bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bipolar Electrochemistry for the Synthesis of Anodic TiO2 Nanotube Layers
Authors: Sopha Hanna , Macak Jan M. 
Published: November 2022

Self-organized TiO2 nanotube (TNT) layers have attracted considerable scientific and technological interest over the past 17 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of these TNT layers is carried out by electrochemical anodization of valve Ti metal substrates in various F--containing electrolytes using a conventional 2-electrode set-up with the Ti substrate as anode and a Pt-foil as cathode.
Instead of using a conventional set-up, also bipolar electrochemistry can be employed for the anodization of valve metals [3-7]. In this set-up, the Ti substrate is placed in an electrolyte between two so-called feeder electrodes, which are connected to the potentiostat. Due to the electric field between the feeder electrodes, the Ti substrate is polarized. If the applied potential between the feeder electrodes is high enough, redox reactions can be driven on the Ti substrate. This method opens new doors for the preparation of TNT layers with gradients in dimensions (i.e. diameter and length of the nanotubes) [3-5] as well as for the preparation of TNT layers on Ti substrates, which cannot be directly connected to the potentiostat, e.g. Ti spheres [8].
In this presentation, the preparation of TNT layers on small Ti spheres [8] as well as on 3D printed Ti substrates [9] using bipolar electrochemistry will be shown and discussed. Furthermore, we will also show the possibility of using closed bipolar electrochemical cells, consisting of two closed half-cells with the Ti substrate as obstacle between the cells [10].
References:
[1] J.M. Macak et al., Curr. Opin. Solid State Mater.
2007, 11, 3.
[2] Lee, K. et al., Chem. Rev.
2014, 114, 9385.
[3] G. Loget et al, J. Mater. Chem A
2014, 2, 17740.
[4] G. Loget et al., Langmuir
2014, 30, 15356.
[5] W. Wei et al., Electrochim. Acta
2015, 176, 1393.
[6] H. Asoh et al., RSC Adv.
2016, 6, 90318.
[7] H. Asoh et al., J. Electrochem. Soc.
2018, 165, C295.
[8] H. Sopha et al., Electrochem. Commun.
2020, 111, 106669.
[9] H. Sopha et al., Nano Lett.
2021, 21, 8701.
[10] H. Sopha et al., ChemElectroChem
2021, 8, 3827.
Visualization of Hydrogen Penetration Generated in an Atmospheric Corrosion and a Crevice Corrosion
Authors: Azumi Kazuhisa , Katsuie Yosuke 
Published: November 2022

Hydrogen could form in the corrosion reaction and sometimes causes hydrogen-related deterioration of steel. Spatial distribution of hydrogen penetration in steels has been observed using a photocurrent mapping method. In this method, hydrogen penetrated from the backside of the steel sheet formed by the cathodic polarization or corrosion reaction causes an enhancement of photocurrent intensity under the photo-irradiation to the passive film in the anodic biased condition. This photocurrent enhancement may be provided by the photo-generated holes that oxidize hydrogen atoms efficiently on the passive film surface. This work conducted hydrogen penetration mapping using a photo-charge mapping method newly developed for rapid mapping measurement. In this method, a polarization current during single UV-light pulse irradiation was integrated to obtain the charge Q
a, and then a charge Q
b during the irradiation was subtracted to obtain a photo-charge Q
PC = Q
a-Q
b for a single pulse. This process was performed by the electronics circuit controlled by the computer. Combination of pulse system and X-Y galvano-mirror-scanning device for a light beam emitted from pulse UV (405 nm, 0.2 W) pulse laser, rapid photocharge mapping was achieved, e.g., 24 s for 40 x 40 = 1600 pixel map.
In the experiments, a Devanathan-type cell composed of a top cell of a humidity control room and a bottom electrochemical cell was constructed. A UV laser beam was induced to the bottom cell via a quartz window to scan the bottom iron surface. Fig. 1 shows an example of the time-transition of photocharge maps measured for an iron sheet. In the experiment, a droplet of NaCl solution was put on the surface, and the humidity of the top cell was changed to wet/dry/wet conditions. In the figure, a droplet grew with absorbing moisture at 48 ks, rust expanded and precipitated in the droplet at 131 ks, dried to form rust at 668 ks, and soaked again at 534 ks. In this process, penetration of hydrogen was observed at the bottom face. Initially, hydrogen appeared only at the center of the droplet and then expanded to the lateral direction by increasing the photocharge.

Fig. 1. Time-transition of top images of an iron sheet (0.1 mmt) with a single NaCl solution droplet and photocharge maps measured for the bottom side of the iron sheet polarized at 0.7 V vs. Ag/AgCl in pH8.4 borate solution.

Figure 1
Stress-Affected ORR on Stainless Steel
Authors: Hangarter Carlos M , Anderson Rachel M. , Policastro Steven A 
Published: November 2022

Oxygen reduction reaction (ORR) is an important cathodic reaction that often drives galvanic corrosion. In atmospheric environments, this reaction is responsible for accelerated corrosion from enhanced transport associated with discontinuous electrolytes. In load bearing structures, galvanic couples are subject to mechanical stresses that often necessitates these dissimilar metal unions. Greater understanding of mechanical stress effects on fundamental reactions of galvanic corrosion, such as ORR, is important from a forecasting perspective for improved prediction of component lifetimes and service requirements. Furthermore, extension of this behavior to confined, concentrated electrolytes is important to understand stress effects in atmospheric environments.
This work reports the impact of tensile stress upon oxygen reduction reaction (ORR) for stainless steel fastener materials. Chronoamperometry was used to observe and quantify the influence of tensile stress profiles on ORR under NaCl droplet electrolytes. NaCl was utilized as a seawater proxy at concentrations of 0.6 M NaCl and 4.6 M NaCl, the latter corresponding to 80% relative humidity, which is near the deliquescence point for NaCl. The ORR current was shown to increase with tensile stress and displayed reversible behavior with simple stress profiles. Deoxygenated experiments were performed to isolate ORR contributions from oxide dynamics. Details of current transients during strain ramping are used to demonstrate these features are distinct from the ORR current shift observed during static tensile stress. Polarization experiments were performed during static tensile holds in the elastic and plastic regime for greater insight of stress effects on reduction kinetics. EIS and Mott-Schottky experiments were conducted to gain insight into the oxide behavior.
(Invited) Empirical Modeling of Broadband Insertion Losses in TSV-Interconnects
Authors: Coakley Kevin J , Kabos Pavel , Moreau Stephane , Obeng Yaw 
Published: November 2022

The reliability of through silicon via (TSV)-interconnects depends
on various factors including construction materials, fabrication
location on wafers, thermal history, operating conditions and
integration schemes. The magnitude of the frequency-dependent
$S_{21}$ microwave scattering parameter quantifies insertion losses
in TSV-interconnects. We attribute these losses (which affect device
reliability) to reorientation of electrically active defects, cracks,
voids, dielectric constant variation, and water molecules affected
by heat. We model these insertion losses with an equivalent circuit
model. We estimate model parameters with a stochastic optimization
implementation of the Levenberg-Marquadt method. For TSV-interconnects
from two different providers, we quantify how estimated model
parameters vary spatially (on a wafer), and how estimated parameters
vary with thermal cycles for TSV-interconnects fabricated at particular wafer
locations.
Quantification of the Mesoscale Spatiotemporal Heterogeneities in Nickel-Rich Layered Oxide Cathodes By Raman Spectroscopy
Authors: Agrawal Shubham , Gupta Rohit , Sittisomwong Poom , Singamaneni Srikanth , Bai Peng 
Published: November 2022

Lithium-ion batteries consisting of the particulate porous electrodes, are the dominant energy storage devices, however, they suffer from random failures and safety-related accidents. Such arbitrary incidents arise from the spatiotemporal heterogeneities occurring due to the material thermodynamics[1] which results to local hot and cold spots and early battery failures. The past investigations of the heterogeneities in the battery materials rely on the sophisticated synchrotron X-ray methods[2]–[4], which are not easily accessible. Instead, in this study, we employ Raman spectroscopy on an in situ benchtop setup which provides several advantages while investigating the true electrochemical kinetics in graphite electrodes, such as: (i) the setup houses practical porous NMC532 cathodes under realistic electrochemical surroundings; (ii) the high resolution of 1-2 µm provides sufficient information on the larger cathode particles; (iii) the method can analyze hundreds of particles, statistically representing the entire composite electrode; and (iv) the spectra can be quantified to reveal the actual reaction area, thus revealing high-fidelity real-time electrochemical performance. We use this simple but precision method to track and analyze the active reaction regions at the mesoscale in the NMC532 electrode to obtain the true local current density, which was found to be an order of magnitude higher than the globally-averaged current density adopted by the existing studies.
Raman spectroscopy can distinguish the vibrational modes of NMC532 with varying Li ion concentration. Since NMC532 is a solid-solution material, the Raman spectrum at each selected location can be deconvoluted into three distinct phases: empty, completely lithiated and partially lithiated. The partially lithiated regions participate in the surface reaction and can be identified to reveal the active reaction area. Thus, we quantified the active area fraction under slow galvanostatic conditions and generated a map of active regions with varying global Li ion fractions. Our results show that only 18% – 50% of the total particle area is active at any instant leading to higher local current densities than the globally-averaged electrode responses. The methods developed in this study are critical to estimate the kinetic parameters using true electrochemical responses and further aid in the design of the particulate porous electrodes.

References

[1] S. Agrawal, P. Bai, Cell Reports Phys. Sci.
2022, 3, 1.
[2] S.J. Harris, A. Timmons, D.R. Baker, C. Monroe, Chem. Phys. Lett.
2010, 485, 265.
[3] C. Tian, Y. Xu, D. Nordlund, F. Lin, J. Liu, Z. Sun, Y. Liu, M. Doeff, Joule
2018, 2, 464.
[4] S. Fang, M. Yan, R.J. Hamers, J. Power Sources
2017, 352, 18.
Cobalt and Nickel Free Disorder Rock Salt Cathodes – Recent Developments
Authors: Nanda Jagjit , Self Ethan 
Published: November 2022

Disordered Li-excess rock salt (DRX) cathodes are a promising class of high capacity (and voltage) cathodes for next-generation Li-ion batteries. Compared to conventional Li-ion cathodes which are generally restricted to Co/Ni-based compositions with specific cation ordering, DRX materials have a wide compositional design space based on earth abundant metals such as Mn, Ti, Mo, Al, Zr, V, and Nb. Furthermore, Li-rich oxyfluoride DRX cathodes have demonstrated specific energies up to 1,000 Wh/kg which exceeds that of state-of-the-art layered LiNixMnyCo1-x-yO2 (NMC) cathodes (~700 Wh/kg). Despite such scientific advancements, widespread adoption of DRX cathodes has been hindered by several technical challenges. First, most of the high fluorine content DRX compositions are synthesized using mechano-chemical synthesis that has inherent limitation in scalability and maintaining a uniform particle-size and morphology. Further, DRX compositions have about 3-4 order lower electronic conductivity compared to layered cathodes requiring a high carbon loading in the electrode (up to 25%) compromising energy density. The focus of this talk will be on developing alternate synthesis method for Li-Mn rich DRX compositions. Specifically solid-state and sol-gel synthesis methods to produce DRX cathodes with the nominal composition Li1.2Mn0.4+xTi0.4-xO2-xFx (x = 0-0.3). Detailed advanced characterization (i.e., neutron total scattering and electron microscopy) and modelling efforts (i.e., Reverse Monte Carlo simulations) to understand how SRO impacts cathode performance will be presented. Different choice of precursors based on thermodynamic and kinetic consideration that minimizes formation of LiF impurity phases will be proposed.
Acknowledgment
This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725
(Digital Presentation) 3D Electrochemical Model Revealing Electrode Manufacturing Parameters’ Effects on Battery Performance
Authors: Liu Chaoyue , Lombardo Teo , Xu Jiahui , Ngandjong Alain C. , A. Franco Alejandro 
Published: November 2022

Electrode manufacturing is in the core of Li-ion battery manufacturing process. The electrode mesostructure and the associated electrochemical performance is determined by the adopted manufacturing parameters. However, in view of the strong interdependencies between these parameters, evaluating their influence on the performance is not a trivial task, and our ERC-funded ARTISTIC project1,2 is providing a theoretical framework to rationalize and optimize the manufacturing process of Li-ion battery cells. Over the years, the discussion of importance of electrode mesostructure in cell behavior has become increasingly lively. Many modeling researchers have been conducted studies to explain the influences of electrode mesostructure on its electrochemical performance3–6. However, many studies did not include manufacturing parameters as inputs, which hinders universality in regards of these electrochemical models’ application. With the aim of going into the scope of real electrode manufacturing parameters, we present here a calibrated 3D-resolved electrochemical model for NMC111-electrodes which reveals how slurry formulation and compression rate affect the electrode performance. A series of electrodes with different formulations and compression rates were manufactured. Corresponding models were built based on the basis of these manufacturing parameters, using the manufacturing process simulation workflow previously developed in ARTISTIC7. The results of simulations and experiments were compared individually. We found that one of the major factors affecting the electrode performance is the carbon-binder domain (CBD) distribution, which highly changes the conductive network within the electrode. A well-connected conductive network throughout the electrode is vital for ensuring full utilization of active material. Other features such as porosity, tortuosity factor, active material particle packing, and etc. also play important roles in different ways. This work provides systematic insights on the essence of how electrode manufacturing process takes effect on electrode performance, through a digital twin experimentally validated under multiple experimental conditions.
References

Artistic http://www.erc-artistic.eu/.

Artistic http://www.erc-artistic.eu/scientific-production/publications.

X. Lu et al., Energy Environ. Sci., 14, 5929–5946 (2021).

M. E. Ferraro, B. L. Trembacki, V. E. Brunini, D. R. Noble, and S. A. Roberts, J. Electrochem. Soc., 167, 013543 (2020).

X. Lu et al., Nat. Commun., 11, 2079 (2020).

L. S. Kremer et al., Energy Technol., 8, 1900167 (2020).

T. Lombardo et al., Batter. Supercaps, 5, e202100324 (2022).
1-D Modeling of an Electroactive Electrolyte for Advanced Primary and Secondary Li Batteries
Authors: Harris Kailot , Parke Caitlin D. , Albertus Paul 
Published: November 2022

In the search for more energy- and power- dense battery materials, the cathode is most often the component that is engineered to boost operating voltage and capacity. However, new approaches to battery design have yielded performance improvements by designing electrolytes with reactive species that increase capacity and energy density of full-cells. These approaches borrow insights from commercial battery technologies such as Pb-H2SO4, Li-SO2, or Li-SOCl2, where the cathodic reaction involves liquid-phase active species1–3, while employing solid-phase cathode materials.
To better understand how specific examples of electroactive electrolytes improve rather than impede performance, our work focuses on two battery chemistries: a primary Li-CFx cell with an irreversible electrolyte reaction, and a secondary Li-LMR cell with a reversible electrolyte reaction. For each case, we develop a 1-D COMSOL model to investigate how the reaction of electrolyte species affects cell impedance, impacts Li cation transport, alters the electrolyte conductivity, and finally how each of these mechanistically impact the energy and power density of the cell. Our modeling work is complemented by experimental studies that measure important electrolyte and cathode properties at various states of discharge or cycling.
(1) Park, H.; Lim, H.-D.; Lim, H.-K.; Seong, W. M.; Moon, S.; Ko, Y.; Lee, B.; Bae, Y.; Kim, H.; Kang, K. High-Efficiency and High-Power Rechargeable Lithium–Sulfur Dioxide Batteries Exploiting Conventional Carbonate-Based Electrolytes. Nat. Commun.
2017, 8 (1), 14989. https://doi.org/10.1038/ncomms14989.
(2) Schlaikjer, C. R.; Goebel, F.; Marincic, N. Discharge Reaction Mechanisms in Li / SOCl2 Cells. J. Electrochem. Soc.
1979, 126 (4), 513–522. https://doi.org/10.1149/1.2129078.
(3) Ruetschi, P. Aging Mechanisms and Service Life of Lead–Acid Batteries. J. Power Sources
2004, 127 (1–2), 33–44. https://doi.org/10.1016/j.jpowsour.2003.09.052.
Improve the Zinc Slurry-Air Battery Performance: New Operational Mode to Separate Effects
Authors: Li Yuanshun , Washington Brian , Goenaga Gabriel , Zawodzinski Thomas A. 
Published: November 2022

In recent years, zinc air batteries received substantial interest as a viable next generation of batteries based on their merits of high energy densities, high performance, environmentally friendly, inexpensive, and abundant electrode material. Traditional secondary zinc air flow batteries use zinc metal as an anode. Severe dendrite growth and passivation limits the cycling behavior, which hinders commercialization in the industry. By substituting the zinc plate with a zinc slurry (zinc particles suspended in the alkaline media, typically with a high concentration of potassium hydroxide), the battery can in principle achieve higher energy density and attain more cycles but with very limited performance. Important questions related to such systems include the accessible percentage of Zn capacity, controlled by the formation of passivating layers on the particle and the intrinsic resistance of the slurry.
Here, we present a new operational mode to investigate the performance of zinc slurry air battery. The anode of the test battery system consists of 5 cm2 nickel plate as current collector for 5 cm3 zinc slurry. The cathode consists of air electrode, bipolar plate, and current collector. Zinc particles (Spectrum) were suspended in 4M KOH stabilized by polyacrylic acid (PAA). In our testing, the polarization loss was measured and is separated from that associated with the air electrode using a reference electrode. The conductivity of the slurry was measured by the simply modified configuration of the cell. The utilization of zinc is measured by chronopotentiometry. The battery can work at 1.1 V with 200mA/cm2, and the slurry can achieve 48.7% utilization.

Acknowledgements

The authors gratefully acknowledge the support of the US Department of Energy Office of Electricity Storage Systems Program directed by Dr. Imre Gyuk and the University of Tennessee Governor’s Chair Fund for support of this work.

Figure 1
(Digital Presentation) Electrodeposition and Characterization of a Selective Coating on Aluminum for Scale-up in Thermo-Solar Applications
Authors: Cetina-Dorantes Marco , Lizama-Tzec Francisco , Herrera-Zamora Dallely , García-Valladares Octavio , Gómez-Espinoza Victor , Rodriguez Gattorno Geonel , Oskam Gerko 
Published: November 2022

Flat-plate solar collector systems are devices used to convert solar energy to thermal energy. These devices require a selective coating that absorbs all sunlight but does not emit energy in the near IR; hence, a multilayer system of metal/IR-reflector/metal oxide is often used. Many substrates are used, including metals such as copper, stainless steel, and aluminum. Aluminum is an interesting substrate for its lower cost and good optical properties. Electrodeposited materials have gained importance in the industry for the easy handling and good results in scale-up. However, in general it is difficult to electrodeposit onto aluminum due to the ever-present thin insulating oxide film. In this work, we propose an adherent interlayer film based on copper, which is electrodeposited onto aluminum, and serves as a basis for the subsequent electrodeposition of a selective coating consisting of bright nickel and the absorber film of electrodeposited black nickel. Solar collectors based on aluminum substrates and this electrodeposited selective coating are specifically useful for thermo-solar applications at low to medium temperature.
Electrochemistry studies including cyclic voltammetry, rotating disk cyclic voltammetry, and galvanostatic curves are carried out for all the different layers. The properties of the coatings are subsequently characterized by reflectance spectra using UV-Vis, NIR and IR spectrophotometers equipped with integrating spheres. The solar absorptance is calculated by weighting the reflectance spectrum against the solar radiation spectrum ASTM G173-03. The thermal emittance is calculated weighting the reflectance spectra against the black body radiation function at 100 °C. The morphology and homogeneity of the film are evaluated with scanning electron microscopy, and energy dispersive spectroscopy. X-ray photoelectron spectrometry is used to determine the film composition. The crystalline structure of the films is studied by X-ray diffraction and Raman measurements. The second and third layer, bright nickel, and black nickel, respectively, are electrodeposited on top of the Cu layer using a previously reported method. We characterize the selective coating electrodeposited onto aluminum/Cu/bright nickel and show that this is a viable technology for the fabrication of low-cost and high efficiency flat plate solar collectors. In addition, we demonstrate the scale-up of the electrodeposition process, and characterize the performance of a complete flat-plate solar collector device of 1.8 m2 gross area.
Acknowledgements
The authors gratefully acknowledge CONACYT, Módulo Solar S.A. de C.V. and IER-UNAM for funding through the Mexican Center for Innovation in Solar Energy (CeMIE-Sol), Project P-81.