bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enabling Rhenium Electrodeposition in Water-in-Salt Electrolytes through Isolated Anodic Reactions
Authors: Rutledge Amanda , McBride Michael , Hooks Daniel E 
Published: August 2024

Perfluorosulfonic Acid (PFSA)/Polytetrafluoroethylene (PTFE) copolymer and cation-exchange membranes were used to elongate the use water-in-salt electrolytes for rhenium electrodeposition. Water-in-salt electrolytes are a common technique used to minimize the amount of free water in solution by including high concentrations of salts, thus solvating the water molecules and lowering activity of the solution. This expands the electrochemical window in which deposition is possible and minimizes unnecessary hydrogen evolution reactions (HER) in the electrodeposition system by reducing available protons.
Lithium chlorine (LiCl) is a common salt for this purpose due to low costs. However, in the LiCl electrolyte, the necessary oxygen evolution reaction (OER) competes with chlorine evolution, which increases water activity and is visually identifiable with a color change from clear to yellow. When chloride ions are depleted, further deposition is no longer possible, and the electrolyte breaks down.
A solution to this issue is using membranes to isolate the anode and cathode, thus preventing the chlorine evolution reaction from occurring. Since rhenium is a system with a small electrochemical window, possible oxide intermediates, and an overpotential for hydrogen evolution, the system requires the use of a stable water-in-salt electrolyte for elongated deposition.
In this experiment, three membranes were examined to compare the impact on rhenium depositions in an H-cell. To compare the impact of each membrane, the change of pH of the DI side of the H-cell was monitored across time alongside the volume changes on both sides of the H-cell as a function of time due to LiCl inclusion. The quality and thicknesses of the coatings was examined by SEM as well as the impact on the morphologies of the rhenium of the deposits between each of the membranes.
The Resurgence of Hydrogen Depolarized Anodes: A Catalyst for Change in Industrial Electrochemistry
Authors: Akuzum Bilen , Hackl Lukas , Bandaru Siva Rama Satyam , Pohlman Garrett 
Published: August 2024

This presentation delves into the remarkable history of Hydrogen Depolarized Anodes (HDAs) and their relevance to modern industrial electrochemistry. HDAs were originally developed in the early 1970s, but their use has been confined to fuel cell technology and power generation. In the wake of a growing green hydrogen economy and the escalating price of precious metal catalysts, this technology is now emerging as a useful tool to boost the energy efficiency and lower both capital and operational costs of electrified chemical manufacturing processes. Our discussion recounts the evolution of HDA technology, from its conceptual beginnings to its current role as an innovative solution in electrochemical processes.
The recent renaissance of HDAs is driven largely by economic and environmental factors. As chemical industries strive to electrify their processes, they also grapple with the rising cost of conventional anode materials. The increasing affordability and availability of hydrogen presents HDAs as a viable and efficient alternative. This shift is not just about cost-saving; it's about embracing a technology that aligns with the principles of sustainability and circular economy.
We will explore various applications where HDAs are making a significant impact, such as in the manufacturing of acids and bases, the production of metals such as iron, copper, and zinc, and more experimental processes such as cement production. These examples not only demonstrate the versatility of HDAs, but also underscore their potential in achieving higher energy efficiency than conventional technologies and reducing environmental footprint of a range of industrial operations.
Furthermore, our talk will illuminate how HDAs are a stepping stone towards a broader adoption of hydrogen as a cornerstone of industrial electrochemistry. The implementation of HDA technology is more than an innovation; it's a transformative step forward, signaling a new era in chemical manufacturing where sustainability and efficiency go hand in hand.
Minimize Energy Consumption of CO2 Release in a Flow Electrolyzer By Optimizing Direct Air Capture Solvents
Authors: Xin Gao , Omosebi Ayokunle , Patrick Aron , Liu Kunlei 
Published: August 2024

Under the 2015 Paris Agreement, almost 200 nations have committed to the global goal of limiting the rise in average temperatures to 2.0 °C above preindustrial levels, with an even more ambitious aim of striving for 1.5 °C. Achieving the 1.5 °C objective requires a 45% reduction in global greenhouse gas emissions by 2030, ultimately reaching net-zero emissions by 2050. Numerous industries are increasingly making commitments to combat climate change by minimizing their CO2 emissions. However, certain sectors face challenges due to the current high costs associated with emissions reduction through available technologies, though these costs are expected to decrease over time. Moreover, in specific industries like cement production, there are emissions sources that cannot be entirely eliminated, such as those arising from the inherent calcination process. Given these constraints, realizing the emissions reduction pathway to the 1.5 °C target requires the adoption of negative emissions processes, including technologies like direct air capture (DAC), to actively remove CO2 from the atmosphere.
The operational concept of the DAC process explored in this study is based on the utilization of both the solvent-based method and alkaline water electrolysis. This involves regenerating the solvent through pH fluctuations generated by a carbonate electrolyzer. As depicted in Figure 1, the consumption of OH- ions during O2 evolution leads to a decrease in pH at the anolyte loop, while the production of OH- ions through water splitting causes an increase in pH at the catholyte loop. Consequently, the lowered pH environment facilitates the release of CO2 gas from dissolved carbon species such as CO32-, while the heightened pH environment promotes the formation of alkaline hydroxides for carbon capture in an air absorber.
In this work, we will aim to analyze the energy consumption per mole of CO2 released from the anolyte loop of a flow electrolyzer. Utilizing a combination of theoretical predictions and experimental validations, significant insights were obtained for optimizing the DAC solvent. This optimization involves minimizing energy consumption by adjusting alkalinity levels and incorporating supporting electrolytes.

Figure 1
Observing Electrochemical Performance Trends with the Physical Scaling of Bipolar Membrane Electrodialysis for the Capture and Concentration of Atmospheric CO2
Authors: Crow Allison M , Shin Grace , Deutsch Todd G , Smith Wilson A 
Published: August 2024

Bipolar membrane electrodialysis (BPMED) is a proven technology for separating ionic species driven by electrochemical potential through ion conductive membrane separators. When using a bipolar membrane (BPM) as the separator, a pH gradient is created by the generation of acid and base via water dissociation at the internal interface of an anion conductive and a cation conductive membrane. BPMED can been used for the capture and concentration of atmospheric CO2, for example when using a liquid alkaline capture sorbent, where the acidification of the capture stream can be used to regenerate pure CO2 while further basification of the remaining effluent regenerates the alkaline capture sorbent to be re-used in the direct air capture process. Current commercial BPMs require high overpotentials to drive water dissociation and can only operate at low to moderate current densities. While considerable work has gone into the development of efficient, electrochemically active BPMs through improved membrane polymer chemistries and high-activity water dissociation catalysts, little work has been done to physically scale up these materials and use them in electrodialysis-driven carbon capture and concentration systems beyond lab scale (i.e., >1 cm2).
In this presentation, we will report a scalable BPMED cell that can sense the resistive contributions of the individual membrane components (i.e., the anion exchange and cation exchange membranes, and the water dissociation at the internal BPM interface) with increasing membrane active area from 1 cm2 to 25 cm2. With this BPMED cell, changes in the BPM and water dissociation catalyst compositions and structures are related to electrochemical performance metrics (overpotential and CO2 recovery efficiency) at increasing physical scales. Electrochemical impedance spectroscopy (EIS) was used to reveal resistive contributions to the cell at increasing active area, while the inlet and outlet pH were measured to confirm the overall acidification and basification of the dialysis cell to promote carbon capture and conversion, as well as sorbent regeneration. This study aims to build a bridge between the necessary improvements in the membrane and water dissociation catalyst compositions with industrially relevant energy efficiency and conversion performance, accelerating the development of high performance BPMs.
Next Generation Lab-Scale Bipolar Membrane Electrodialysis Test System
Authors: Vulpin Olivia T. , Boettcher Shannon W. 
Published: August 2024

The world of electrochemical devices has witnessed remarkable progress in recent years, with particular emphasis on the development and advancement of bipolar membranes (BPMs). This progress has predominantly centered around BPM applications within membrane electrode assembly (MEA) systems, encompassing technologies such as fuel cells and electrolyzers. The exploration of BPM in these MEA systems has allowed for an almost complete elimination of the BPM overpotential for water dissociation and has dramatically changed the playing field and viability of BPM. This rapid advancement in understanding BPM fundamentals has in part come from the commercially available and universally utilized lab-scale electrolyzer/fuel cell systems. These devices have allowed labs around the world to focus on finite aspects of the BPM without being slowed by the debates of varying test stands.
With the development of advanced, MEA optimized BPM and increased understanding of BPM fundamentals, the time is right to embark on the next phase of BPM research. This next phase looks to expand the use of BPM to non-MEA systems, including CO2 sequestration systems, electrodialysis, brine remediation, organic acid/base production, and more. These non-MEA systems present unique challenges and opportunities that demand innovation. To begin the expansion of advanced BPM to non-MEA applications we present here a lab-scale BPM electrodialysis system that allows for small membrane sizes and full system monitoring. This system is cheap to build, highly modular, easy to operate, and allows for a wide range of non-MEA systems to be explored. With this, we hope to speed up the translation of advanced, MEA optimized BPM to non-MEA applications.
Design of Lithium Metal Anode and Other High-Capacity Alloy Anodes Solid-State Batteries in Context of Contact Loss between Anode and Solid Electrolyte Separator
Authors: Molel Leshinka Leshinka , Fuller Thomas 
Published: August 2024

Cyclic volume changes and non-uniform electrodeposition/stripping, among other cycling-induced chemo-mechanical degradation of lithium metal and lithium-alloy solid state batteries, lead to contact loss between the anode and the solid electrolyte separator[1, 2]. In-operando experiments have shown ac-
celerated short-circuiting behavior due to contact loss in “anode-free” solid-state batteries[2]. Simulations reveal the relationship between active area fraction and the ratio of effective conductivities in made-up active area configurations[3]. Through modeling experiments using imputed active con-tact area of lithium-metal anode batteries, we quantify the effects of this contact loss in terms of accelerated chemo-mechanical degradation and de-creased rate capability. Specifically, we (1) quantify the interfacial resistance due to this contact loss, (2) show non-uniform local current density distribution such that local current densities could exceed lithium filament growth critical current densities, (3) show uniaxial stress inhomogeneity due to non-uniform reaction at the anode/separator interface, and (4) show non-uniform reaction distribution at the positive electrode.
Besides allowing for the optimization of designs to minimize contact loss, our work sheds light on tradeoffs in the design of solid electrolyte separators.

References

[1] John A. Lewis, Francisco Javier Quintero Cortes, Yuhgene Liu, John C. Miers, Ankit Verma, Bairav S. Vishnugopi, Jared Tippens, Dhruv Prakash, Thomas S. Marchese, Sang Yun Han, Chanhee Lee, Pralav P. Shetty, Hyun Wook Lee, Pavel Shevchenko, Francesco De Carlo, Christo-pher Saldana, Partha P. Mukherjee, and Matthew T. McDowell. Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography. Nature Materials, 20(4):503–510, 4 2021.
[2] John A. Lewis, Stephanie E. Sandoval, Yuhgene Liu, Douglas Lars Nelson, Sun Geun Yoon, Runzi Wang, Ying Zhao, Mengkun Tian, Pavel Shevchenko, Emilio Martı́nez-Pañeda, and Matthew T. McDowell. Ac-celerated Short Circuiting in Anode-Free Solid-State Batteries Driven by Local Lithium Depletion. Advanced Energy Materials, 2023.
[3] Evans Leshinka Molel and Thomas F. Fuller. Application of Open-Source, Python-Based Tools for the Simulation of Electrochemical Systems. Journal of The Electrochemical Society, 170(10):103501, 10 2023.
(Invited) Trials and Tribulations on Scaling Metal Recovery Technology from Lab to Market
Authors: Lippert Cameron , Landon James , Rassoolkhani Alan , Boehme Lindsay 
Published: August 2024

PowerTech Water, Inc. d/b/a ElectraMet (ElectraMet) is a cleantech company founded in 2014 in Lexington, KY with the goal of applying carbon and electrochemistry to solve fundamental challenges in wastewater and process water applications. There exists a broad array of separation applications that could be tackled through electrochemical routes, and ElectraMet has worked on many of them.
Early in ElectraMet’s history, focus was directed towards salt removal applications such as salt-free water softening, brackish water desalination, and ultra-pure water production. While some traction was found in these spaces, penetration of a new technology versus entrenched incumbents such as reverse osmosis and distillation made the sales process difficult. Limitations in what the technology could and could not do were also determined. Therefore, within the first few years of operation, focus shifted towards particular customer pain points, specifically metals separation applications. Problematic metals concentrations are present in drinking water, industrial effluents, and storm runoff, just to name a few. As a growing but still small business, it is important to choose a beachhead market where you can have the strongest value proposition, and electrochemical separations of metals offered a unique opportunity to solve challenges in the metals separation space. Therefore, considerable work has gone into developing these separation processes for specific metals and specific markets.
In this talk, the early history of the company will be reviewed, including technology, funding, and market applications. The impact of strategic advisors and early successes will be discussed with regards to the direction of the company. Ultimately, product-market-fit and the strategies and struggles in building a small business will be presented. Efforts will be made to highlight possible pitfalls, roadblocks, and opportunities as seen through this particular journey.
(Invited) Achieving Circularity in the Battery Industry through Salt Splitting Electrolysis
Authors: Akuzum Bilen , Hackl Lukas , Pohlman Garrett , Bandaru Siva Rama Satyam 
Published: August 2024

In an era focused on sustainability, Aepnus Technology introduces a transformative approach in electrochemical engineering that enables circularity in the manufacturing of battery chemicals. Aepnus’ innovation centers on advanced gas diffusion electrodes (GDEs), engineered to significantly boost efficiency and lower the costs of electrolytic salt splitting processes. GDEs offer a cost-effective alternative to traditional planar electrodes, and open new reaction pathways for versatile product generation. For example, GDE’s can improve on the incumbent technologies capable of converting sodium sulfate waste into useful chemicals such as sodium hydroxide and sulfuric acid. Aepnus’ GDEs are poised to revolutionize the recycling of sodium sulfate, the largest waste product of the lithium battery supply chain.
The application of these GDE’s can extend into the synthesis of various metal hydroxides and other essential commodity chemicals. Aligning with the principles of circular economy and eco-manufacturing, our project addresses challenges in electrolyzer design, catalyst advancement, and reactor optimization. We underscore the translation from academic research to scalable solutions, integrating our technology seamlessly into existing industrial processes.
This presentation will delve into the environmental and operational advantages of Aepnus GDEs, their role in reducing the ecological footprint of chemical manufacturing for the battery industry, and our journey to manufacture chemicals in ways that are circular and carbon neutral. Additionally, we will provide insights into the setbacks of existing electrochemical technologies such as membrane electrolysis and bi-polar electrodialysis (BPED), while demonstrating the real-world applicability of our technology through performance data at lab and pilot-scales.
(Invited) Accelerated Three Electrode Cell (TEC) Testing for Optimizing Electrodes in Conventional Alkaline Electrolysis and Anion Exchange Membrane Water Electrolysis
Authors: Abellán Gonzalo , Lloret Vicent , Seijas Da Silva Alvaro 
Published: August 2024

The merging of conventional Alkaline Electrolysis (AEL) and Proton Exchange Membrane Water Electrolysis (PEMWE) has led to the development of Anion Exchange Membrane Water Electrolysis (AEMWE). At this juncture, both AEL and AEMWE technologies offer an advantage over PEMWE as they do not require critical raw components and materials (CRM).[1] While AEMWE has demonstrated higher efficiencies than AEL with thin membranes and low concentrations of KOH, AEL technology addresses the significant stability challenge posed by anionic membranes by employing KOH electrolyte with novel zero-gap configurations, relying on stable diaphragms. Consequently, AEL technology offers a more cost-effective and scalable solution for current large-scale hydrogen production, while AEMWE remains a promising solution that will most probably be implemented on larger scales in the following decade. In any case, both technologies require more efficient and scalable catalysts for lowering the overall cell voltage of electrolyzers. Along this front, Matteco’s patented processes stand at the forefront of manufacturing highly active and stable catalysts and electrodes crafted from Layered Double Hydroxides (LDHs), which have gained increasing attention due to their low overpotentials and promising stabilities.[2] However, Beyond the intrinsic qualities of the catalysts, a myriad of factors —electrolyte concentration, substrate type, and the catalyst/substrate interface— play pivotal roles in determining electrolyzer activity and stability, forming a complex multiparameter matrix that will condition the final performance of the electrolysers. Contrary to three-electrode catalyst testing conditions for PEMWE, in which acids are used to simulate the real conditions of electrolyzers, AEL- and AEMWE-TEC testing can be performed using realistic conditions, from 0.1 to 7M alkaline electrolytes.
Thus, this work presents the results of Matteco’s accelerated TEC testing to decipher the complex multiparameter alkaline electrolysis matrix, obtaining the most promising catalysts, substrates, and processes that deliver the best performances and stabilities of AEL and AEMWE technologies.

References:

[1] N. Du, C. Roy, R. Peach, M. Turnbull, S. Thiele and C. Bock, Chemical Reviews, 122, 11830 (2022).
[2] L. Hager, M. Hegelheimer, J. Stonawski, A. T. S. Freiberg, C. Jaramillo-Hernández, G. Abellán, A. Hutzler, T. Böhm, S. Thiele and J. Kerres, Journal of Materials Chemistry A, 11, 22347 (2023).
Effect of Thickness and Sidewall Slope of Photoresist Mask on Etch Profile of Copper Interconnect
Authors: Cho Yoon Jae , Ha Su Myung , Chung Chee Won 
Published: August 2024

We performed high density plasma reactive ion etching of copper thin films using organic gas mixture to define fine patterns less than 10 μm for the application of display devices. However, since redeposition in dry etching of copper thin films frequently occurs due to extremely low reactivity, the etch variables which affect the formation of redeposition were investigated. In this study, the photoresist (PR) masks were employed to etch copper thin films. The effects of the thickness of PR and the sidewall slope of PR on etch profile and redeposition were examined.
The thickness of PR mask were in the range of 3 μm ~ 1 μm and the sidewall slopes of the PR mask were in the range of 90° ~ 45°. The etch profile and etch mechanism of dry etching using different masks were evaluated using field emission scanning electron microscopy and X-ray photoelectron spectroscopy. Finally, an etching method to reduce and/or avoid the redeposition in dry etching of copper thin films will be proposed.
Acknowledgement : This research was supported by the MOTIE(Ministry of Trade, Industry & Energy (20019504) and KSRC(Korea Semiconductor Research Consortium) support program for the development of the future semiconductor device.