bluuebunny/crossref_metadata_2025 huggingface dataset:
Comparing the immediate effects of different neural mobilization exercises on hamstring flexibility in recreational soccer players
Authors: D’souza Cyanna Joseph , Rajasekar Sannasi , Shetty Ruchit L.
Published: February 2024

Background: Hamstring strain injuries remain a challenge for both athletes and clinicians given the high incidence rate, slow healing, and persistent symptoms. Increased tension in the neural structures is a known causative factor for hamstring tightness for which neural mobilization has emerged as a significant adjunct to routine stretching techniques.

Objective: To compare the short-term effects of neural sliding and neural tensioning on hamstring length in male recreational soccer players with hamstring tightness.

Methods: Sixty-two participants between ages 18 and 30 years were randomly assigned to one of the two groups viz. neural sliding or neural tensioning. Participants in either group performed the given stretching protocol in three sets. The Active Knee Extension Test (AKET) and Sit and Reach Test (SRT) were recorded before intervention, immediately after intervention, and after 60[Formula: see text]min. between- and within group-analysis was done using analysis of variance.

Results: Between-group analysis showed that neural tensioning was more effective than neural sliding in improving hamstring length on both measures, however this difference was negligible. Within-group analysis demonstrated that the mean post-test scores on the AKET test and SRT were significantly greater than the pre-test scores in both groups ([Formula: see text]). A reduction in the post-test scores was observed after 60 min, irrespective of the type of stretching ([Formula: see text]).

Conclusion: There was no difference in short-term effects of neural sliding or neural tensioning on hamstring flexibility in male recreational soccer players. Both groups showed improved flexibility immediately after the intervention with reduction in the effect after 60[Formula: see text]min.
Erosion rate investigation and multi-objective optimisation on electrical discharge machining of Ti64 using deep cryo-treated electrodes
Authors: Tharian B. K. , Dhanish P. B. , Manu R. , Oza Ankit D. , Kaur Kirtanjot
Published: February 2024

Due to its inherent properties, Ti64 has set many challenges in industries during its machining using conventional machining processes. Traditional machining of Ti64 is not a feasible option considering the economic and environmental perspectives. Non-conventional techniques like electrical discharge machining (EDM) are promising methods for machining Ti64 despite challenges like higher tool wear and lower machining rates. The current paper investigated the erosion rates while machining Ti64 using deep cryo-treated electrodes. The peak current (Ip), pulse on time (Ton) and gap voltage (Vg) were used as control parameters while investigating erosion rates, viz., Material Removal Rate (MRR) and Tool Wear Rate (TWR). Experiments were planned according to the RSM-based Central Composite Design (CCD). Considering the multi-objective nature of the current problem, Grey Relational Analysis (GRA) has been incorporated to find a single parametric condition that will satisfy both MRR and TWR. Peak current, [Formula: see text][Formula: see text]A, Pulse On time, [Formula: see text][Formula: see text][Formula: see text]s and Gap voltage, [Formula: see text][Formula: see text]V was found to be the optimal setting giving [Formula: see text][Formula: see text]mm3/min and [Formula: see text][Formula: see text]mm3/min. Furthermore, topographical analysis of the EDMed surfaces has been performed using SEM, XRD and 3D optical profilometry techniques to characterise the surface and to investigate the possibility of other intermetallic compounds formed on the machined surface.
Characterization of High Zinc Al-Zn-Mg-Cu Alloy By Electrochemical Noise and Current Transient Measurements
Authors: Kumar Ankur , Chaudhari Gajanan , Nath S.K
Published: February 2024

Electrochemical noise (EN) method and current transient measurements have been used in to characterize metastable pitting in high zinc Al-Zn-Mg-Cu alloy. The outcomes are evaluated against those from scanning electron microscopy and atomic force microscopy. Results of transient electrochemical analysis and image analysis are compared and explained based on heterogeneity of microstructures arising from presence of different precipitates.
Anodic Oxide Layers on Aluminum-Lithium Alloy
Authors: Navas Diaz Shirley , Dick Luis F. Frederico
Published: February 2024

Al-Cu-Li alloys regained attention with Cu as the major addition and Li around 2 %wt. However, oxide blistering of is frequently found by the sulfuric acid anodizing of these alloys, which has been sometimes attributed to Li-rich precipitate dissolution or to thermomechanical stresses in the anodic oxide layer. In this work, anodic layer properties (composition, morphology, pitting resistance) were studied in dependence of anodizing process parameters. Blisters form by higher anodizing charges, independent of the applied current density and its density increases at lower temperatures, at which the anodizing efficiency is higher. Blistering cannot be associated to second phase precipitates, as their diameters (100-200 µm) are much larger than the precipitates size. The 45º-cracks at the mid section of the porous film are typical of compressive stresses perpendicular to the growth direction, indicating that blistering is possibly caused by a higher molar volume compared to other Al-Cu alloys.
Novel Battery Concepts Based on Semi-Solid Electrodes: The Injectable Battery
Authors: Muñoz-Torrero Castaño David , Borlaf Mario , Pérez-Antolín Daniel , Ventosa Edgar
Published: February 2024

Energy storage systems are present in our day-to-day life in portable devices or electric vehicles amongst others, being Li-ion batteries the technology that dominates the market due to its high energy and power densities. However, the increasing battery demanding requirements together with the concerns related to the availability of materials such as Co or Li, have brought much attention towards innovative battery concepts such as redox flow batteries or batteries based on semi-solid electrodes (SSEs). In particular, SSEs, which are dense slurries that are made of active and conductive materials and electrolyte in the absence of binder, offer some advantages in comparison to conventional electrodes. SSEs can reach higher mass loading than conventional electrodes increasing the battery areal capacity.[1] Their properties can be easily tuned by changing the ratio between active material, electrolyte and conductive material. In addition, the lack of binder confers to SSEs flowability and plasticity. These features make SSEs a promising type of electrodes for a wide range of battery application.

This contribution will focus on the properties of SSEs and their application in batteries. In the first part of this contribution, recent progress on two innovative battery concepts based on SSEs will be presented: the easily-recyclable injectable battery (Figure 1a) and the shape-conformable injectable batteries (Figure 1b). The former concept is based on the fabrication of a cell leaving cavities to be filled with SSEs in a subsequent step. Once the end-of-life is reached, SSEs are dejected, having the entire cell ready to be injected with fresh SSE. In the latter concept, 3D printed injectable batteries are fabricated with complex shapes by combining additive manufacturing and SSEs. In the second part of the contribution, essential developments of analytical techniques for the study of intrinsic properties of SSEs will be discussed. It should be noted that the special features of SSEs, which can be easily tuned by adjusting their formulation, require specific tools to study their properties. Several specially designed cells for investigating various properties of SSEs will be disclosed.

Acknowledgments

This work has received funding from the Spanish Ministry of Science and Innovation and NextGenerationEU (TED2021-131651B-C21). This work was also supported by the Regional Government of Castilla y León (Junta de Castilla y León) and by the Ministry of Science and Innovation MICIN and the European Union NextGenerationEU / PRTR

References

[1] D. Muñoz-Torrero, J. Palma, R. Marcilla, E. Ventosa, Al-Ion Battery Based on Semisolid Electrodes for Higher Specific Energy and Lower Cost, ACS Appl. Energy Mater. 3 (2020).

Figure 1
Modified Solid Electrolyte Interphases with Alkali Chloride Additives for Aluminum-Sulfur Batteries with Enhanced Cyclability
Authors: Xu Cheng , Liu Xu , Passerini Stefano
Published: February 2024

Al-S batteries are promising energy storage devices, employing high-capacity and low-cost Al (2980 mA h g-1, 8050 mAh cm-3) and sulfur (1672 mAh g-1) as the anode and cathode, respectively. However, Al-S batteries suffer from the notorious shuttle effect of polysulfides as other intensively investigated metal-sulfur batteries. Up to now, several strategies have been proposed to improve the poor reversibility and lifespan of Al-S batteries. At the cathode side, materials that can adsorb polysulfides have been employed as the host material of sulfur to reduce the dissolution of polysulfides,1,2 e.g., heteroatom-functionalized and/or hierarchical porous carbonaceous materials, metal-organic frameworks (MOFs), boron nitrides, and Mxenes.3,4 Nonetheless, AMAs, which also play an important role in the shuttle process, have received little attention up to now. Suitable engineering of electrolytes enabling an electronically insulating solid electrolyte interphase (SEI) on AMAs may suppress the deposition of low-solubility Al2S3 and/or short-chain polysulfides further promoting the cell cycling performance.

Herein, alkali chlorides are, for the first time, proposed as electrolyte additives to modify the SEI on AMAs and suppress the polysulfide shuttle in Al-S batteries.5 It is demonstrated that adding NaCl to the conventional [AlCl3]1.3[EmimCl]1 electrolyte can enhance the cyclability of Al-S batteries by forming a thicker, NaxAlyO2-containing SEI layer on AMAs. In addition to NaCl, LiCl and KCl as electrolyte additives also lead to improvement of Al-S batteries’ lifespan. These findings provide a new path to suppress the detrimental polysulfides shuttle effect in Al-S batteries, resulting in their improved cycle performance.

References

(1) Smajic, J.; Wee, S.; Simoes, F. R. F.; Hedhili, M. N.; Wehbe, N.; Abou-Hamad, E.; Costa, P. M. F. J. Capacity Retention Analysis in Aluminum-Sulfur Batteries. ACS Appl. Energy Mater.
2020, 3 (7), 6805–6814.

(2) Zhang, Y.; Ma, L.; Tang, R.; Zheng, X.; Wang, X.; Dong, Y.; Kong, G.; Zhao, F.; Wei, L. The Host Hollow Carbon Nanospheres as Cathode Material for Nonaqueous Room-Temperature Al–S Batteries. Int. J. Hydrogen Energy
2021, 46 (7), 4936–4946.

(3) Guo, Y.; Jin, H.; Qi, Z.; Hu, Z.; Ji, H.; Wan, L. J. Carbonized-MOF as a Sulfur Host for Aluminum–Sulfur Batteries with Enhanced Capacity and Cycling Life. Adv. Funct. Mater.
2019, 29 (7), 1–6.

(4) Wang, Z.; Zheng, X.; Chen, A.; Han, Y.; Wei, L.; Li, J. Unraveling the Anchoring Effect of MXene-Supported Single Atoms as Cathodes for Aluminum−Sulfur Batteries. ACS Mater. Lett.
2022, 4, 8, 1436-1445.

(5) Xu, C.; Diemant, T.; Liu, X.; Passerini, S. Modified Solid Electrolyte Interphases with Alkali Chloride Additives for Aluminum–Sulfur Batteries with Enhanced Cyclability. Adv. Funct. Mater.
2023. 2214405.
Inkjet Printed Ti3C2 Electrodes for Anode-Free Zinc-Ion Battery
Authors: Gibertini Eugenio , Montanelli Vittorio , Bussetti Gianlorenzo , Magagnin Luca
Published: February 2024

Additive manufacturing techniques are coming to the fore in many technological fields as cheaper and more versatile manufacturing routes alternative to the physical deposition methods. In particular, when miniaturized, thin-film or patterned structures are needed, Inkjet printing (IJP) has been widely demonstrated as suitable techniques to fabricate coated electrodes and microdevices for many applications including energy storage 1. In this regard, Zinc-ion batteries (ZIBs) are a promising alternative to the traditional lithium-ion batteries due to the abundance and low cost of zinc. In ZIBs, a metallic Zn chips is usually employed as the anode and a variety of materials, such as metal oxides or polymers, as the cathode. Zinc-ion batteries have the potential for high energy density and long cycle life, however they suffer of the well-known issue of Zn dendritic growth and poor efficiency of the plating-dissolution process 2. Ti3C2 MXene have been recently demonstrated as a high-performance “zincophilic” substrate for smooth and efficient zinc with high reversibility 3,4.

In this work, we investigate inkjet-printed Ti3C2 MXene thin coatings as an ideal substrate for anode-free ZIBs. Stable aqueous Ti3C2 MXene inks were formulated and successfully inkjet printed on different substrates. The zinc metal nucleation phenomena on MXene 2D sheets were investigated by electrochemical potentiodynamic polarization techniques as well as galvanostatic ones, comparing them to a zinc metallic foil. Ex-situ electron scanning microscopy (SEM) analyses were employed to observe the plated Zn morphology after cycling at both low and high current density. Taking advantage of the smooth inkjet-printed Ti3C2 MXene coatings, electrochemical atomic force microscopy (EC-AFM) was used for the first time to perform in-operando investigation of the Zn plating process, allowing to reveal the early stage Zn plating mechanism on the as-printed

Bibliography

C. Li, F. Bu, Q. Wang, and X. Liu, Advanced Materials Interfaces, 9, 2201051 (2022).

K. Wang, ACS Omega, 5, 10225–10227 (2020).

J. M. Park et al., Journal of Energy Chemistry, 76, 187–194 (2023).

Z. Gong et al., Journal of Colloid and Interface Science, 625, 700–710 (2022).
Improved Iron Flow Battery Designs for Low-Cost Grid Storage
Authors: Jayathilake Buddhinie Srimali , Ivanovskaya Anna N. , Overland Alexandra E. L. , Chandrasekaran Swetha
Published: February 2024

To achieve grid-scale energy security through widespread deployment of flow batteries we need to rapidly advance low-cost, scalable, and durable technologies. Even though, earth-abundant iron-based technologies offer low-cost storage solutions projecting levelized cost for storage >$0.05/kWh, durability is yet a major issue hindering the commercialization.Hybrid nature of the system is also another barrier to achieve energy-dense scalable systems compared to all soluble flow batteries. Our present study focuses on understanding the factors affecting long-term durability of the full-cell device and overcoming them by improving electrolyte properties, key reactor components including membrane separators and electrode structures and the kinetics of metal deposition/ dissolution process.

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Funding was provided by Lawrence Livermore National Laboratory Directed Research and Development (LDRD) Grant 22-DR-014. IM release number: LLNL-ABS-847140.
Impact of Power Electronic Converter Ripples on Vanadium Redox Flow Batteries
Authors: Dutta Oindrilla , Wittman Reed M , Mueller Jacob
Published: February 2024

The worldwide effort to decarbonize the electricity grid has made battery energy storage system (BESS) an essential technology. A promising technology for long duration storage on the grid is Vanadium Redox Flow Batteries (VRFBs), which can support the grid by regulating peak load, reducing intermittency of large-scale renewables, and as emergency power supply. There are two primary methods of integrating a BESS to the grid. Frist, the BESS is directly connected to the DC-link of a DC-AC converter that interfaces with the grid. Second, the BESS is connected to a DC-DC converter that in turn interfaces with the DC-link of a DC-AC converter. These converters all have a characteristic ripple voltage and current during operation. The magnitude and frequency of the ripples depend on topology and switching frequency of a converter, controller design and protocol, type of connection to the grid, voltage magnitude and load characteristics. Currently, studies on the impact of ripples have been limited to Lithium-ion and Lead-Acid batteries. The impact of ripple current and voltage has not been studied in VRFBs. In a VRFB, potential impact includes excessive gassing of hydrogen and carbon corrosion of the bipolar plate and porous electrode and cell heating. To better integrate and operate VRFBs to the electricity grid, the impact of ripples needs to be studied in detail.

Using a novel experimental platform, where both magnitude and frequency of ripples will be incorporated, we will emulate the performance of different power electronic converter configurations. It will comprise standard 5cm2 VRFB cells with a carbon felt electrode and Nafion ion exchange membrane. The various converter ripples in an electricity grid setting will be emulated by superimposing the signals from a potentiostat (constant current) and a high frequency transformer (modulated ripples), which will be connected to the cathode of the cells.

The experimental testbed will be used to cycle the VRFB cells at various states of charge with ripples that emulate the performance of power electronic converters during grid operations and disturbances. Varied parameters will include ripple amplitude, ripple frequency, electrolyte flow rate, applied current density and state of charge. Measurement data from monitoring voltage of each electrode, cell voltage and current, gas generation, electrolyte crossover and electrolyte loss will be analyzed to determine the impact of ripples on VRFB cells. Finally, the cells will be monitored for signs of gas generation and postmortem signs of carbon corrosion.

Our analysis will determine the impact of various ripple magnitude and frequencies on VRFBs in a simulated grid integration environment. This work will facilitate the development of design standards for power electronic converters that are intended for battery applications, while also informing future efforts to optimize VRFB cell and stack performance.
Techno-Economic Optimization of Flow Batteries Using the Optimization Potential to Prioritize Different Optimization Possibilities for the Development of Industrial Scale Applications
Authors: Gerlach Daniel , Noack Jens , Dev Rabin Siva , Davaasuren Ganzorig , Roznyatovskaya Nataliya , Trupp Sabine , Pinkwart Karsten
Published: February 2024

The challenges of climate change are becoming more and more relevant to society. This also increases the need for a wider use of renewable energies, which, due to their fluctuating availability, also increases the need for the possibility of intermediate storage in other forms of energy. Flow batteries (FB) have the advantage that they store electrical energy chemically in electrolytes and are scalable in terms of power and energy. To achieve a successful broad market entry of FBs, not only the technical performance but also the economic efficiency of the system is important. Known FBs must therefore be optimized techno-economically for specific applications. In this regard, not every technically possible improvement has the same positive impact on the economically relevant performance or the energy-related specific costs.

Therefore, an existing techno-economic model [1] based on a 10 kW / 120 kWh Vanadium FB (VFB) was further developed and a standardized laboratory scale FB was defined for further research which only differs in the used electrolyte. Based on extensive validation measurements using standardized test cycles, VFBs and organic FBs (MV/TEMPOL and AQDS/BQDS) in different molarities were analyzed and compared with this model.

The component-wise sensitivity analyses of that model show battery-specific optimization potentials. With those techno-economically appropriate optimizations can be planned.

The additionally developed stand-alone software, into which the model was transferred, can simulate various aqueous flow batteries, which offers versatile application possibilities. Additional areas relevant to the evaluation, such as infrastructure and financing costs, can also be included. Upscaling of simulated FBs to industrial application is also possible. In this talk, some results of this techno-economic approach will be presented.

[1] J. Noack, L. Wietschel, N. Roznyatovskaya, K. Pinkwart, and J. Tübke, Energies, 9, 627 (2016).

Figure 1
Stress Corrosion Cracking of Copper in Humid Bentonite Powder
Authors: Fujimoto Shinji , Miyabe Sayaka , Tsuchiya Hiroaki
Published: February 2024

Copper is one of the candidate materials for over pack of nuclear waste geological disposal. Overpack would be exposed to hot oxygenated humid atmosphere in the initial stage of disposal, because air introduced during burying operation. In the present work, the authors examined the corrosion behavior of copper, which is contact with bentonite powder in humid environment.

Specimens were prepared from oxygen-free pure copper sheets. The surface was ground

with SiC papers up to #2000 and then mirror-finished with alumina suspensions. Bentonite powder (Kunigel VI; Kunimine Ind., Co., Ltd.) was exposed to an air of 63, 75 and 80 % relative humidity at 60 ℃. Th bentonite power absorbs water, but is still keeping powder fluidity.

The cupper specimens was buried in the humid bentonite power to observe behavior of corrosion, and also the Slow Strain Rate Testing (SSRT) was performed in the humid bentonite powder.

Cathodic stripping voltammetry of specimens immersed in the humid bentonite power showed

two peaks derived from copper oxide and copper sulfide to reveal thickness of corrosion products. Tarnish rupture type SCC of cupper was also confirmed by SSRT in the humid bentonite powder. In this presentation, correlation between properties of corrosion products and SCC susceptibility will be discussed.
(Invited) Earth-Abundant Cathode Active Materials: Research and Development on Mn-Rich Oxides
Authors: Croy Jason R. , Gutierrez Arturo , Chen Jiajun , Mallick Subhadip , Kwok Chun Yuen , Balasubramanian Mahalingam , Vu Anh , Lee Eungje , Shi Boyu , Tewari Deepti , Srinivasan Venkat , Gim Jihyeon , Thackeray Michael M
Published: February 2024

The United States Department of Energy (DoE) has recently released its vision for the future of batteries in the United States, titled The National Blueprint for Lithium Batteries. This document outlines the key areas of investment most critical to enabling a more secure and independent ecosystem around lithium-based batteries for the U.S. and is heavily influenced by the ideas of sustainable technological development. In this regard, earth-abundant cathode active materials are particularly attractive.

Although Ni is considered an earth-abundant element and it plays a critical role in high-performance vehicle applications, concerns over Ni demand and the stability of supply chains have already surfaced and the cost-effectiveness of high-Ni cathodes could remain an issue. In addition, the environmental impact of increased Ni processing to meet demand, specifically of low-grade ores, should be addressed.

Mn is substantially more abundant in the earth’s crust than Ni or Co and significantly less expensive. In addition, Mn has a rich history and still promising future in energy storage applications.1

This presentation will explore research and development efforts within the DoE’s Vehicle Technologies Office ‘Deep Dive’ program, Earth-abundant Cathode Active Materials (EaCAM), led by Argonne National Laboratory. This seven-lab consortium is focused on enabling new designs in high Mn, low Ni, Co-free cathodes towards diversifying the portfolio of viable materials for commercial applications.

1. A. Gutierrez, D. Tewari, J. Chen, V. Srinivasan, M. Balasubramanian, and Jason R. Croy, Earth-Abundant, Mn-Rich Cathodes for Vehicle Applications and Beyond: Overview of Critical Barriers, 2023 J. Electrochem. Soc.
170030509DOI 10.1149/1945-7111/acbee4
Organic Coating for Oxide Removal on Copper Surfaces
Authors: Kaur Jashanpreet , Singh Vikram , Li Yuanjiao , Liberati A.C. , Asadiankouhidehkordi Golnoush , Moreau Christian , Aloisio Mark , Crudden Cathleen , Mauzeroll Janine
Published: February 2024

The oxidation of copper surface decreases the surface functional quality, which can be detrimental for several industrial applications. The objective of my research project is the one-pot reduction of copper oxides on copper surfaces, followed by the formation of a stable coating composed of organic molecules that prevent further oxidation. The organic coating will be deposited using four approaches: immersion, resonant acoustic mixing, vapor phase deposition, and electrochemical deposition. By applying mentioned deposition methods, preliminary tests were performed and further characterized by using X-ray photoelectron spectroscopy (XPS) and matrix assisted laser desorption ionization (MALDI), which confirmed the presence of organic molecules on the copper surface. To obtain best coating, optimization is being done by varying various parameters such as concentration of organic molecule solution, time of immobilization, solvent type and influence of temperature. After achieving an optimal coating, next step forward is to conduct bulk corrosion studies to understand the real effect of the coating. Protecting copper surfaces in such a manner can extend the lifetime of copper surfaces, thereby saving resources, time and money in target industrial applications.

Figure 1
N-Heterocyclic Carbene Based Nanolayer for Copper Film Oxidation Mitigation
Authors: Gross Elad
Published: February 2024

The wide use of copper is limited by its rapid oxidation. Main oxidation mitigation approaches involve alloying or surface passivation technologies. However, surface alloying often modifies the physical properties of copper, while surface passivation is characterized by limited thermal and chemical stability. Herein, we demonstrate an electrochemical approach for surface-anchoring of an N-heterocyclic carbene (NHC) nanolayer on a copper electrode by electro-deposition of alkyne-functionalized imidazolium cations. Water reduction reaction generated a high concentration of hydroxide ions that induced deprotonation of imidazolium cations and self-assembly of NHCs on the copper electrode. In addition, alkyne group deprotonation enabled on-surface polymerization by coupling surface-anchored and solvated NHCs, which resulted in a 2 nm thick NHC-nanolayer. Copper film coated with a NHC-nanolayer demonstrated high oxidation resistance at elevated temperatures and under alkaline conditions.The ease of preparation and well-controlled growth process of electrochemically-induced NHC nanolayer make it an easily-applicable method for large-scale coating to provide thin and effective passivation layer for copper surfaces. Moreover, the electro-induced mechanism of NHC-nanolayer formation makes it possible to selectively deposit the protective layer on conducting copper wires without changing the optical properties of the entire device. These advantages make the presented technology highly suitable for applications that require high transparency, such as solar cells and electroluminescence devices.
(Invited) Effect of Carbonaceous Materials on the Performance of Supercapacitors
Authors: Singhal Rahul
Published: February 2024

Carbonaceous materials such as carbon blacks, activated carbons, multi walled/single walled carbon nanotubes (CNTs), graphene oxide (GO), reduced graphene oxide (rGO), and biochar are found to be useful for energy storage applications because of their large specific surface area, high conductivity, high mechanical strength, good thermal stability, and low cost.

In order to optimize the concentration of MWCNT in MnO2/MWCNT nanocomposite, we have synthesized MnO2/MWCNT nanocomposite with varying concentration of MWCNT such as pure MnO2, 1mg/ml, 4 mg/ml, and 10 mg/ml MWCNT in reaction mixture. The samples were identified as MnO2, M-CNT 100, M-CNT 400, and M-CNT 1000. From cyclic voltammetric studies at various scan rate, we plotted a graph between peak current () versus the scanning rate () and found that the slope of anodic (cathodic) peak for MnO2, M-CNT 100, M-CNT 400, and M-CNT 1000 were found to be 0.48 (0.42), 0.70 (0.61), 0.60 (0.54), and 0.52 (0.47), respectively. We also found that at a current density of 0.5 A/g, pure MnO2 has a specific capacitance of 124 F/g. The addition of MWCNT initially increases the specific capacitance to 145 F/g for M-CNT 100 nanocomposite; however, at the 400-mg and 1000-mg concentrations the specific capacitance decreases to 135 F/g and 102 F/g, respectively.

Besides this, we have also studied the effect of binder on capacitive performance of MnO2/CuS/rGO samples and found that the specific capacitance of the composite materials increased upon decreasing the binder. The detailed results of our recent investigations on carbonaceous materials for supercapacitor applications will be presented at 244th ECS meeting.
Optimization of Laser-Induced Graphene Electrodes for High Voltage Micro-Supercapacitors
Authors: Zaccagnini Pietro , Reina Marco , Arcoraci Davide , Baudino Luisa , Serrapede Mara , Pedico Alessandro , Molino Davide , Martellone Simone , Bianco Stefano , Lamberti Andrea
Published: February 2024

With the development of grid-based distributed sensing with low-power electronics, the need for delocalized power supplies, Energy Storage Devices (ESDs) are moving toward miniaturized scales. Among ESDs, micro-supercapacitors (µSC) are currently under development as an alternative or complementary power supply/backup to batteries. Laser-induced graphene (LIG) is an emerging technology based on the laser conversion of polymers into graphene-based conductive materials. Polyimide (PI) is the most investigated polymer, moreover, it finds several applications in the electronics field. Laser scribing of polymers fastens the device processing reducing the number of wet chemistry steps carried out to fabricate micro-devices.

PI Kapton foils of 125 µm thickness were used as substrate materials to produce LIG samples. A CO2 laser was exploited to convert polymeric samples and to pattern hard masks to print devices of optimized geometry and material properties. Further, electrodeposition processes can be used to increase the material capacity by depositing transition metal oxides with pseudocapacitive features. Among them, maganese oxide can be electrodeposited anodically without recurring to any thermal step. Tuning the LIG storage mechanism, and combining them, allows several degrees of freedom to design devices able to work in organic electrolyte environments in voltage windows ranging from 2.5 V up to 4.5 V. Moreover, optimization of electrode charges allows for improving the overall device lifetime and energetic efficiency.
Resolving the Dependence of Aluminum Alloy Corrosion on Grain Orientation by Scanning Electrochemical Cell Microscopy
Authors: Li Yuanjiao , Mauzeroll Janine , Morel Alban
Published: February 2024

The study of grain-dependent corrosion behaviors of practical polycrystalline metals remains challenging due to the influences of other microstructural features, such as intermetallic particles and grain boundaries. In this work, we employed the oil-immersed scanning electrochemical cell microscopy (SECCM) to investigate the effect of grain orientations of a practical aluminum alloy AA7075-T73 on the surface electrochemical behaviors. Thousands of spatially resolved microscopic potentiodynamic polarization (PDP) measurements were performed, allowing the extraction of information only from grain interior areas excluding intermetallic particles and grain boundaries. The differences in the corrosion behaviors between grains were revealed. Cathodic currents exhibited a strong grain orientation dependence with a decreasing order of {101} > {001} > {111}, agreeing with the prediction from the order of atomic planar density. By contrast, the dependence of anodic currents on grain orientation was weak, and pitting was independent of grain orientation, which could be due to the limited mass transport of ions within the surface oxide film. This work highlights the capability of oil-immersed scanning electrochemical cell microscopy in resolving small electrochemical differences, which will greatly promote the study of grain-dependent behaviors of practical polycrystalline samples.
Minimize Surface Change for Corrosion Study Using a Chronopotentiometric Approach Method in SECCM
Authors: Zhou Hu , Morel Alban , Mauzeroll Janine
Published: February 2024

In the realm of single-channel scanning electrochemical cell microscopy (SECCM), two primary methods are utilized for approaching the micropipette onto the substrate surface, specifically the chronoamperometric and chronopotentiometric methods. The chronoamperometric method is typically employed in corrosion studies utilizing SECCM, although it has been observed that negative approach potentials can influence subsequent microscale electrochemical measurements as a result of cathodic degradation of the metal oxide film. In this study, we investigated the practicality and stability of utilizing the chronopotentiometric approach method in SECCM-based corrosion research, and we found that the metal surface change during the approach process can be reduced by applying a 0 A approach signal, allowing for the acquisition of primitive electrochemical information of the surface.
Understanding the High Scan Rate PDP Curves Obtained By Seccm
Authors: Zhou Hu , Morel Alban , Mauzeroll Janine
Published: February 2024

Scanning electrochemical cell microscopy (SECCM) is progressively employed for investigating corrosion behaviors at localized sites on metal surfaces. Normally, hundreds of potentiodynamic polarization (PDP) measurements are conducted on the sample using a high potential scan rate to reduce the experimental duration. However, polarization curves obtained under such conditions would yield inaccurate Tafel kinetics. In this research, we performed PDP measurements on Al sample at various scan rates using SECCM and obtained reproducible results. The experimental polarization curves were successfully simulated by a high field model that accounted for the cathodic contribution from oxygen reduction reaction and the anodic contribution from Al oxide film growth. By utilizing this model, we were able to extract the true corrosion kinetic properties from the high scan rate polarization curves, which has not been reported previously. This study represents a significant contribution towards enhancing SECCM-based micro-polarization as a robust quantitative technique for corrosion study.
Operando Neutron Diffraction Analysis of Commercial Positive Electrodes of Lead Batteries
Authors: Hussey Daniel Seth , Rodriguez-Gomez Miguel , Larrea Arbaizar Angel , Campo Javier , Orera Alodia , de la Fuente Fernando , Valenciano Jesus , Fricke Holger , Chen Yan , Yu Dunji , An Ke
Published: February 2024

We have analyzed by operando neutron diffraction the charge/discharge crystallographic transformation processes inside the positive active mass (PAM) of industrial lead batteries, getting information onthe spatial distribution of the phases. Our study was focused on the positive electrode because it is there where the main limitations to the charge/discharge efficiency are originated. The experiments were carried out in the VULCAN instrument at the Spallation Neutron Source of the Oak Ridge National Laboratory (Tennessee, USA) using the volume gauge technique. VULCAN is a high brightness time-of-flight diffractometer which provides fast volumetric mapping and, therefore, the possibility to study kinetic behaviors. Accordingly, both static and dynamic mapping experiments were performed during charge-discharge cycles, comparing fresh and cycled cells. The diffractograms obtained were analyzed using VDRIVE and GSAS software, together with dedicated Python scripts. In addition to compositional maps (Figure 1), information on lattice parameters, crystallinity, stoichiometry and hydration was also obtained as a function of the state of charge. Local inhomogeneities and differences in the behavior between fresh and cycled cells were observed. Moreover, we have used the Pb signal from the positive grid as internal calibrating element to obtain the absolute molar concentration of the component phases, comparing the PbSO4 PbO2 transformation with the effective charge driven by the cell during charge and discharge processes. The b-PbO2 mass utilization during the C5 100% to 20% discharge was about 0.3. In the same way, the charge factor was estimated to about 70%, from the start of charging until the PbO2 concentration reaches a near flat regime, and about 5% after reaching the flat regime. Giving for the full charging cycle a value about 50%.

As far as we know, this is the first time that diffraction information has been obtained from inside commercial thick electrodes (3.4 mm in thickness) during real operation conditions, mapping the PbO2 and PbSO4 evolution in a 2.24 cm x 7.2 cm region of the positive electrode.

Figure 1
Exploring the Mechanisms Driving Thermal Growth of Copper Oxide Nanowires
Authors: Kosicek Martin , Zavašnik Janez , Baranov Oleg , Šetina Batič Barbara , Cvelbar Uros
Published: February 2024

Copper oxide nanowires have gained attention in the scientific community due to their potential in a wide range of applications, including gas sensing, solar cells, energy storage, photocatalysis, and as antibacterial agents. Despite significant research on their thermal growth, the underlying mechanism remains unresolved, and the exact experimental conditions required for their growth are still unknown. To address these knowledge gaps, we conducted thermal oxidation of copper under various conditions and analyzed the resulting nanowires using electron microscopy techniques. Our study aimed to understand the processes occurring inside the copper oxide layers, which serve as the starting point for nanowire growth, as well as the driving force behind the one-dimensional growth of nanowires. Additionally, we explored the effects of experimental conditions on the microstructure of the copper oxide layers and nanowires. Our findings indicate that chemical processes inside the oxide layers are influenced by copper and oxygen concentration gradients, with oxygen concentration being the key factor in determining the prevalent copper oxide phase. Moreover, the microstructure of both the oxide layers and nanowires is affected by stress and defects in the oxide layers. We found that twin boundaries in the CuO grains are the main reason for the unidirectional elongation of nanowires. Our research provides important insights into the mechanisms driving the thermal growth of copper oxide nanowires, which can aid in their synthesis and applications in various fields.
Release of Redox Additives Via Megasonic Energy for High Selectivity/Low-Stress STI CMP
Authors: Caridi Adam T. , Cahue Kiana A. , Keleher Jason J.
Published: February 2024

The advancements in a wide array of semiconductor manufacturing processing have been pivotal for the extension of Moore’s law the Chemical Mechanical Planarization (CMP) process has become an area of focus due to the stringent surface topography requirements. CMP utilizes complex slurry formulations containing abrasive nanoparticles and additives to reduce substrate defectivity and achieve angstrom-level uniformity. One area that has gained significant attention is Shallow Trench Isolation (STI), where the modulation and control of the surface oxidation state of the ceria, specifically the Ce3+ state, is critical to TEOS removal. In the Ce3+ state, defect states (i.e., oxygen vacancies (Ovacs)) on the surface are highly electron deficient (i.e., electrophilic) and allow the nucleophilic substrate to complex. By modulating the electrophilic properties of the particle, the kinetics of surface complexations required for effective TEOS removal can be controlled. This work focuses on developing stimuli-responsive capsules that can be added to STI slurry formulations to promote the controlled release of redox-active additives that can be used to drive the oxidation state of the CeO2 nanoparticle (Ce3+/Ce4+). By encapsulating the additive in a polymeric system, the reactive properties of the slurry are limited until the additive is released. In this work, megasonic action was employed to disrupt the capsules releasing the additives on demand to facilitate the modulation of the CeO2 surface redox states. Results have shown that the addition of a controlled-release capsule with an additive resulted in the increase of Ovacs at the CeO2 surface. This led to an increase from 1800 Å/min to 3450 Å/min using a constant 2.0 W/cm2 continuous flow megasonic flux. Furthermore, the overall defectivity decreased significantly with respect to both particle contamination and surface scratching. Lastly, the nature of the polymeric capsule has been shown to enhance selectivity between TEOS and silicon nitride and preliminarily appears to be megasonic flux dependent.
Effect of Cu Pad Geometry and Dishing in Cu/Sicn Hybrid Bonding Process: A Finite Element Analysis Study
Authors: PARK So-Yeon , Kim Cha-Hee , Oh Gwang-Sik , Yun Young Su , Kang Jiho , Kim Sarah Eunkyung , Lee Won-Jun
Published: February 2024

The Cu/dielectric hybrid bonding is a face-to-face wafer bonding technology that utilizes the thermal expansion of the Cu pad embedded in dielectrics. It is receiving significant attention due to the advantage of achieving high interconnect density through submicron-level fine-pitch bonding. The finite element method (FEM) is beneficial for hybrid bonding research because it provides insight on the bonding mechanism by simulating the expansion of the Cu pad with increasing temperature. The effects of pad shape and dishing by chemical-mechanical polishing (CMP) were studied by FEM for fixed dimensions of Cu pads, 4 or 10 μm in size and 0.5 μm in thickness [1] [2]. However, studies on the hybrid bonding process for Cu pads with finer dimensions and various geometries using FEM analysis are currently lacking.

In this study, we simulated the Cu/SiCN hybrid bonding process using ANSYS to investigate the effects of Cu pad geometry and Cu dishing by CMP. The diameter and thickness of the circular Cu pad were ranging from 0.1 to 1.5 μm and 0.15 to 0.45 μm. The Cu dishing depth was varied between 2 to 5 nm. For bonding process, at first the dielectrics of the two wafers were in contact with each other at room temperature. Then, the temperature was raised to the annealing temperature to simulate the Cu-to-Cu bonding process. At different annealing temperature, the bonding area was estimated with varying diameter, thickness, and dishing depth of the Cu pad. The Cu-to-Cu bonding area was mapped according to the Cu pad geometry, and the geometry of the Cu pad suitable for hybrid bonding was proposed. The protrusion of the Cu pad caused by the thermal expansion was also investigated for a single wafer to discuss the effect of the Cu pad dimension on the bonding area.

Acknowledgments This work was supported by SK hynix Inc.

References [1] Y. Beiliard et al., International Journal of Solids and Structures 117, 2017, pp.208 [2] C. Sart et al., 6th Electronic System-Integration Technology Conference (ESTC), 2016, pp. 1
(Invited) In-Operando ftir Study on the Redox Behavior of Sulfurized Polymers As Cathode Material for Li-S Batteries
Authors: Pereira Rhyz , Rafie Ayda , Fafarman Aaron , Kalra Vibha
Published: February 2024

Sulfurized polymers are an attractive cathode active material, promising to overcome the intransigent polysulfide shuttle effect sulfur cathodes face via the anchoring of sulfur by a carbon-sulfur (C-S) bond. Both sulfur-diisopropenylbenzene copolymers (SDIB) and sulfurized polyacrylonitrile (SPAN) contain C-S bonds which should function in this way, however, their performance in ether electrolytes still exhibit capacity fade associated with the polysulfide shuttle. We investigate this anchoring effect using in-operando ATR-FTIR spectroscopy to develop a molecular level understanding of the polysulfide speciation reaction in sulfurized polymers and cathode level molecular changes. We find that in SDIB copolymers with sulfur wt % of 80 and 30 wt %, the C–S bond is not active in the voltage window of Li–S batteries (1.8-2.6V vs Li/Li+).

In SPAN, however, we found that the C-S bond is active in the typical voltage window (1-3V vs Li/Li+) contributing to the evolution of polysulfide species in electrolyte with low concentrations of lithium nitrate (LiNO3), however this effect is mitigated when higher concentrations of LiNO3 are used. We attributed the mitigation of the polysulfide shuttle to the formation of a cathode electrolyte interface (CEI), composed of lithium fluoride, established via ex-situ XPS studies on cycled cathodes. Additionally, we observed the reversible behavior of the C-S bond in IR at ~680 cm-1 in electrolytes with high concentration of LiNO3, as opposed to the irreversible behavior of the bond in electrolyte with low concentrations of LiNO3. Moreover, we observed the lithiation of the cyclized PAN backbone, identified by the elimination of the aromatic region of the IR spectrum after the first cycle.
(Invited) Electrochemistry in a Lab of the Future
Authors: Bridges Craig A. , Prasad Thapaliya Bishnu , Sun Xiaoguang , Al-Najjar Anees , Rao Nageswara , Nycz Andrzej , Walters Alex , Meyer Luke , Dai Sheng
Published: February 2024

Advanced research laboratories are producing ever more data and introducing more advanced methods of data analysis and feedback to control these laboratories. These "labs of the future" are intended to revolutionize the way that research is done, enabling in some cases the exploration of higher dimensional problems and better research outcomes. At ORNL, the Autonomous Chemistry Laboratory (ACL) is being developed as a self-driving laboratory to accelerate materials discovery and innovation. A combination of robotic tools are being integrated with computational tools to analyze reaction results and predict optimal directions for future investigation. We have developed an electrochemical workstation integrated with materials synthesis and discovery. The capabilities and concept for the ACL will be presented.
(Invited) Evaluating Urban Water-Energy Systems Based on UN Sustainable Development Goals (SDGs)
Authors: Khandan Nirmal
Published: February 2024

Evaluating Urban Water-Energy Systems Based on UN Sustainable Development Goals (SDGs)

Water, food, and energy are three of the major resource issues facing the world today. To help address these issues, urban wastewater is now being considered as a renewable resource than as a waste- a resource for water, for energy, and fertilizers. It is now well recognized that the traditional urban wastewater infrastructure needs to be re-engineered for improved environmental, social, and economic sustainability by minimizing the energy input for treating the wastewaters and by recovering water, energy, and fertilizers from the wastewater for beneficial reuse. In recent years, several alternate technologies have been proposed to take advantage of the water-energy nexus in urban wastewater infrastructure systems. This paper presents a case study evaluating sustainability of four urban water-energy nexus based on the 17 United Nations Sustainable Development Goals (SDGs) that have been unanimously endorsed by all 193 member countries. A multi-criteria decision making (MCDM) approach is used in this study to evaluate the four alternate urban water-energy systems in terms of 30 criteria spanning environmental, social, and economic sustainability. The 30 criteria selected here were derived from the 17 SDGs. The MCDM approach was selected in this study because of its ability to handle quantitative and qualitative criteria and rank the options on a numerical scale. The four wastewater treatment alternatives were evaluated under 12 different scenarios considering high/low priorities of decision-makers towards six different water-energy nexus attributes (pathogen removal, energy consumption, gaseous emission, resource recovery, footprint, and past records).