon , Sunariwal Neelam , Tomich Anton , Vu Anh D. , Johnson Christopher S.
Published: December 2024

Sodium-ion batteries have received extensive attention in recent years with the growing demand for sustainable energy storage systems. As a low-cost alternative to lithium-ion batteries, achieving secure, economical, and diverse materials supply chains is necessary for the successful market penetration of the technology. This presentation will introduce research and development efforts at Argonne National Laboratory aimed at advancing sodium-ion batteries that are based on earth-abundant elements. Synthesis, structure, and properties of Nax(Ni,Mn,Fe)O2 layered cathodes will be presented and some key commercialization challenges and insights will be discussed.
Morphology-Dependent Reaction Kinetics in Synthesizing LiNiO2
Authors: Shi Chenguang , Brim Elliot , Richards Ryan , Lin Feng
Published: December 2024

High nickel cathode materials have captured global interest for their impressive capacity, although their structural transformation during synthesis remains ambiguous. In order to unravel Ni activation and lithiation behaviors at different levels, we initially synthesized high surface area precursors Ni(OH)2 and NiO. Given that high-temperature calcination, typically essential in these processes, can dramatically alter the morphology, we explored the possibility of lowering the calcination temperature as a strategy to preserve the initial morphology while transforming to LiNiO2, therefore ensuring decent electrochemical performance. Our comparative analysis of the lithiation processes for Ni(OH)2 and NiO revealed that although both undergo similar transformations, they occur at differing rates. Specifically, NiO converts into layered LiNiO2 more rapidly than Ni(OH)2, suggesting NiO allows for faster lithiation process than Ni(OH)2 at a lower temperature verified by spectroscopy and high-resolution microscopy techniques, contributing to the reasonably good battery performance of the final LiNiO2. Additionally, we examined the critical temperature necessary for complete lithiation and layered phase formation, considering the high surface areas of precursors, which could lower energy consumption during synthesis. Our insights provide a detailed understanding of the mechanisms behind layered structural transformation during synthesis, offering guidance for future improvements in high-nickel cathode material manufacturing.
(Invited) Strategies for Enabling Stable Cycling in High-Capacity Li-Ion Cathodes
Authors: Tong Wei
Published: December 2024

While significant advancements have been made with the prevailing layered oxide cathodes, there remains a need for the development of next-generation cathodes for high-energy Li-ion batteries to support the electrification needs of modern society. Li excess disordered rocksalt (DRX) cathodes present a promising avenue for achieving even higher capacities. However, this family of cathodes often faces a challenge in maintaining both high capacity and stable long-term cycling. Due to their structural flexibility, a wide range of compositional variations has been explored, including adjusting the Li/TM ratios, transition metal species, and anions. Through a deeper investigation into DRX chemistry, we have identified that the capacity and energy decay issues are influenced by the combination of transition metals and their respective redox chemistries. This presentation highlights our recent research efforts aimed at developing strategies to ensure stable, long-term cycling in high-capacity DRX cathodes using cost-effective and earth-abundant materials.
Electrodeposition of Tin Dioxide Films for Photoelectrochemical Water Splitting Applications
Authors: Płachta Małgorzata , Syrek Karolina , Kozieł Marcin , Zaraska Leszek
Published: December 2024

To address the rising pollution issues and the eventual depletion of non-renewable energy sources there is a growing focus on discovering clean, reliable, and sustainable energy alternatives. Tin dioxide, due to its conductivity, chemical stability, and wide band gap, is considered a promising material for various energy-related applications [1]. Among these, photoelectrochemical water splitting stands out as a highly promising technique for converting solar energy into storable chemical energy in the form of hydrogen. This approach can offer a renewable pathway for generating clean fuel. Multiple methods have been employed to produce tin dioxide films, including spray pyrolysis, sol–gel processes, thermal plasma deposition, pulsed-laser deposition, and electrodeposition [2]. Within this range of techniques, electrodeposition stands out for its simplicity and cost-effectiveness making it a prime candidate for large-scale production [3]. Therefore, the aim of the research was a comprehensive study of the electrodeposition of SnO2 films with a focus on their application in photoelectrochemical water splitting systems.

Nanostructured SnO2 films were successfully obtained by electrodeposition using various process conditions in an electrolyte containing tin(II) chloride dihydrate and nitric acid. The study explored the impact of deposition temperature and duration on the morphology, composition, and properties of the materials. Moreover, the influence of post-treatment variables including annealing time, temperature, and atmospheric conditions was thoroughly investigated. The crystal structure of the samples was analyzed using X-ray diffraction (XRD), while their morphology was examined via scanning electron microscopy (SEM). Furthermore, their photoelectrochemical activity was verified by recording the photocurrents under illumination with both monochromatic and simulated solar light. As a result, it was found that the surface morphology, thickness and photoelectrochemical performance of the deposited SnO2 layers are closely associated with the conditions employed during electrodeposition and post-treatment. Photoelectrochemical measurements demonstrated that the obtained tin dioxide films could possibly serve as electrodes in photoelectrochemical water splitting systems.

References

[1] Bhande, S. S., Taur, G. A., Shaikh, A. v., Joo, O. S., Sung, M. M., Mane, R. S., Ghule, A. v., & Han, S. H. (2012). Materials Letters, 79, 29–31.

[2] Rasouli, S. S., Najafisayar, P., & Hessam, R. (2023). Journal of Electronic Materials, 52(2), 896–906.

[3] Chen, X., Liang, J., Zhou, Z., Duan, H., Li, B., & Yang, Q. (2010). Materials Research Bulletin, 45(12), 2006–2011.

Acknowledgments

The authors acknowledge the financial support of the National Science Centre, Poland (Project no. 2018/30/E/ST5/00531)
Mass Transfer Limitation within Molecular Crowding Electrolyte Reorients Preferential (100) and (101) Texture for Dendrite-Free Zinc Metal Batteries
Authors: Wang Ziqing , Mullins Charles Buddie
Published: December 2024

Aqueous zinc metal batteries have significant potential for use in portable devices and large-scale energy storage systems.1 Nevertheless, the growth of zinc dendrites and parasitic reactions worsen the stability of zinc metal electrodes.2 Therefore, strategies must be found to prevent zinc dendrites and other unfavorable reactions. In this study, we develop a macromolecular crowding electrolyte (MCE) by using polyvinylpyrrolidone (PVP) as a crowding agent. The strong hydrogen bonds between PVP and H2O molecules effectively suppress water activity, resulting in an enlarged electrochemical stability window and wide operating temperatures (−20 to 50 °C). Furthermore, the adsorption of PVP on the electrode surface enables progressive nucleation in the MCE, providing promising reversibility and long-term stability during the zinc plating/stripping process. More importantly, the deep insights into Zn deposition morphology and crystallinity illustrate the crystallographic reorientation into (100) and (101) facets, exhibiting vertical and uniform zinc deposition. Density functional theory calculations confirm that the preferential exposure of crystal facets is due to the adsorption of PVP molecules on the zinc metal surface. Furthermore, the electrochemical tests employing a rotating disc electrode and a three-electrode system demonstrate the notable mass transfer limitation in the MCE, which mainly contributes to the reoriented zinc deposition. The vertical arrangement of deposited zinc is more beneficial than parallel deposition to contact the ions outside the depletion region to overcome mass transfer limitation in the MCE. As a consequence, the preferential zinc deposition by exposing (100) and (101) facets enables Zn/Zn symmetric cells to cycle for over 3000 hours at different current densities. Additionally, Na0.33V2O5/Zn and MnO2/Zn full cell batteries in MCE exhibit favorable cycling stability and capacity across a wide temperature range from −20 to 50 °C. This work unveils a unique approach to reorienting the preferential crystallography of deposited zinc, providing a new direction to regulate and control the favorable orientation of zinc deposition.

References:

C. Li et al. Joule
2022, 6 (8), 1733-1738.

Q. Zhang et al. Angew. Chem. Int. Ed.
2020, 59 (32), 13180-13191.

Figure 1
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
Electrodeposition of Metal Nanoclusters
Authors: Zamborini Francis , Thapa Binu
Published: December 2024

Here we describe the electrodeposition of Au nanoclusters in the 1-2 nm diameter range directly on indium tin oxide coated glass electrodes (glass/ITO) by reduction of Au ionic complexes in the presence of phosphine stabilizers. Anodic stripping voltammetry and UV-vis spectroscopy determines the size and coverage of the Au nanoclusters. The coverage is very large and the voltammetry and UV-vis confirm that the clusters range from less than 1 nm to 2 nm in diameter. The nanoclusters show low temperature and oxidative stability as expected for clusters of this size. They are also highly reactive to exchange with Ag and Cu ions to prepare metal alloy nanoclusters. With high coverage, small size, and ability to tune the metal composition, these clusters have strong potential applications for electrocatalysis related to energy applications.
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.
(Electrodeposition Division Research Award) Using Electrodeposition for Batteries and Electrocatalysis
Authors: Gewirth Andrew A.
Published: December 2024

In this talk we discuss activities leveraging electrodeposition to enhance batteries and electrocatalysis. In the area of batteries, we discuss how different electrolytes can enhance the electrodeposition of cations such as Mg2+. Ca2+, and Zn2+. A particular focus is the use of high concentration or solvate electrolytes, the structure of which can control the discharge process at the solid liquid interface. We show how different characterization techniques provide unique insight to battery-relevant electrodeposition properties. In the area of electrocatalysis, we discuss how electrodeposition can alter properties of different catalysts, yielding materials with enhanced activity. Examples from ammonia oxidation, oxygen reduction, and oxygen evolution will be presented. The work shows that beyond increasing active surface areas, electrodeposition can yield materials with properties such as altered d-band centers, and enhanced stability particularly with regard to oxidation.