bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Cryo-Based FIB/SEM Characterization of Salt Film on Metal
Authors: Li Tianshu , Perea Daniel , Schreiber Daniel , Wirth Mark , Orren Graham , Frankel Gerald S.
Published: December 2020

Metal salt films play a critical role in high rate dissolution processes such as within an active pit.1-5 To better understand the film growth mechanism, the salt film structure and composition must be characterized with high resolution, which however, is challenging owing to the dynamic nature of the dissolving interface. In this work, a novel cryogenic specimen preparation approach to preserve the pit solution and salt film was introduced, allowing ex situ characterization of the native structure formed on the dissolving metal surface. The salt film formed on a 304 stainless steel one-dimensional artificial pit electrode was preserved by flash freezing in liquid nitrogen while under an external driving potential, processed using cryo-based focused ion beam, and investigated with cryo-based scanning electron microscopy cross sectional imaging. The salt film exhibits a porous structure, with many voids and gaps between salt crystallite clusters, forming channels to provide ionic connection between the metal/film and film/solution interfaces. A spatial separation of Cr and Fe was observed in the salt film using energy dispersive X-ray spectroscopy, while Ni was found to follow the distribution of Fe, indicating the existence of co-precipitated salt containing Fe2+ and Ni2+.

Acknowledgments: This work was supported as part of the Center for Performance and Design of Nuclear Waste Forms and Containers, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0016584.

Reference

G. S. Frankel, T. Li, and J. R. Scully, Journal of the Electrochemical Society,
164 (4), C180-C181 (2017).

T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society,
165 (9), C484-C491 (2018).

T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society,
165 (11), C762-C770 (2018).

T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society,
166 (6), C115-C124 (2019).

T. Li, J. R. Scully, and G. S. Frankel, Journal of The Electrochemical Society,
166 (11), C3341-C3354 (2019).
(Invited) 4D Nanoscale Imaging of Corrosion through Coherent x-Ray Diffraction Imaging
Authors: Cherukara Mathew Joseph , Chan Henry , Loeffler Troy , Narayanan Badri , Sankaranarayanan Subramanian , Harder Ross
Published: December 2020

Bragg coherent X-ray diffraction imaging (BCDI) is a powerful means of operando materials characterization at the nanoscale. With the ability to measure 3D structure and strain in materials at few nm resolution and under real-world conditions, BCDI has provided unique insight into a variety of materials processes. We apply BCDI to directly image the 3D structural and strain field evolution in copper nanoparticles corroding in saline solution. We observe a defect driven, anisotropic corrosion process that is accompanied by nanoscale pit formation and lattice strain variation. To understand the origin of these phenomena, we build experimentally informed atomistic models of the corrosion process.

Figure 1
(Invited) Novel in-Situ Methods for Real-Time Monitoring of Corrosion
Authors: Virtanen Sannakaisa
Published: December 2020

The presentation will introduce recently developed new techniques that allow real-time monitoring of corrosion processes. The approach is based on simultaneous measurement of the cathodic kinetics of the H2 evolution reaction (HER) and the O2 reduction reaction (ORR) in real-time. The universal and non-destructive, in-situ methods based on monitoring the rates of the cathodic reactions enable the determination of sensitive, real-time corrosion rates for both atmospheric corrosion and immersion.

In the case of immersion, HER monitoring e.g. with gravimetric buoyancy H2 measurements is well established. Recently it was shown that gravimetric H2 measurements are also suitable to monitor atmospheric H2-type corrosion (for Mg alloys) [1]. A novel approach to measure HER rates during atmospheric exposure is introduced in this work. This is based on determining the pressure increase in a hermetically closed chamber with a pressure sensor. Regarding ORR, both volumetric measurements and pressure sensor based techniques are applicable to monitor the rate of consumption of O2 gas. In addition, a fibre optic O2 sensor can be employed to monitor ORR rates both under immersion and atmospheric corrosion conditions. A combination of these methods enables to monitor ORR and HER simultaneously. Therefore, also corrosion systems where both HER and ORR contribute to the cathodic reaction can be monitored (e.g., Fe and Zn corrosion). Examples for the different corrosion cases studied with this new respirometric approach will be demonstrated [2]. Combining the above described approaches with a flow cell setup expands the possible corrosion scenarios to be investigated. The flow cell enables switching between exposure conditions (such as, electrolyte composition, temperature, flow rate, etc.) with a real-time response of the corrosion rate.

In addition of being of interest for corrosion monitoring, the techniques described moreover reveal details on time-dependent mechanisms of corrosion reactions.

[1] M. Strebl, S. Virtanen, J. Electrochem. Soc. 166 (2019) C3001-C3009.

[2] M. Strebl, M. Bruns, S. Virtanen, J. Electrochem. Soc. 167 (2020) 021510.
(Invited) Oxidation of Alloy-X in Near Supercritical and Supercritical Water
Authors: Karmiol Zachary , Chidambaram Dev
Published: December 2020

Supercritical water is a growing medium for power production, hazardous waste remediation, and chemical synthesis. These broad applications require robust materials that can withstand exposure to the high operating temperatures and pressures of supercritical water, while achieving these conditions necessitates that water transitions from the subcritical state to the higher enthalpy supercritical state. This region of transition has been observed to be the region with the greatest variation in thermophysical properties, with reports of a local maximum in corrosion rate. Experimental procedures have been employed to study the effects of exposure of Alloy X to the near supercritical and supercritical region in the supercritical water loop at The University of Nevada, Reno, which is of a design that allows for controlled exposure to the transition region between subcritical and supercritical water. An investigation into the oxidation of Alloy X included characterization by Raman spectroscopy, X-ray diffraction pattern analysis, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. Observation and characterization of the oxidation as a result of exposure will allow for the evaluation of Alloy X as a candidate for application in processes utilizing supercritical water, as well as increased understanding of the specific demands of exposure to the transition region between subcritical and supercritical water.

Acknowledgements: The SCWL was funded by the Department of Energy through a Nuclear Energy grant: DE-NE0000454. Kenny Osborne serves as the program manager for the DOE award. This work was performed under the auspices of the US Nuclear Regulatory Commission Faculty Development Program under contract NRC-HQ-11-G-0039. Nancy Hebron-Isreal serves as the grants program officer for the NRC award.
Effects of Dissolved Oxygen Concentration in Electrolyte Film on Atmospheric Corrosion of Carbon Steel
Authors: Araki Sho , Tsuchiya Hiroaki , Fujimoto Shinji
Published: December 2020

Steel is used for infrastructures such as bridges due to its superior mechanical properties as well as low cost. However, atmospheric corrosion of steel causes the deterioration of strength of the steel. As corrosion rate of steel in atmospheric environment strongly depends on the oxygen reduction reaction on rusts of the steel as well as the reduction of the rusts, effects of structure and properties of rust have been examined. In addition, as atmospheric corrosion proceeds under an electrolyte film, the oxygen reduction rate is not necessarily diffusion-limited, that is, the corrosion behavior is reported to be different form that in bulk aqueous electrolyte. Furthermore, steels used for bridges are used for the most of their life time with the presence of rust layer on the steels. Therefore, investigations on the corrosion behavior of rusted steel under an electrolyte film are required to assess the corrosion life time of bridges. The present work aims at revealing the dissolved oxygen concentration in rust layers under an electrolyte film by simultaneous measurements of electrochemical parameters and the dissolved oxygen concentration in an electrolyte film on rusted steel.
Effects of Cathodic Process on Corrosion Fatigue of Type 316L Stainless Steel in 0.9 % NaCl Solution
Authors: Nakatsu Mayuko , Miyabe Sayaka , Fujimoto Shinji
Published: December 2020

Type 316L stainless steel exhibits superior corrosion resistance in aqueous environments, due to a protective passive film formed on the surface. Therefore, the stainless steel is used in diverse fields. However, during cyclic deformation of the steel in environments that contain chloride ions, the breakdown of the passive film on the steel surface occurs around stress concentration zones, causing the anodic dissolution of underlying steel. On the other locations, oxygen reduction reaction mainly occurs as cathodic reaction. Therefore, both anodic and cathodic reactions have to be taken into consideration to examine corrosion related phenomena. However, effects of cathodic reaction still remain unclear. In the present work, cyclic deformation test of Type 316L stainless steel with different cathode areas was performed to clarify effects of cathodic process on corrosion fatigue of the stainless steel.
Effect of Gradient of Soil Aeration on Corrosion Rate at Different Depths from Ground Surface
Authors: Fujihashi Kenta , Oshikawa Wataru
Published: December 2020

In recent years, the number of photovoltaic electric power systems has drastically increased in Japan. Currently, metal piles are used in the foundations of these systems. However, a section of the metal foundation piles near the ground surface corrodes faster than . This problem has not been widely investigated.

In our study, exposure tests were carried out in soil at three test sites, and macrocell current densities were measured at different soil depths based on the gradient of soil aeration. Soil samples from these sites were collected at every 50 mm of depth below the ground surface. Thereafter, the soil samples were used as electrolytes for AC impedance analysis of the components. The exposure test indicated that there were environment in which severely corroded in soil near the ground surface, and this environment was poorly drained. However, the results of the macrocell current density measurement and the AC impedance analysis indicated that the electrode corrosion rate near the ground surface was NOT faster than, but similar to, those for the other sections in deeper soil.

Accordingly, a corrosion test was conducted by simulating the test site environment. For the corrosion test, a columnar soil tank (ϕ 200 mm × H 300 mm) and 18 steel electrodes (3.2 mm × 30 mm), each placed at 2 mm distance, were used. The macrocell current was measured using this tank of Arakita soil (paddy soil) that contained 15 wt.% water. Arakita soil used in this experiment was dried at 160 °C, milled, and passed through a sifter with 1 mm mesh net. were short-circuited. The voltage at both ends of the shunts was measured every 30 s, and the corresponding current was calculated using Ohm’s law. The spontaneous potentials of the electrodes were measured every 1 h Thereafter, AC impedance analysis of soil samples used as electrolytes that were collected from this tank at depths of ~50 mm and 250 ~ 300 mm were conducted.

The experimental results suggested that a macrocell was formed at a depth of ~10 mm. The corrosion rates of the electrodes were calculated using the macrocell current. The electrode set at a depth of 5 mm near the ground surface exhibited the maximum corrosion rate of 0.07 mm/year. The spontaneous potential of this electrode was lower than that of all other electrodes, except for two electrodes set at the depths of 40 and 45 mm. The electrode set at a depth of 5 mm was significantly corroded, which corresponded to the corrosion mass loss measured by the exposure test. AC impedance analysis. From the results, the significant corrosion at the ground surface can be considered to be due to macrocell corrosion caused by the gradient of soil aeration. However, it is not clear whether the spontaneous potentials of the electrodes at depths of 40 and 45 mm are lower and whether the anodic current flows through these electrodes.

Figure 1
Influence of Microstructure on Initial Corrosion Behavior of Steel Materials Using Kelvin Force Microscope
Authors: Uda Aimi , Yoshimoto Ryosuke , Murase Yoshiharu , Katayama Hideki , Hoshi Yoshinao , Watanabe Hikari , Shitanda Isao , Itagaki Masayuki
Published: December 2020

Improvement of the efficiency of power engines and reduction of the vehicles weight are important to boost the fuel efficiency of transportation equipment such as automobiles. One of the countermeasures is to expand the application of ultra-high tensile steel materials to structural members. However, the surface of ultra-high tensile steel becomes often non-uniform due to the metallographic control during manufacturing. Surface non-uniformities are more likely to lead to corrosion. Therefore, in order to further expand the application of ultra-high tensile steel materials, it is necessary to fully understand local corrosion behavior such as selective corrosion depending on the metal structure and grain boundaries. The purpose of this study is to research an influence of the non-uniformity of surface microstructure on corrosion of steel material, and the surface potential of each metallographic structures was measured by the Kelvin force microscope (KFM).

Carbon steel (S45C) was heat-treated under conditions of holding it at 1250°C for 30 minutes and cooling in the furnace. After the sample surface was mirror-polished, the sample surface was smoothed by performing ion milling as a pretreatment for the KFM measurement. The KFM measurement was conducted for a predetermined range with 0.30 Hz of a scanning frequency, and the surface shape image was also measured in AFM mode. Furthermore, a corrosion test was conducted by immersion in a borate buffer containing 0.01 mol dm-3 NaCl for 1 hour, in order to clarify the relationship between the surface potential distribution obtained by KFM measurement and the initial corrosion behavior. After that, the sample surface was thoroughly washed with distilled water, dried, and KFM measurement was performed again.

The surface morphology and the potential of the samples before the corrosion test changed periodically corresponding to the ferrite and cementite phases in pearlite. The potential of the cementite phase was about 10 mV lower than that of the ferrite phase. It was suggested that the interface between the cementite phase and the ferrite phase becomes an origin of corrosion, since the place showing the large potential difference is likely to be the starting point of corrosion. In comparing the surface morphology of the samples before and after the corrosion test, the width of the cementite phase was clearly narrower than that before the corrosion test. The surface potential of this part of the sample before the corrosion test showed more negative potential than the surroundings, which is considered that the shape change is attributed to the dissolution of the metal. Therefore, it was concluded that the potential distribution of the sample before the corrosion test is closely related to the corrosion behavior.
(Keynote) Sensor Design, Construction and Validation for in-Situ Water Layer Thickness Determination during Accelerated Corrosion Testing
Authors: Katona Ryan Michael , Tokuda Shimpei , Kelly Robert
Published: December 2020

The design, construction, validation, and application of a sensor to determine water layer (WL) thickness in the range of 0 to 5 mm in salt spray testing using finite element modeling (FEM) and experimental methods is presented. The sensor determines WL thickness based on electrical resistivity, which is a function of the width of the sensor, distance between the electrodes, and solution conductivity. Sensor design, and validation under known WL thicknesses, was informed by FEM results. The utility of the sensor was shown by measuring WL thickness in a continuous salt spray test similar to ASTM B117 (3.5 wt % NaCl at 35 ˚C) and the range of specifications allowed within the standard were explored. Within the realms of accelerated corrosion testing, the angle of exposure played the largest role in WL thickness. Furthermore, it was found that above an angle of 20˚ from vertical the WL experiences semi-periodic run-off events causing a transient decrease in the WL by up to 80%. Finally, the angle of sample exposure in salt spray environments determines if thin film conditions are achieved, influencing the rate of corrosion. The large allowances for sample angle present in most standards for laboratory corrosion chamber testing pose a large source of test-to-test and chamber-to-chamber variability.

Acknowledgements

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. This document is SAND2020-5133 A
In-Situ Raman Analysis of Precipitates Formed By Cathodic Polarization for Study of Atmospheric Corrosion in Marine Relevant Environments
Authors: Knight Andrew , Schaller Rebecca Filardo , Katona Ryan , Bryan Charles
Published: December 2020

Dry storage of spent nuclear fuel (SNF) in the United States exists across the country at independent fuel storage installations sites. At these sites the SNF is stored in stainless steel (SS) canisters equipped with a concrete overpack, where airflow through inlet and outlet vents allow for the passive cooling of the payload. While SS canisters are known for their enhanced corrosion resistance, when placed in a marine and near-marine environment they have shown to be suspectable to localized corrosion. In these environments, sea salt aerosols can adhere to the SS surface and, under certain temperature and relative humidity ranges, deliquescence can occur to form chloride rich brines. Under such exposure conditions, SS is known to undergo passive breakdown and pitting corrosion; thus, can be susceptible to subsequent stress corrosion cracking in the presence of residual stresses.

In this study, we explore the relationship between the cathodic polarization and the surface brine present on 304-SS. Corrosion and pitting are a function of both the anodic current demand and the available cathodic current both of which have been shown to be dependent on the environmental exposure conditions. In concentrated salt solutions, certain bulk cations (Mg2+) have a strong thermodynamic driving force to form stable precipitates, such as hydroxides, driven by an increase in pH at the cathode from corrosion reactions, which can block cathodic reduction sites. Using in-situ Raman measurements during a cathodic polarization scan we attempted to identify under which conditions (e.g., potential, pH) precipitates form and what their overall composition is. In MgCl2 rich brines, we observed that the pH of precipitation and the identity of the precipitate were dependent upon the initial MgCl2 concentration, as predicted by thermodynamic modeling. The implications of these measurements demonstrate that the maximum pit size in MgCl2 brine surface environments may be limited as the cathodic reduction sites are blocked by precipitation, perhaps leading to the starvation of the pit and eventual brine dry out.

Sandia National Laboratories is a multi-mission 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.

Figure 1. In-situ Raman of SS in 0.189 M MgCl2 brine showing the formation of microcrystalline brucite.

Figure 1
Microstructure and Electrochemistry of Al-Rich Primer
Authors: Wang Shan-Shan , Palani Siva , Rose Alan , Frankel Gerald S.
Published: December 2020

Al-rich primer (AlRP) is designed to be anodic relative to high strength Al alloys, so that it drives the mixed potential of Al alloy substrates (e.g. AA2024) into the cathodic region below the breakdown potentials of the Al alloys, preventing localized corrosion. The Al-rich primer (AlRP) under study is composed of spherical Al-Zn-In pigments in an epoxy binder. The 2D and 3D microstructure of the AlRP was studied using a combination of X-ray microscopy, plasma focus ion beam/scanning electron microscopy, and transmission electron microscopy techniques. The primer contained Al-Zn-In particles with various sizes ranging from tens of nanometers to microns, epoxy binder and a significant volume of voids. Potentiodynamic polarization testing was performed to measure the electrochemistry of the Al-Zn-In bulk alloy under neat primer in NaCl solution to simulate the environment which Al-Zn-In pigments are exposed to in the real primer. The bulk alloy under neat primer exhibited higher breakdown potential than the bare bulk alloy exposed to NaCl solution. The polarization curves of the bulk alloy under neat primer provide more accurate boundary conditions for modeling of the galvanic interaction between the AlRP and an alloy substrate. Galvanic corrosion between an AA2024 sample and Al-Zn-In bulk alloy was also studied using a zero resistance ammeter. A trivalent chromium process treatment on galvanic couples can protect AA2024 substrate from cathodic corrosion.

Acknowledgements: this project is funded by the Office of Naval Research through the Small Business Innovation Research (SBIR) program. We thank Naval Air Systems Command (NAVAIR) for providing Al-rich primer samples. We acknowledge Dr. Mansoureh Norouzi Rad at Zeiss for 3D microstructure reconstruction on Al-rich primer using X-ray microscope, and Thermo Fisher Scientific for 3D microstructure reconstruction on Al-rich primer using Helios Plasma FIB/SEM. We appreciate Dr. Babu Viswanathan at OSU for STEM characterization, and Swagelok Center for Surface Analysis of Materials (SCSAM) at Case Western Reserve University for Ar ion polishing.
(Invited) Developing the Electrodeposition of High Energy Density Anodes for 3D Architectures for Rechargeable Batteries
Authors: Prieto Amy L , Ma Jeffrey , Schulze Maxwell , Nieto Kelly
Published: December 2020

As Li-ion batteries continue to improve in all metrics, new markets are now opening to portable energy. However, the fundamental challenges are still the same: how do we improve how much energy a particular material can store, how quickly it can charge and discharge safely, while enabling effective communication between all components of a particular cell? It is not sufficient to simply discover and improve new materials, we have to also consider the development of efficient, manufacturable architectures that enable the best performance for a particular material.

We are working to incorporate high surface area structures of novel anode materials into a 3D interdigitated solid-state battery architecture. The significant advantage to this architecture is that the diffusion length for Li+between the cathode and anode will be dramatically reduced, which should lead to much faster charging rates. The structure and composition of the anode is critical to the energy density, power density, cycle life, and safety of the overall battery. I will discuss electrodeposited M-Sb (where M = Ni, Cu, Zn) thin films and high surface area structures that have been investigated as alloy anodes for Li-ion batteries to elucidate the effects of both the film composition and substrate interactions on cycling stability and lifetime. The results discussed will demonstrate that important composition and substrate factors for anode cycling performance are being developed that are likely applicable to other systems. A key theme in this work is how to develop materials architectures that not only have attractive properties for the chosen application (energy storage), but that are also ideally suited to elucidating and understanding degradation mechanisms for high energy density materials. I will also discuss my opinions on the need for integrating a big-picture view of manufacturability for applied materials research, as well as the challenges and opportunities in moving research and development from an academic lab into the marketplace.
Ferroelectric HfO2 Capacitors for Varactor Application in GHz
Authors: Lin Yu Wei , Mizutani Kazuto , Hoshii Takuya , Wakabayashi Hitoshi , Tsutsui Kazuo , Tsao Yi-Fan , Huang Ting-Jui , Hsu Heng-Tung , Kakushima Kuniyuki
Published: December 2020

Capacitance extraction of ferroelectric HfO2 capacitors was characterized at a frequency of 1 GHz. By applying a bias voltage in the non-switching region of the ferroelectric HfO2 films, a varactor operation was confirmed.

Introduction

The ferroelectric HfO2 layer has attracted attraction in CMOS and memory applications due to its scaling ability and process compatibility. Generally, ferroelctric capacitors show increase in the capacitance near the coercive field. By setting a proper bias to the ferroelectric capacitors, they can work as varactors under non-switching mode. As there is an increasing demand on-chip varactors for monolithic microwave ICs (MMICs) [1,2]. In this research, we measured the capacitance of the ferroelectric HfO2 capacitors at high frequency and confirmed the capacitance control. Measruements were done under on-wafer probing system in the frequency range of 10 MHz to 1 GHz [3].

Experiments

Figure 1 shows the schematic cross-section of ferroelectric HfO2 capacitors. A 1 mm plasma SiO2 layer was first deposited on a high-resistive Si wafer f. A 12-nm-thick 5 mol% Y-doped HfO2 film were deposteid by atomic layer deposition (ALD). The top and bottom electrode were both W deposited by sputtering and patterned by reactive ion etching (RIE). Annealing to transform the HfO2 layer into ferroelectric pahse was conducted at 500 oC. Metal contacts of Au/Ni/Ti were deposited by thermal evaporation.

Results and discussions

Capacitance-voltage measurement taken from LCR meter at 10 kHz is shown in fig. 2. After polling process, the capacitance can be tuned by 32 % by controlling the bais voltage in the non-switching region. The capacitance values under different bias voltage, extracted from the S-parameters of capacitors with proper calibration patterns, are shown in fig. 3. Although the capacitance tuning was narrow compared to those obtained by the LCR meter, the varactor operation was confirmd with ferroelectric HfO2 capacitors.

Conclusion

A varactor operation in ferroelectric HfO2 capacitor at 1 GHz was confirmed.

References

[1] N. Setter, et al., J. Appl. Phys. 100, 051606 (2006)

[2] A. Vorobiev, et al., Appl. Phys. Lett. 83, 3144 (2003)

[3] K. Lee, et al., IEEE Trans. Microw. Theory Tech., vol. 54, no. 12, pp. 4141-4148 (2006)

Figure 1
(Invited) Multifunctional Materials for Emerging Optoelectronic Technologies
Authors: Rosei Federico
Published: December 2020

As the age of fossil fuels is coming to an end, now more than ever there is the need for more efficient and sustainable renewable energy technologies. This presentation will give an overview on recent developments in solar technologies that aim to address the energy challenge. In particular, nanostructured materials synthesized via the bottom–up approach present an opportunity for future generation low cost manufacturing of devices [1]. We demonstrate various multifunctional materials, namely materials that exhibit more than one functionality, and structure/property relationships in such systems, including new strategies for the synthesis of multifunctional nanoscale materials to be used for applications in photovoltaics, solar hydrogen production, luminescent solar concentrators and other emerging optoelectronic technologies. [2-31].

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Durability and Reliability of EV Batteries Under Electric Utility Grid Operations: Impact of Frequency Regulation Usage on Cell Degradation
Authors: Baure George , Beck David , Dubarry Matthieu
Published: December 2020

The usage of electric vehicle batteries to assist the main electric grid for the storage of energy provided by intermittent sources should become an essential tool to increase the penetration of green energies. However, this service induces additional usage on the cells and, therefore, could degrade them further. Since degradation is path-dependent, it is of paramount importance to test the impact of all the different grid applications on the batteries. In this work, we tested the additional usage induced by using electric vehicle batteries for frequency regulation at moderate rates during rest or charge and found no detrimental effect after around 2000 cycles on the cells.

The main takeaway from our study was that some frequency regulation V2G usage at moderate rates (from C/5 to C/3 as a maximum current) did not accelerate the cell degradation despite close to 15% additional usage. In addition, there was no noticeable difference between performing this ancillary service during rest or charge or at maximum current fluctuations up to C/3 during rest and C/4 during charge. These results are extremely positive for the possible application of V2G/G2V strategies. However, it must be noted that our results hold for these specific cells and the duty cycle tested. More research is necessary to generalize the results. We already verified the results on another batch of commercial cells based on graphite//Nickel Cobalt Aluminum oxide.

Due to the lack of differences in the degradation between duty cycles, the benefits of modulating the charge to eliminate the additional usage on the cells could not be verified. Experiments on other chemistries with more aggressive usage will be launched to test the hypothesis further.

As for the diagnosis for the degradation, a new approach of coupling IC and DV analysis yielded four indicators for automatic diagnosis. This methodology will allow faster diagnosis and bolsters the value of the FOI approach for BMS implementation. However, our study also showed that under some conditions, in our case the apparent kinetic limitations, some of the FOI may become ineffective with time. Therefore, proper validation using full fits and sensibility analysis to check for the range of efficacy of chosen FOI is still essential.

Finally, some cells showcased the 2nd stage of aging and we were not able to predict it from the voltage variations. This suggested that it was not induced by a widespread degradation of the electrodes but was more likely because of localized effects. The cells that did not perform any frequency regulation seemed to be the most affected, but those results need to be moderated by the fact that the differences were probably within what to expect between cells performing the same duty cycles.
Voltammetrically Deposited Nife on Modified Ni Foam As an Efficient and Stable Electrocatalyst for Oxygen Evolution Reaction
Authors: Narayanaru Sreekanth , Gopinathan M Anilkumar , Tamaki Takanori , Yamaguchi Takeo
Published: December 2020

Environmentally safe and efficient production of renewable fuels are of great demand to meet the current global energy crisis and global warming. As a fuel, hydrogen has been considered as the most suitable source of clean and sustainable energy, which indeed promote the importance of electrochemical water splitting [1-3]. Efficient and stable electrocatalyst for both hydrogen and oxygen evolution reactions are inevitable for the commercialization of water electrolyzer. Comparatively, the oxygen evolution reaction (OER) is more sluggish than the hydrogen evolution reaction (HER), which in turn affect the overall efficiency of the water electrolysis [4]. The non-noble metal oxides-based catalysts in alkaline solution have been shown promising OER activity [5] however, the high alkaline condition and high oxidation potential affects the stability of the metal oxides.

Bimetallic oxide of NiFe system has been found as an efficient catalyst for OER [6]. Various methods were demonstrated for the synthesis of NiFe catalyst and studied their OER activity. In the present work, we made NiFe catalyst through electrochemical deposition method. We deposited NiFe over Ni foam and modified Ni foam through the constant potential method and voltammetric method. The OER activity and stability of these catalysts were measured in alkaline solution. Among the various catalysts synthesized, the NiFe deposited over modified Ni foam through constant potential method has shown better OER activity, attained 10 mA/cm2 at 1.45 V (vs RHE) but after electrolysis the potential increased to 1.47 V, indicating the poor catalytic stability. Whereas the NiFe catalyst prepared through the voltammetric method has attained 10 mA/cm2 at 1.46 V and remained unchanged after electrolysis, indicating better catalytic activity and stability (Figure 1).

Figure 1. Linear sweep voltammogram measured before and after electrolysis in 1 M KOH of electrodeposited NiFe catalyst prepared through (a) constant potential method and (b) voltammetric method.

Acknowledgement

This presentation is based on results obtained from a project commissioned by the New Energy and Industrial Technology Development Organization (NEDO)

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8, 23–39 (2014).

Figure 1
A Regenerable, Electrodeposited, Iron-Group Electrocatalyst for the Oxygen Evolution Reaction
Authors: Zhang Yujia , Kizilkaya Orhan , Bilan Hubert K. , Kurtz Richard L. , Podlaha Elizabeth J.
Published: December 2020

Fe-Ni-based oxides and oxyhydroxides have been recognized as interesting oxygen evolution reaction (OER) electrocatalysts, and thus could be alternatives to replace rare and expensive metal oxides (e.g., IrO2 and RuO2) for water electrolysis in the generation of hydrogen to store energy from intermittent sources, such as solar and wind. However, these materials may suffer from deactivation during the OER due to changes in the active phases. In this study, a methodology to regenerate the OER activity of aged, electrodeposited Fe-Ni-Co electrocatalysts in an alkaline electrolyte is presented.

The Fe-Ni-Co thin films were electrodeposited over a range of current density from a boric acid electrolyte onto rotating cylinder electrodes (RCE). The resulting deposits had different Fe and Ni compositions, containing a small amount of Co, and were used to characterize the OER in 1 M KOH. Linear sweep voltammetry was used to generate a surface oxide and measure the OER kinetics. The electroactive surface areas were accessed using an electrochemical ferricyanide/ferrocyanide redox reaction. The OER kinetics were found to be a function of deposit composition, with the lowest Tafel slope and overpotential (at 10 mA/cm2) observed at a metal weight percentage ratio, Fe/(Ni+Co), of 1.2. The electrocatalyst became less active upon chronopotentiometric aging at 10 mA/cm2 for 30 hours. Notably, when the aged catalyst was reduced by applying a cathodic current density, the electrocatalytic activity recovered. The spectra of Fe, Ni, Co L-edge and O K-edge from X-ray absorption near edge spectroscopy (XANES) suggested that the aging and recovery are due to the redistribution of the electron density between O, and Fe and Ni. Co was found to be predominately in the metallic state.
Iron−Group Metal Boride/Heteroatom-Doped Vertically Oriented Graphene As Efficient Catalyst for Overall Water Splitting in a Wide pH Range
Authors: Jiang Bin
Published: December 2020

Electrocatalytic water splitting for the generation of H2 and O2 is one of the most efficient strategy for the development of clean energy fuels. Though tremendous development has made on the fabrication of several electrocatalysts, yet these are limited for practical applications owing to their high cost, poor stability, activity, and scarcity. The cost–effective bifunctional electrocatalysts for overall water splitting with good stability and activity in a wide pH range are rarely reported. We report on a newly designed
Iron−Group Metal Boride
/Heteroatom-doped vertically oriented graphene (IMB/HVG) electrocatalysts, fabricated via single−step electrodeposition method. IMB/HVG hybrid catalysts have potential to enhance interfacial electron transfer, improve the catalytic performance, and withstand in a wide pH range (pH 0–13.8). The hybrid catalysts showed an excellent electro–catalytic activity for overall water splitting reactions in a wide pH range (pH 0–13.8). The as–synthesized electrocatalysts exhibited excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities with low overpotentials at a current density of 10 mA cm−2 in all pH values. The electrocatalysts also showed prominent electrochemical stability. We strongly believe, this study may provide a facile design for the fabrication of cost–effective and non–noble metal bifunctional electrocatalysts material for overall water splitting withstand in different pH conditions.
Electrodeposition Assisted Formation of Anodized TiO2-CuO Heterojunctions for Solar Water Splitting
Authors: Sherazi Syed Tauqir A. , Jabeen Sadia , Ullah Rahim , Khan Yaqoob
Published: December 2020

The anatase phase titanium dioxide nanotubes (ATNTs) is investigated for photocatalytic water splitting in pristine form and after copper oxide (CuO) incorporation. ATNTs are grown using titanium substrate by one and two step anodization followed by annealing at 450 ºC for transformation to anatase phase. Both of the anodization steps are performed by electrochemical process using ammonium fluoride, ethylene glycol and deionized water as electrolyte. The ATNTs are then modified with CuO nanoparticles, electrochemically and also through dip-coating process. The growth of ATNTs and deposition of CuO nanoparticles is confirmed with X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) spectroscopy. Well organized and vertically aligned nanotubes are confirmed under FESEM. Linear Sweep Voltammetry (LSV) technique is performed for photocurrent responses in distilled water in the dark environment as well as in the light of solar simulator at applied potential of 1.0V. ATNTs grown with two steps anodization offered promising results for photocatalytic water splitting compared to single step anodization. The CuO modification in ATNTs shown a reasonable increase in photocurrent densities compared to pristine ATNTs. Moreover, the ATNTs modified with CuO through electrochemical deposition exhibited greater photocurrent responses than the dip coating method.

Figure 1
Effect of the Concentration of Cupric Oxide By Composite PEO on Thermal and Electrochemical Performances
Authors: Chung Wonsub , Son Kyeongsik
Published: December 2020

Plasma electrolytic oxidation (PEO) is an environmentally friendly process to generate the dense passivation oxide film on the surface of light metals, such as Al, Mg, and Ti. The created oxide layer was performed for enhancing the thermal transfer performance on an Al alloy by cupric oxide (CuO) particles in a conventional PEO electrolyte. The copper and cupric oxide has high thermal conductivity and high emissivity, therefore the composite PEO surface was expected high thermal transfer performance. The chemical bonding of composited PEO surface was inspected by X-ray photoelectron spectroscopy (XPS), not only Al-O bonding which was generated from substrate but also Cu-O were deposited. Laser flash analysis (LFA) method was adopted to measure thermal diffusivity to evaluate the velocity of heat transfer. And thermal radiation was evaluated by using Fourier transform infrared spectroscopy (FT-IR). The condition and quantity of cupric oxide was optimized through repeated experiment. As a result, the composite PEO surface was enhanced thermal conductivity and thermal radiation property in comparison with conventional PEO. And the thermal transfer performance was evaluated to applied LED module.
Transition Metal-Based Ternary Catalysts Prepared By Electrodeposition for Hydrogen Evolution Reaction
Authors: Hong Seokjin , Kim Junhyeong , Kim Hyunki , Han Gyeong Ho , Ahn Sang Hyun
Published: December 2020

To solve the global warming problem caused by indiscriminate use of fossil fuel, hydrogen production technology via water electrolysis is drawing attention. It is known that the Pt catalyst has been reported to be excellent for hydrogen evolution reaction (HER), which inhibits commercialization of water electrolysis due to its high price. For this reason, non-noble metal-based catalysts have been investigated to achieve cost-effectiveness with acceptable catalytic performance. It has recently been studied focusing on transition metals (Ni, Co, Mo, etc.) combined with non-metals (B, N, O, S, P, etc.) and reported indicating improved HER performance of transition metal borides and transition metal phosphides. In this study, nickel based complex containing phosphides and borides catalysts (Ni-P-B) were prepared on the carbon paper substrate using electrodeposition method. Phosphorous is reported to act as an active site due to its abundance of electrons and high electronegativity, and thus the catalytic performance of transition metal phosphides to HER increased with an increase in P ratio. On the other hand, boron has a different aspect. In transition metal borides, boron was expected to act as an active site due to its abundance and high electronegativity, but in practice the boron's electrons increase catalyst activity by donating electrons to the empty d-orbital. Nickel-based compounds containing phosphorus and boron (Ni–P–B) may be catalysts for HER, given the advantages of nickel phosphides and borides, but little research has been done on this. An experiment was conducted to increase the performance of the transition metal by adjusting the ratio of P and B in combination with the different properties of the transition metal phosphides and borides. Deposition parameters such as deposition potential/time and bath configuration were changed to control their morphology and composition. Their catalytic activity for HER was tested in half-cell measurement with the acidic electrolyte. Then the activity orders based on geometric current, specific activity, and mass activity were connected with the results from analysis on material properties. Furthermore, employing the optimized catalyst in cathode, the performance of proton exchange membrane water electrolyzer was tested.
Synthetic Training Data for Artificial Intelligence-Based Li-Ion Diagnosis and Prognosis
Authors: Dubarry Matthieu , Beck David
Published: December 2020

Accurate lithium battery diagnosis and prognosis is critical to increase penetration of electric vehicles and grid-tied storage systems. Both diagnosis and prognosis are complex due to the intricate, nonlinear, and path-dependent nature of battery degradation. Data-driven models are anticipated to play a significant role in the behavioral prediction of dynamical systems such as batteries. However, they are often limited by the amount of training data available.

In this work, we will present a proof-of-concept methodology to generate big data training datasets for intercalation batteries. It will use a mechanistic approach that combines both modeling and experimental techniques to provide a universal tool for the creation of synthetic voltage curves practically indistinguishable from real data. This approach offers the benefits of the broad applicability of the model to various cell chemistries, designs, and operating modes, as well as the high fidelity as inhered from the detailed extraction of the experimental data. The methodology could be applied to the generation of training datasets encompassing the entire degradation spectrum as well as different operating conditions such as rate and temperature. Scenarios leading to lithium plating with adjustable reversibility can be added and the addition of random noise on the data could be considered to make the datasets even more realistic and consider the impact of real-life testing machines' precision and accuracy

The proof-of-concept datasets are over three orders of magnitude larger than what is currently available in the literature. With benchmark datasets, results from different studies could be easily equated, and the performance of different algorithms can be compared, enhanced, and analyzed extensively. This will expend critical capabilities of current AI algorithms, tools, and techniques to predict scientific data.
Welcome Remarks - E01: Electrodeposition for Energy Applications 5
Authors: Vereecken Philippe M.
Published: December 2020

Welcome to E01: Electrodeposition for Energy Applications 5! Take a moment to listen to welcome remarks from the lead organizer, Philippe Vereecken.
Hydrogen Evolution Reaction of BaSnO3-
δ Thin Film on p-Si
Authors: Kim Haein , Lee Joonbong , Lee Ho Jin , Cho Ayoung , Choi Taekjib
Published: December 2020

Oxide perovskites are proposed as photoelectrodes for the hydrogen evolution reaction(HER) in alkaline solutions. The cubic perovskite BaSnO3 can be used as a photoelectrode due to the edge position of conduction band, which is lower than the reduction potential. However, since it has a wide band gap of 3.1 eV, it is limited to use energy of a long wavelength including visible light. In this research, we investigated photoelectrochemical characteristics of BaSnO3 thin film deposited by Pulsed laser deposition(PLD) with promoting oxygen vacancy. The HER performance was enhanced due to band gap adjusted oxygen vacancy concentration. Furthermore, Electrochemical Impedance Spectroscopy(EIS) was measured to confirm surface charge resistance and charge transport. Thus, this study introduces that BaSnO3-δ/p-Si can be an efficient electrode for HER.