bluuebunny/crossref_metadata_2025 huggingface dataset:
The Ongoing Importance of Lithium Primary Batteries: 50+ Years and Going Strong
Authors: Takeuchi Esther S. , Takeuchi Kenneth J. , Marschilok Amy C.
Published: November 2022

Lithium anode primary batteries display numerous outstanding characteristics including high energy density, long shelf life, low self-discharge, and ability to function under a broad temperature operating range. This has led to the design and implementation of lithium primary cells for a variety of applications in the commercial, military, space, and medical fields. The development of these primary batteries has required understanding and resolution of complex reaction mechanisms as well as optimized electrode and cell designs to meet the needs of the target applications. Notably, a variety of cathode materials have been paired with lithium metal anodes including carbon monofluoride (CFx), manganese oxide (MnO2), thionyl chloride (SOCl2), and sulfur dioxide (SO2). A specific application of primary lithium battery systems is to power implantable medical devices. These primary systems utilize lithium metal anodes with cathodes such as iodine, manganese oxide, carbon monofluoride, silver vanadium oxide, and hybrid cathodes. While the specific performance requirements of applications vary, lithium batteries can provide the solutions for single use power source needs.
(Invited) Key Aspects in Enabling Lithium Metal Batteries
Authors: Meng Shirley
Published: November 2022

Lithium metal batteries hold the promise for next generation rechargeable batteries. The recent breakthroughs in electrolyte formation, pressure control algorithm and quantitative characterization tools have made this promise closer to reality. In this talk, I will provide an overview of those recent breakthroughs and share a few new perspectives on the surprisingly challenging issues in enabling rechargeable lithium metal batteries.
0D Physics-Based Modeling of High Energy Lithium Metal Batteries with Pulsing Requirements
Authors: Parke Caitlin D. , Harris Kailot , Albertus Paul
Published: November 2022

Lithium metal batteries are promising candidates for high energy storage solutions. To further increase capacity, electrolyte components can have a secondary function of storing charge through electrochemical reactions. This work focuses on modeling high-energy lithium metal anode and metal oxide cathode material and potentially other materials with additional capacity from electrolyte components. Physics-based modeling can be utilized to explore design space and predict battery performance under various conditions. This work utilizes a zero-dimensional model with thermodynamics, kinetics, transport, and morphology changes of the solution and solid-phase species. The effect of the additional electrolyte components on the transport, capacity, and voltage behavior will be explored. Pulse power will also be discussed, and this talk may include comparisons to experimental data.
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.
Novel Adsorption-Catalysis Design of CuO Impregnated CeO2 Nanorods As Cathode Modifier for Lithium-Sulfur Battery
Authors: Azam Sakibul , Wang Ruigang
Published: November 2022

Lithium sulfur batteries (LSBs) are a promising candidate to be used in modern commodities like electric vehicles, grid energy storage, electric aviation, and many others because of the exceptionally high theoretical capacity of sulfur (1675 mAh g-1), almost 5 times higher than the conventional lithium-ion batteries. However, the problem of polysulfide shuttling effect originating from the dissolved lithium polysulfides in the electrolyte results in poor cycling stability, hindering the commercialization of LSB. Significant advancement has been made over the years due to a great deal of research on novel materials development and structural design for lithium polysulfide (Li2Sn: 4≤ n ≤8) adsorption synergy to counter the polysulfide shuttling effect 1. However, rather than focusing only on the adsorption synergy (Physical confinement and chemical binding), novel catalysts that can accelerate the polysulfide conversion reaction kinetics are needed to design the next generation LSB. Previously, our group investigated shape-controlled cerium oxide (CeO2) to accelerate the polysulfide conversion reactions by generating the intermediate steps of thiosulfate and polythionate 2, 3. Copper oxide (CuO), being a p-type semiconducting material, is another promising material that can activate thiosulfate formation as its redox potential is 2.53 V vs Li/Li+, which lies in the potential window of 2.4 V < E° ≤ 3.05 V that selectively triggers the formation of thiosulfate. Herein, we investigated 10 wt% of CuO impregnated on the CeO2 nanorods (10 wt%CuO/CeO2) as a cathode host for LSB. The CuO impregnation on the surface of CeO2 nanorods attributed strong interaction between the surface defect rich CeO2 nanorods and the copper oxides (CuOx: Cu2O and CuO) promoting excellent electrocatalytic activity. The 10 wt%CuO/CeO2 sample provides adsorption-catalysis dual synergy to chemically bind and further catalyze the polysulfide conversion by polythionate and thiosulfate generation. As a result, the derived LSB exhibited excellent electrochemical performance with high capacity of 1141 mAh g-1 at 0.2 C with a sulfur loading of 1.33 mg cm-2 and a capacity loss of only 0.04% per cycle after 60 cycles.

Key words:
lithium sulfur batteries, lithium polysulfides, shuttle effect, cerium oxide, catalysis.

Xiong, D. G.; Zhang, Z.; Huang, X. Y.; Huang, Y.; Yu, J.; Cai, J. X.; Yang, Z. Y., Boosting the polysulfide confinement in B/N–codoped hierarchically porous carbon nanosheets via Lewis acid–base interaction for stable Li–S batteries. Journal of Energy Chemistry
2020,
51, 90-100.

Azam, S.; Wei, Z.; Wang, R., Cerium oxide nanorods anchored on carbon nanofibers derived from cellulose paper as effective interlayer for lithium sulfur battery. J Colloid Interface Sci
2022,
615, 417-431.

Wei, Z.; Li, J.; Wang, R., Surface engineered polar CeO2-based cathode host materials for immobilizing lithium polysulfides in High-performance Li-S batteries. Applied Surface Science
2022,
580.
R&D in Primary and Secondary Lithium Metal Batteries
Authors: Xiao Jie
Published: November 2022

Electrochemical energy storage has been a very hot topic in the last decades. Many efforts have been pursued in identifying new battery materials and technologies for a broad range of applications such as grid energy storage, vehicle electrification, mobile electronics and so on. This talk will highlight the importance of this interdisciplinary research and emphasize the urgent to identify and address real challenges at relevant scales for battery R&D. Both secondary and primary Li metal batteries will be discussed in this talk.
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.
Electrodeposition of Cu-Based Nanofoams and Sodiophilic Metals for Highly Stable Anode-Free Sodium Batteries
Authors: Accogli Alessandra , Bertoli Luca , Mellina Gottardo Alessandro , Panzeri Gabriele , Magagnin Luca
Published: November 2022

Sodium-ion batteries (SIBs) represent a cost-effective and sustainable alternative to lithium-ion battery (LIBs).1 One of the main issues of SIB technology is the higher ionic radius of sodium, compared to lithium, which limits the cyclability due to unfavourable intercalation of Na+ ions into carbon-based anodes.2 Anode-free batteries represents a promising approach to improve the cyclability, changing the working principle at the anode from intercalation of Na+ ions to electrodeposition metallic sodium.3 Moreover, thanks to the anode-free configuration the energy density of the overall device can be drastically increased. To efficiently control the electrodeposition of the metallic layer of sodium, the current collector must be carefully designed. Copper nanofoams were produced by dynamic hydrogen-bubble template (DHBT) as high-surface area template for the sodium electrodeposition, as an innovative alternative to the traditionally flat electrodes. The electrodeposition of sodiophilic materials, i.e. tin and antimony, onto the nanofoam, was also investigated to control the nucleation of the metallic layer at the anode.4 Sn and Sb baths were optimized to guarantee an homogeneous distribution of the sodiophilic metal on the nanofoam. The morphology and the composition of the nanofoams was characterized and electrochemical characterization was performed in half-cell configuration, showing coulombic efficiency higher than 99% and good cyclability for 100 cycles, for both Sn and Sb compositions compared to the bare Cu. This demonstrates the feasibility of the usage of sodiophilic nanofoams as current collectors in anode-free sodium batteries.

Vaalma, C., Buchholz, D., Weil, M. & Passerini, S. A cost and resource analysis of sodium-ion batteries. Nat. Rev. Mater. 2018 34
3, 1–11 (2018).

Irisarri, E., Ponrouch, A. & Palacin, M. R. Review—Hard Carbon Negative Electrode Materials for Sodium-Ion Batteries. J. Electrochem. Soc.
162, A2476–A2482 (2015).

Cohn, A. P. et al. Rethinking sodium-ion anodes as nucleation layers for anode-free batteries. J. Mater. Chem. A
6, 23875–23884 (2018).

Seh, Z. W., Sun, J., Sun, Y. & Cui, Y. A highly reversible room-temperature sodium metal anode. ACS Cent. Sci.
1, 449–455 (2015).
(Invited) Impact and Perspective of Electrodeposited Nanostructured Materials for Energy Applications
Authors: Toimil Molares Maria Eugenia
Published: November 2022

During the last decades, researchers have demonstrated in many inspiring and creative ways that electrodeposition is an essential and versatile technology to fabricate tailored nanostructures relevant to many different applications. The combination of excellent know-how on how electrodeposition parameters influence and control the composition, morphology and structure of the resulting materials, as well as applying inventive approaches using tailored and complex substrates, templates, and new methodologies, have resulted in a plethora of three-, two-, one- and zero-dimensional materials and coatings of many different compositions and combinations. This talk will provide an overview of remarkable advances achieved in designing and synthesizing nanostructured materials by electrodeposition, especially for energy applications, such as electrodes for batteries, photo- and electrocatalysis, and thermoelectrics, and discuss the upcoming perspectives and challenges in the field.
Ruthenium Doped Lscf Based Cathode for Enhanced Performance of Solid Oxide Fuel Cells
Authors: Ullah Abid , Hussain Syed Sajid , Hussain Basharat
Published: November 2022

Recently, a tremendous upsurge in the research of Solid oxide fuel cells (SOFCs) has been documented due to cheap electricity production and without harming the environment. The development of efficient SOFCs requires more robust cathode for oxygen reduction. Until yet a copious amount of research has been done on varieties of materials including LSCF. In this work, Ruthenium is doped on the LSCF forming nanostructured Ru-LSCF with various Ru stoichiometric quantities. The Ru-LSCF catalyst is prepared via simplistic technique “Glycine combustion process”, producing evenly embedded Ru in LSCF perovskite materials leading to increased oxygen reduction reaction (ORR). The nanostructured Ru-LSCF cathode showed polarization resistance of approximately 0.031 Ωm2 at 750 0C. The peak powers of approximately 1760.5, 1480.1, 893.3 mW/cm2 were recorded at 750, 700, and 650 0C, respectively. Ru LSCF was quantitatively optimized for enhanced power production with high precision calculation. The results show that the Ru-LSCF optimum fabricated nanostructured cathode is promising catalyst for the reduction of oxygen at the cathode side for highly durable SOFCs.
Electrodeposition of Metal Alloy Carbon Composites for the Electrochemical Detection of Methylene Blue and Pyocyanin
Authors: Bahrololoomi Arash , Podlaha Elizabeth J.
Published: November 2022

Electrodeposited nickel-iron nanoclusters and nickel-iron-graphene oxide onto a carbon electrode was fabricated to enhance charge transfer while at the same time permitting adsorption of organic molecules to the carbon surface. Ni–Fe and Ni–Fe–graphene oxide were prepared from a sulfate-boric acid and sulfate-boric acid-graphene oxide water dispersion electrolyte at a pH of 3 by a pulse galvanostatic method onto a glassy carbon disk electrode. Electrochemical impedance spectroscopy (EIS) was conducted on the Ni–Fe/glassy carbon and Ni–Fe–graphene oxide/glassy carbon composite electrodes in a phosphate buffer solution (PBS) containing various concentrations of methylene blue (MB) or pyocyanin (PYO). MB is used as a dye and is a pollutant, and can serve as a comparable model for PYO due to similar structure and redox potential. PYO is a metabolite of the Pseudomonas aeruginosa, a gram-negative bacterium, associated with disease in humans responsible for chronic infection in people with cystic fibrosis and in burn patients; thus its detection is of interest. The RsC parameters determined from EIS equivalent circuit models for the interfacial region of the Ni–Fe/glassy carbon electrode with an aqueous electrolyte containing MB or PYO had a larger signal as the analyte concentration decreased, in contrast to conventional voltammetry techniques. The fractional adsorption with concentration for MB followed a Langmuir adsorption isotherm, the adsorption energy determined, and compared with PYO. The electrode fabricated with graphene oxide in the electrolyte increased the RsC value under PYO detection.
(Digital Presentation) Fundamental Insights into Electrodeposition of Mixed Chromium Metal-Carbide-Oxides from Trivalent Chromium – Formate Electrolytes
Authors: Ankora Maxine , Mamme Mesfin Haile , Lammers Koen , Wijenberg Jacques , de Vooys Arnoud , Terryn Herman Albert , Mol Arjan
Published: November 2022

Recent restrictions on industrial usage of hexavalent chromium under new REACH legislation have further sparked the development of hexavalent chromium-free chromium plating processes. An industrially important development in this field is Trivalent Chromium Coating Technology (TCCT®), a chromium electroplating technology for packaging steel developed at Tata Steel. In this process, aqueous trivalent chromium electrolytes rather than hexavalent chromium electrolytes are employed for the electrodeposition of metallic chromium. However, to deposit metallic chromium from a trivalent chromium electrolyte, it is necessary to incorporate a complexing agent given the kinetic inertness of aqueous trivalent chromium complexes. Formate plays this role in the TCCT® process yielding coatings comparable to the conventional hexavalent chromium-based process [1-4].

However, understanding the mechanism and kinetics of chromium electrodeposition from this system is quite limited. Fundamental knowledge of the deposition process is key for industrial process optimization. Essential to determining the reaction mechanism and kinetics is the identification of the chemical species involved in the reaction. Using a hybrid multiscale experimental and computational approach, insights into chromium complexation in the bulk electrolytes and how this speciation influences the composition of the deposit have been gained.

Samples electroplated in electrolytes of varied formate concentrations were characterized using X-ray Fluorescence (XRF) spectroscopy and X-ray Photoelectron Spectroscopy (XPS). Results from these analyses show that metallic chromium is only deposited when the electrolyte contains formate ions. In the absence of formate, only oxide and carbide species are deposited. The characterization results also show a current efficiency of the TCCT process of ~ 40%. From observations from surface characterization as well as spectroscopic analysis and density functional theory (DFT) and ab initio molecular dynamics studies (AIMD) of the bulk electrolyte, the coordination and complexation of formate ion in the chromium complex responsible for metallic chromium deposition have also been identified. Voltammetric studies coupled with ex-situ XPS and scanning electron microscopy (SEM) surface characterization also lead to a clear definition of the reaction mechanism of metallic chromium deposition that the incorporation of formate in trivalent chromium electrolytes makes possible.
Study on Thermoelectric Property of Te Wire-Based Organic-Inorganic Hybrid Thermoelectric Composites through Electrochemical Process
Authors: Lee Min-Jeong , Kim In Yea , Kim Chae Yoon , Lim Gi hwan , Kim Jaehun , Kim Dong Hyun , Lim Jae-Hong
Published: November 2022

Energy demand and importance are increasing with the industrial development and the development of high technology in modern society. However, the global supply of energy is facing problems such as fossil energy depletion and environmental pollution, and research and interest in alternative energy are increasing. Among them, research on thermoelectricity is being actively conducted. The thermoelectric characteristics are represented by the Seebeck coefficient, electrical conductivity, and thermal conductivity at the operating temperature. This is expressed as a thermoelectric performance index (ZT). ZT appears in proportion to the electrical conductivity and Seebeck coefficient, and inversely proportional to the thermal conductivity. Thermoelectric materials are divided into inorganic thermoelectric materials and organic thermoelectric materials, both of which have advantages and disadvantages. The inorganic thermoelectric material has high thermoelectric performance, but it is highly toxic and has low electrical conductivity. On the other hand, organic thermoelectric materials have lower performance than inorganic materials they are easy to obtain and have high electrical conductivity. In this study, organic-inorganic hybrid thermoelectric material was studied by combining the advantages of each material.

In this study, Te nanowires (NWs) were synthesized at 50 Co by galvanic replacement reaction. We used Si (1 0 0) wafer as substrate of NWs. The substrate was degreased with acetone and ethanol. The solution of cadmium(1M), hydrofluoric acid (HF 51.0%, 4.5M) and tellurium dioxide (TeO2, 2mM). After the reaction, the synthesized Te NWs were washed with deionized water and IPA. The prepared Te NWs reacted with solution (silver nitrate in ethylene glycol) for topotactic reaction. After the reaction, the wires are washed several times with ethanol. The hybrid TE was fabricated by coating PEDOT:PSS on Ag-Te NWs with different ethylene glycol (EG) doping.

A composite thermoelectric material was manufactured using Te (inorganic thermoelectric material) and PEDOT:PSS (organic thermoelectric material). Ag-topotactic reaction was conducted to increase the electrical conductivity of NWs. As the EG doping concentration of PEDOT increased, the electrical conductivity because the layer of PEDOT:PSS became thinner and didn’t fill the gap of NWS sufficiently. In conclusion, the Te NWs coated with PEDOT:PSS with 10% EG doping showed the best electrical conductivity and power factor. The more details will be presented.

Figure 1
Toward "Electrochemical/Materials Processing for Space Engineering" Symp
Authors: Fukunaka Yasuhiro
Published: November 2022

Several symposium have been hosted such as “Electrochemistry in Space”, 236th ECS Atlanta(2019) and “ISRU”, Call for Papers: ACS Earth and Space Chemistry for Special Issue: Materials of the Universe : the Final Chemical Frontier(2020). However, their scopes are rather shifted to space exploration concept, primarily led by the Space Agency. Those are not geared toward training graduate students for the future space engineering using basic science, especially Space Environmental Utilization Research is not intensively covered. It is our thought that the Electrochemical Society (ECS) shall organize such an interdisciplinary education & research program collaborating with TMS society (Light Metal and Materials Processing Divisions). The research subjects on Space Energy & Resources must be newly stimulated to make recognize and support the field of Electrochemical/Materials Processing, encompassing:

[1] Basic Science with Drop Tower, Rocket & ISS

(for example: Nucleation & Growth of Ice in Space, Gas Electrode Behavior)

[2] Microgravity Research like Protein or Semiconductor Crystallization

[3] Energy Conversion and Storage System for Space Engineering

(Unitized Regenerative FC), LIB, Nuclear Battery)

[4] Sensor System for Rover Eng. & X-ray Astrophysics

[5] Life Supporting System including Desalination Technology and CO2 Reduction

[6] ISRU, Materials Processing/Thermodynamic Measurement with ELF

[7] Computational Chemistry/Interfacial Reaction Dynamics

[8] Ion Transfer through Cell Membrane in Bio-physics

[9] Global Environmental Observation System

[10] Others
Insights into Cu Surface Chemistry Via in-Operando nanoparticle Enhanced Vibrational Spectroscopy and Mass Spectrometry Measurements
Authors: Raciti David , Tackett Brian , Braun Trevor Michael , Hight Walker Angela , Moffat Thomas P
Published: November 2022

Copper electrodeposition is a central process in the metallization of microelectronics and more recently has found use as an important electrocatalyst in the conversion of CO2 to hydrocarbons. Gaining mechanistic insight into the nature of the respective reactions requires in situ and better still in operando measurements. Herein the utility of shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) and electrochemical mass spectrometry (EC-MS) to study the potential dependent anion adsorption and hydride formation on low index Cu single crystals surface will be detailed. SHINERs enables monitoring of competitive adsorption between Cl- and SO4
2- on Cu(100) and Cu(111) surfaces (Figure 1a). Saturated ordered halide adlayers are formed at potentials slightly below the open circuit potential while moving to more negative values halide is disrupted resulting with the emergence of a sulfate mode near 970 cm-1. In the case of Cu(111) the desorption of the halide adlayer is coupled to the formation of a hydride phase (Figure 1b) as evident in both SHINERS and EC-MS measurements. SHINERS was also employed to examine the adsorbate dynamics associated with superconformal electrodeposition of Cu. Specifically, competitive adsorption between Cl- and sulfonate terminated thiol/disulfide accelerators molecules was examined during Cu deposition on planar and patterned surfaces (Figure 1c). The ability of the nanoparticle reporters to float on the advancing surface is demonstrated and used to probe the additive evolution on the growth front associated with superconformal electrodeposition. This work demonstrates the capabilities of operando electrochemical measurements and their importance in achieving future technological breakthroughs.

Figure 1. Capturing Cu interfacial chemistry with operando SHINERS (a) on a c(2x2)-Cl covered Cu(100) surface, (b) coupling to EC-MS to reveal the existence of hydride on Cu(111) in Cl containing electrolyte and (c) to track accelerator coverage on electrodeposited pattern surfaces.

Figure 1
Compressive Stress and Charge Redistribution during CO Adsorption Onto Pt
Authors: Stafford Gery , Schwarz Kathleen , Vinson John , Raciti David
Published: November 2022

Electroorganic reactions, where energy is either stored or released from chemical bonds within carbon-based molecules, are essential to help achieve a circular carbon-based economy. Central to electrochemical conversion of organic molecules is carbon monoxide (CO), which serves as both an intermediate in electrochemical CO2 reduction to hydrocarbons and electrochemical oxidation in fuel cells that operate via oxygenated hydrocarbons (e.g., ethanol, methanol). For the latter, Pt has been the predominate catalyst of choice, and substantial effort has been spent to identify the mechanistic details for complete oxidation of alcohol-based fuels. With CO conversion serving as an important if not rate-limiting step of the oxidative process, it is critical to understand the state of a catalytic surface when CO is present.

The change in surface stress associated with the adsorption and oxidative stripping of CO on (111)-textured Pt is examined using the wafer curvature method in 0.1 mol/L KHCO3 electrolyte.1 The curvature of the Pt cantilever electrode was monitored as a function of potential in both CO free and CO-saturated electrolyte. Although CO adsorbs as a neutral molecule, significant compressive stress, up to -1.3 N/m, is induced in the Pt. The magnitude of the stress change correlates directly with the CO coverage, and within the detection limits of the stress measurement, is elastically reversible. Density functional theory calculations of a CO bound Pt surface indicate that charge redistribution from the first atomic layer of Pt to subsurface layers account for the observed compressive stress induced by the charge neutral adsorption of CO. A better understanding of adsorbate-induced surface stress is critical for the development of materials platforms for sensing and catalysis.

References

D. Raciti, K.A. Schwarz, J. Vinson, and G.R. Stafford, The Journal of Physical Chemistry C , 126, 4446-4457 (2022).
Machine Learning Lithium-Ion Battery Safety Risk Level Classification
Authors: Jia Yikai , Xu Jun
Published: November 2022

Due to inevitable external mechanical abusive loadings, lithium-ion batteries (LIB) will suffer damages or defects. If the safety risk level of the cell is unknown, an early decision cannot be made. In this work, we develop a Random Forest (RF) based classification model to implement online safety risk level classification with low time cost and high accuracy. Four levels of battery cell safety risk are defined: a). Normal; b), Latent risk (defective cells, short circuit but normal operation); c). Low risk (short circuit without possible TR triggering); d). High risk (short circuit with possible TR triggering). The training dataset combines experimental data and simulation data from the multi-physical model. The training samples consist of voltage, current, and temperature signals under different operating conditions and different risk level scenarios. The prediction results show that the classifiers have a good performance and robustness. This approach will provide insight into the identification, monitoring, and early warning of battery safety issues.
(Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award) Electrochemically Grown Highly Textured Thick Ceramic Oxide Films for Energy Storage: A New Manufacturing Paradigm for Cathode Materials
Authors: Patra Arghya , Braun Paul V.
Published: November 2022

Electrochemical synthesis of materials has contributed to significant breakthroughs in materials processing by replacing high temperature, cost and energy intensive pyrometallurgical processes. Noteworthy examples include aluminum extraction by Hall–Heroult process, electrowinning of copper, titanium extraction through the Kroll process, electrolytic production of steel, and electrochemical synthesis of cement. Increasing the energy and power density of alkali ion intercalated transition metal oxide cathodes which power electric cars and portable electronics, has been a growing topic of global techno-economic interest. Our work demonstrates a direct electrodeposition of thick ternary ceramic oxide films as an alternate scalable manufacturing technique for fabrication of binder-and-additive free cathode materials for secondary battery. Employing an intermediate temperature (200-400°C) molten hydroxide-based electrodeposition method, a general electrochemical growth strategy for multiple Li and Na ion cathode chemistries is demonstrated for the first time including NaCoO2, NaMnO2, LiCoO2, Li2MnO3, LiMnO2, LiMn2O4, (A. Patra, P.V. Braun et. al, PNAS, 2021) in a thick (> 50 µm) thick film form factor. In-plane and through-plane texture can be electrochemically architectured in LiCoO2 and NaCoO2 films across multiple textures: <003>||ND (Li/Na ion blocking sites parallel to the normal direction), <101>||ND, <104>||ND, <110>||ND (fast lithium ion conducting sites parallel to the normal direction). An accurate control of crystallization dynamics leads to highly anisotropic, grain boundary engineered structure with low tortuosity and fastest electron and Li ion conducting pathways (<110>||ND) oriented normal to the current collector. The highly textured (<110>||ND), dense (>95%) electroplated cathodes can perform even at ultrahigh thickness of ~ 200 µm (areal capacity of ~13.6 mAh/cm2) in comparison to 40-60 µm for conventional slurry cast cathodes (areal capacity of ~3-4 mAh/cm2 with a porosity of ~10-20%), a fivefold increase in areal capacity and volumetric energy density (A. Patra, P.V. Braun et. al, to be submitted). In order to enable a high voltage (> 4.5 V vs. Li) cathode design, a functionally graded architecture is also demonstrated with a core capable of providing high-capacity and rate capability (LCO <110>||ND); and multiple capping layers (LCO <003>||ND and Li2MnO3) to suppress harmful side reactions occurring at voltages beyond the normal operation range (beyond 4.2 V vs. Li). Our work paves the way towards an electrosynthesis platform for functional oxides with the ability to generate micron scale ordering with controllable in-and-through-plane orientation in thick ceramic oxide films important for electrochemical energy storage.
Electrochemical Immobilization of Arsenic
Authors: Repukaiti Reyixiati , Diaz Aldana Luis , Lister Tedd
Published: November 2022

Arsenic handling and immobilization are critical issues in the mining of sulfarsenide minerals, due to arsenic’s toxicity to the environment. Significant amount of arsenic can be present in Cu, Zn, Ni, and Co minerals. Cobaltite (CoAsS) for example, is one of those sulfides from which cobalt can be mined as the primary mineral. However, cobalt extraction from cobaltite generates equivalent mass of arsenic per extracted cobalt. To unlock the domestic cobalt production, efficient arsenic immobilization techniques are needed. Compared to traditional hydrometallurgical and pyrometallurgical processes, an electrochemical method is proposed to efficiently immobilize arsenic from cobaltite. An electrochemical cell was assembled to promote the immobilization of arsenic, in the presence of iron, via the precipitation of crystalline scorodite (FeAsO4 · 2H2O). Various electrochemical mechanisms were studied to maximize the oxidation and precipitation rates, such as galvanostatic and potentiostatic techniques. Results using both surrogate solution of arsenic, iron, and cobalt, as well as cobaltite solution show high immobilization rates of arsenic.
(Invited) Molecular Design for Reactive Redox Separations
Authors: Luca Oana , Petersen Haley
Published: November 2022

This talk presents the rational molecular design of next-generation redox-active sorbents for the capture of carbon dioxide from dilute sources such as air. We discuss the electrochemical generation of organic nucleophiles (C and O-nucleophiles), with a focus on chemical species known to rapidly capture CO2 under cathodic conditions, and that release the bound CO2 under anodic conditions. We first introduce the thermodynamics of redox-reactive CO2-binder chemical space for electrochemical reactive capture and release of CO2 by electrochemically-generated nucleophiles. We then use this thermodynamic understanding to guide the synthetic development of new robust redox-reactive media for the capture of CO2 from dilute sources that take advantage of the beneficial bulk properties of ionic liquids and the well-established redox chemistries of reduced quinones.
Electrochemical Recovery and Concentration of Noble Metals
Authors: Cotty Stephen Richard , Su Xiao
Published: November 2022

Noble metals are integral materials to chemical and electronics industries for their unmatched chemical inertness, electrical conductivity, and catalytic activity. However, the growing demand for noble metals such as Pt, Pd, and Au is outpacing the dwindling supply, and without new recycle strategies these critical noble metal resources will run out. Therefore, energy and resource efficient noble metal recycling technologies are critical to develop sustainable use of these scarce and valuable resources. Recently, electrification of chemical process units has been receiving justifiable attention as an easily scalable means of increasing energy and material sustainability in industry, particularly for chemical separations. In particular, the incorporation of redox-active materials has been met with great success for chemical energy storage and chemical separations due to enhanced charge transfer and easily tunable target ion interactions. Here, we introduce an electrochemically mediated platform for capture, release, and up-concentration of noble metal complexes from mining ore, electronic waste, and valuable elements in industrial manufacturing, where favorable charge transfer binding of noble metals to electrode bound redox sites enables selective capture of target noble metals over other common competitors – all with the flick of a switch. Highlights of our system are its high uptake (>200 mg/g), selectivity (>5 vs competing ions), energy efficiency (<5 kJ/g-PGM), cyclability (>5000 reuse cycles), and scalability to flow system. Technoeconomic analysis of our system compared to current industrial separation technologies indicates economically significant improvements in capital and operating costs with our electrochemical noble metal recycling platform. By lowering the economic barrier of noble metal recycling, these critical materials can be sustainably used and reused for years to come.
Comprehensive Evaluation of Affordable Cathode Materials in Direct Electrochemical Selenite Reduction
Authors: Yang Zilan , Zhao Jiaxiang , Sullivan Graf , Zou Shiqiang
Published: November 2022

Selenium (Se) is a naturally occurring metalloid that has been widely sourced for health care, clean energy technology development, and agricultural activities. These activities have accelerated Se release into the aquatic environment, urging engineered solutions to mitigate aquatic Se pollution and their ecological impact. Our lab previously demonstrated a direct electrochemical reduction approach to convert 97% of soluble selenite into elemental Se(0) on a gold cathode. This study builds upon our prior success in selenite separation to further explore alternative cathode materials to gold. Six economically competitive materials (Ni, graphite, Cu, Fe, stainless steel, and Ti) were evaluated for key performance parameters, including Se removal efficiency, Faradaic efficiency, energy consumption, and electrode durability. Preliminary cyclic voltammetry scans revealed that Ni and graphite could sustain Se(IV)/Se(0) reduction in diluted water matrices within their electrochemical window. The subsequent 24-h chronoamperometry (CA) test demonstrated 67% selenite removal using a Ni cathode, while graphite offered a better removal efficiency (92%). Separated selenite ions were primarily plated as elemental Se(0) on the cathode surface (Ni & graphite) or within the electrode structure (graphite). While graphite has better selenite removal than Ni, it demands more energy input and has lower Faradaic efficiency (C-3.7% vs. Ni-12.7%). Switching from a CA mode to a chronopotentiometry (CP) mode did not significantly impact selenite removal performance, and the energy consumption was increased by 15%. Continued exfoliation is observed on the graphite electrode surface, potentially due to the expansion of inner gas bubbles and the lattice destruction caused by Se(0) insertion. Our results suggest graphite offers comparable selenite separation performance to a gold cathode. Still, electrode exfoliation and higher energy input due to parasitic reactions must be appropriately addressed in future research efforts.