bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimization and Kinetic Study of the Electrochemical-Assisted Leaching of Valuable Metals in Lithium-Ion Batteries
Authors: Molina Montes de Oca Daniel E , Shi Meng , Klaehn John , Diaz Aldana Luis , Lister Tedd 
Published: November 2022

Efficient recycling of lithium-ion batteries (LIB) is required to meeting future demand of materials and support sustainable decarbonized energy systems. At the center of the recycling process is the recovery of valuable active metals in LIBs. Hydrometallurgical recovery processes are considered cleaner and less expensive than pyrometallurgical processes, and we previously reported a hydrometallurgical process for the leaching of valuable metals in mixed shredded LIBs. [1] In this process the reductant Fe2+, at low concentration, is electrochemically regenerated to complete the leaching of metals of interest Co, Ni, Li, Mn, and removal of Cu from LIB black mass, eliminating the need of H2O2. To accelerate this process and reduce chemical and energy consumption, the effect of process variables needs to be better understood. In this work, we study the effect of added electrochemical mediator concentration (Fe), total current and agitation level on the kinetics and leaching efficiency the EC-leaching process. Moreover, we propose a new multi-stage leaching scheme for the adjustment of final pH and recirculation of iron in the system.
References
1. Diaz, L.A., et al., Electrochemical-assisted leaching of active materials from lithium ion batteries. Resources, Conservation and Recycling, 2020. 161: p. 104900.
Improved Adhesion Strength for Electrodeposited Nickel Onto Titanium Alloys Via the Brush Plating Method
Authors: Thomas Joshua , Milosevic Danijela 
Published: November 2022

Titanium and titanium alloys are attractive materials in a variety of industries such as aerospace due to a high strength to weight ratio and a surface which is naturally resistance to many forms of corrosion. However, tribological properties such as poor abrasion resistance and high friction during metal-to-metal contact have proven difficult to handle without additional treatments. Application of coatings onto the material’s surface is one means of protecting it from those poor tribological properties.
Electroplated nickel coatings retain much of the corrosion resistance desired of titanium alloys while also exhibiting better abrasion and wear resistance. Electroplating onto titanium and its alloys is prohibitively difficult due to the propensity of the material to form a tenacious oxide coating on any fresh surface instantaneously after its exposure. The oxide surface acts as a barrier between the solution and the titanium surface reducing the adhesion strength of the resulting deposit. The oxide layer is most commonly removed and the surface modified by hydrofluoric acid (HF) based treatments. HF is considered highly dangerous to workers and to the environment and work is being done to heavily limit its use.
For this work, a proprietary chloride-based solution was used during the preparatory steps. Brush or selective plating was chosen as the application technique due to its ability to perform the entire operation with the substrate exposed to solution and under potential control. In most applications of electroplating, the surface/part to be plated must be transferred between multiple tanks containing each preparatory solution used to etch and activate the surface which would involve exposure to air at several points. In addition, the brushing action inherent in brush or selective plating creates a surface environment which can be optimized to promote strong adhesion at the nickel/titanium interface.
This presentation will discuss how SIFCO’s brush plating process technology and automation capabilities were used to achieve strong adhesion to the titanium surface without the use of HF. Focus was specifically placed on achieving strong adhesion of a nickel pre-plate onto the titanium surface which allows for a multitude of other coatings to be applied thereafter. The method was performed using a single anode through which the solutions for each step flowed. The samples were under applied potential and immersed in solution throughout the entire process. Applied potential and solution delivery were automated to maximize process consistency.
Samples were measured for tensile adhesion strength via the specification ASTM C633. Several variables related to the preparatory procedure were optimized during the study including the flow rate of the solution, the voltage/current conditions, and the evaluation of preparatory steps taken before the electrochemical procedure.
Electrochemical Dewatering of Cellulosic Nanomaterials
Authors: Vijapur Santosh Hanamant , More Santosh R , Le Huong , Hall Timothy , Taylor E. Jennings , Inman Maria , Snyder Stephen , Nelson Kim , Handler Robert M 
Published: November 2022

Renewable cellulosic nanomaterials exhibit great potential in various applications due to unique properties. Abundant availability of feedstock has led to industrialization of production. A significant cost-limiting factor to utilize cellulosic nanomaterials is dewatering/drying as cellulosic nanomaterials are not economical to ship long distances while containing significant water content (>95 wt.%). This represents a critical driver for increased costs of nanocellulose products.
Accordingly, Faraday Technology in collaboration with GranBio USA, manufacturers of cellulosic nanomaterials, is addressing this need by developing electrochemical based dewatering system and process to dewater cellulosic nanomaterials while maintaining material properties when dried and re-dispersed. Energy-efficient (70% reduction in energy requirements compared to thermal dewatering), environmentally beneficial (51% reduction in greenhouse gas emissions), economical (31% reduction in cost/ton of dried material), and industrially viable electrochemical based dewatering approach to process up to 2 tons/year of dried nanocellulose at alpha-scale has been demonstrated. The approach is capable of achieving >50 wt.% final solids and 18 wt.% final solids, that could be rehydrated under vortex and confirmed for re-dispersibility. Material properties (structure, particle size) were maintained by the dewatered cellulosic nanomaterials. Specifically, this talk will discuss the results of these advancements.

Acknowledgements: The financial support of DOE Contract No. DE-SC0018787 is acknowledged.
Fouling of Cu Catalysts during Electrochemical Hydrogenation and Hydrogenolysis of Furfural in Acidic Media
Authors: May Andrew S. , Biddinger Elizabeth J. 
Published: November 2022

Electrochemical processes offer sustainable means of production when coupled with renewable energy. While thermocatalytic processes require external hydrogen gas for reduction reactions, which generates copious amounts of CO2 in the generation of the hydrogen gas, electrochemical processes have the ability to use protons from the electrolyte in lieu of external hydrogen gas as a reactant. In addition to eliminating the hydrogen gas reactant, electrochemical processes can operate at room temperature and pressure. The development of electrochemical reactors for transformation of biomass derived species is of growing interest for the sustainable production routes it enables of various fine chemicals and fuels. Furfural (FF), one such biomass derived species can be electrochemically reduced to furfuryl alcohol (FA), a resin, and 2-methylfuran (MF), a potential fuel. To produce both FA and MF, acidic electrolytes and Cu catalysts can be used. While Cu electrodes allow for high selectivity to furfuryl alcohol or 2-methylfuran, the Cu electrodes suffer from stability issues caused by things such as fouling over longer durations of electrolysis.
In this work, we intentionally operated FF ECH under conditions to promote fouling so that the impact of fouling could be investigated. This consisted of 200mM FF in the catholyte with pH 0 electrolyte in 20:80 acetonitrile:water. We used a Cu flag working electrode of 6cm2. We then recycled the Cu electrode for 3 runs of ECH at 3 hours, refreshing the catholyte after each run. A polymeric substance was observed on the Cu electrode surface after multiple uses which had identical IR spectroscopic features to poly(furfuryl alcohol). The impact of the polymeric coating was investigated further using electrochemical impedance spectroscopy, the chemical characterization was determined using x-ray photoelectron spectroscopy, and morphology was imaged using scanning electron microscopy.
Modeling Electrochemical Direct Air Capture of CO2 using Redox-Functionalized Electrodes
Authors: Ali Fawaz , Kwabi David G. 
Published: November 2022

Increasing research attention is being devoted to designing electrochemical systems that can capture CO2 from air and thus mitigate climate change, as decarbonization of the energy sector is occurring very slowly. The low concentration of CO2 in air however makes large scale, energy-efficient and rapid CO2 capture challenging. Understanding how the energetic cost of CO2 capture depends on operational and material parameters that describe electrochemical systems is important for designing practical and cost-effective devices.
We have previously shown that electrochemical CO2 capture is possible using a pH swing cycle that is driven by proton-coupled electron transfer (PCET) involving organic molecules [1]. More recently, we have begun to consider a new design for electrochemical CO2 capture in which PCET-active species are conformally attached to the internal surface area of a highly porous electrode, and effect a reversible pH swing in an adjacent layer of aqueous electrolyte upon redox cycling. We develop a continuum reaction-transport model that simulates reactive CO2 capture into and release from the electrolyte layer, as well as transport of (bi)carbonate species, and protons, in response to an applied current or voltage. The model permits an assessment of the energetic cost of CO2 separation under various current densities and concentration gradients, and decomposition of that cost into thermodynamic, kinetic, mass transport-related and Ohmic contributions. We then highlight potential pathways to achieving an energetic cost of CO2 capture from air of 100 kJ/molCO2, and discuss preliminary results from an experimental prototype.
[1] Jin. S, Wu M., Gordon R., Aziz M., Kwabi D., pH Swing Cycle for CO2 Capture Electrochemically Driven through Proton-Coupled Electron Transfer
(Digital Presentation) The Role of Iron in the Zinc Electrodeposition from Chloride Media for Recovering Zinc from Spent Pickling Liquors
Authors: Zakiyya Hanna , Kekesi Tamas 
Published: November 2022

Electrodeposition of Zn from chloride media had been studied by potentiodynamic method to understand the characteristics of Zn recovery from spent pickling liquor (SPL). Various concentration, pH, agitation speed and impurities contamination were examined in the series of experiments. The influence of Zn concentration in the range of 30-150 g/dm3 relevant to the real SPL were studied along with acidity level change (pH 1.5-5.5). It was found that the cathodic deposition started with the uniform patern followed by sponge-like deposit and as the concentration of the electrolyte near the cathode surface decreased, the dendritic deposition start to grow, especially at the edge of the cathodes.
It was found that the effect of iron concentration on the polarization curves of zinc from SPL is complex. Initially it has a negative effect on the generated cathodic current because of the enhancement of hydrogen bubble formation. At a higher concentration range, however, iron deposits at a relatively higher rate. Further increased iron concentrations may make the composition of the Zn-Fe deposit dominantly in favor of iron, resulting in a hydrogen dominated cathodic mechanism. It is also characterised by the loss of the dendritic structure – attributed mostly of zinc deposition when hydrogen bubbles are not blocking the cathode. As the gas evolution becomes more characteristic, the deposit tends to become more powdery. Under such conditions the cathode becomes smoother and the active surface is reduced. Increasing the stirring speed, the powder was easily detached from the cathode surface. Iron, however can enhance the cathodic deposition process of zinc. With 30 – 60 g/dm3 iron in the 90 g/dm3 Zn solution, an increased iron concentration resulted in a significant increase in the mass of the deposited zinc. This may be interpreted by a beneficial effect of the increased hydrogen evolution enhancing the zinc ion transport to the electrode surface. However further increments of iron had a contrary effect, possibly by the locally increased – and generally detected – pH of the solution indirectly causing a superficial precipitation of hydroxides. Technically pure zinc could be deposited from only low-iron (< < 30 g/dm3) zinc solutions (of 90 g/dm3 Zn) at relatively vigorous stirring speeds. High iron concentration in the solution is definitely unsuitable for obtaining the aimed quality of cathode zinc.
Analysis of Boron Removal By Capacitive Deionization
Authors: Shocron Amit N. , Guyes Eric N. , Dykstra Jouke E. , Suss Matthew E. 
Published: November 2022

Climate change and water overextraction are some of the reasons for a growing global water stress, with seawater desalination being the leading solution worldwide. The state-of-the-art technology for seawater desalination is reverse osmosis (RO), utilizing mechanical pressure to push seawater through membranes, leaving the dissolved species in the brine. However, boron, which is considered toxic in high concentrations, is poorly removed by RO. This is because under normal conditions boron is present as boric acid, a small neutrally-charged compound. The most common technique to overcome this problem includes multiple RO stages combined with chemical dosage of the effluent, ensuring boron is present as borate, a charged species, present in high pH conditions.
Capacitive deionization (CDI) is an emerging membraneless technique for water treatment and desalination, based on electrosorption of salt ions into microporous electrodes. Large internally-generated pH gradients develop during CDI operation, and thus CDI can potentially remove boron without chemically adjusting the feed pH. Here, we present a novel theoretical framework predicting the adsorption of boron in micropores, while considering pH-dependent chemical surface groups in the micropores, ion transport in the macropores, and local electrolyte pH. Moreover, we account for association and dissociation reactions of boron-consisting compounds in the electrolyte[1].
We analyzed the effects electrodes order have on pH dynamics, where panels a. and b. in the attached figure present spatiotemporal plots of the pH for the case where cathode is placed upstream (panel a., cat-an) and the anode placed upstream (panel b., an-cat). This analysis shows that higher pH in the anode are expected for the an-cat configuration, counter to common-wisdom in the field. Panel c. follows this trend, by presenting the removed boron as a function of scaled flow velocity for both configurations. The results show, both experimentally and theoretically, that an-cat configuration should be preferred. Similarly, we found that an optimum charging voltage exists, even without accounting for parasitic reactions. Moreover, we found that also the discharging voltage significantly affects boron removal. Overall, CDI is a promising technology for boron removal, but a deep theoretical understanding of the problem is crucial towards future optimization.
References:
[1] Amit N. Shocron, Eric N. Guyes, Huub H. M. Rijnaarts, P. M. Bieshuvel, Matthew E. Suss, Jouke E. Dykstra, "Electrochemical removal of amphoteric ions", PNAS, 118, 40, e2108240118, 2021.

Figure 1
Generating and Optimizing Hierarchical Porosity in Electrospun Capacitive Deionization Electrodes through Control of Mesopore Volume
Authors: Waugh John , Liu Min , Komini Babu Siddharth , Pintauro Peter N. , Kang Qinjun , Spendelow Jacob S. 
Published: November 2022

Capacitive deionization (CDI) is a promising technology that has gained interest recently for the desalination of brackish water. Hierarchically porous carbons are commonly used for CDI due to their high surface areas and various pore size distributions that maximize ion adsorption capacity and rate.1 Electrospinning is an effective way of generating nanofibers with high inter-fiber macroporosity that can be converted to carbon fiber and modified to improve surface area, total pore volume, and pore size distribution. This work describes the usage of sacrificial mesopore formers in tandem with a micropore etching technique to induce hierarchical porosity. The combination of mesopores (2-50 nm) and micropores (<2 nm) enables fast ion adsorption rates and capacity.2 Mesopores will be formed via the dissolution of silica nanoparticles (10-20 nm) that are introduced into the fibers during the electrospinning step. Mesopore volume will be controlled by changing silica content in the fiber. An optimum mesopore contribution is found, at which point added mesoporosity maximizes ion transport. Further increasing mesoporosity is detrimental to fiber conductivity and surface area and results in decreased performance as reported in the literature. 3 After mesopore formation, micropores are etched on the surface of the fibers through KOH loading and thermal activation. Micropore formation is optimized to maximize specific surface area while maintaining physical integrity of the fibers. This sequential technique creates a hierarchical network of pores from the inherent microporosity of the fiber network, to the mesopores, and finally micropores to maximize usage of surface area. Fiber electrodes fabricated in this method achieve specific surface areas exceeding 1400 m2 g-1, with pore volumes exceeding 1.0 cc g-1. The pore size distributions are highly controlled, with 80% of total pore volume coming from pores less than 20 nm in radius. In 500 ppm constant voltage CDI tests, these fiber electrodes obtain a salt adsorption capacity of over 14 mg g-1, at a salt adsorption rate of ~3 mg g-1 min-1, showcasing the high capacity matched with high rate of these easily fabricated, inexpensive materials.
References:

Liu, T., Serrano, J., Elliott, J., Yang, X., Cathcart, W., Wang, Z., ... Liu, G. (2020). Exceptional capacitive deionization rate and capacity by block copolymer-based porous carbon fibers. Science Advances.

Baround, T., Giannelis, E. (2019). Role of Mesopore Structure of Hierarchical Porous Carbons on the Electrosorption Performance of Capacitive Deionization Electrodes. ACS Sustainable Chemistry & Engineering.

Pan, H., Yang, J., Wang, S., Xiong, Z., Cai, W., & Liu, J. (2015). Facile fabrication of porous carbon nanofibers by electrospun PAN/dimethyl sulfone for capacitive deionization. Journal of Materials Chemistry A.
(Invited) Battphase – a Convergent, Non-Oscillatory, Efficient Algorithm and Code for Predicting Shape Changes in Lithium Metal Batteries Using Phase-Field Models
Authors: Jang Taejin , Mishra Lubhani , Roberts Scott A. , Subramaniam Akshay , Uppaluri Maitri , Gururajan Mogadalai P. , Zhang Ji-Guang , Subramanian Venkat R. 
Published: November 2022

Electrochemical models at different scales and varying levels of complexity have been used in the literature to study the evolution of the anode surface in lithium metal batteries. This includes continuum, mesoscale (phase-field approaches), and multiscale models.1-5 Thermodynamics-based equations have been used to study phase changes in lithium batteries using phase-field approaches. However, grid convergence studies and the effect of additional parameters needed to simulate these models are not well-documented in the literature. In this talk, using a motivating example of a moving boundary model in one- and two-dimensions, we show how one can properly formulate phase-field models using the immersed interface/domain approach, implement robust and efficient algorithms for the same and analyze the results (Figure 1). An open-access code with no restrictions is provided as well. The talk concludes with some thoughts on the computational efficiency of phase-field models for simulating dendritic growth.

Acknowledgements

The authors would like to express gratitude to Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the DOE through the Advanced Battery Material Research (BMR) Program (Battery500 consortium). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Supported by the Laboratory Directed Research and Development program at Sandia National Laboratories, a multimission 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-NA-0003525. VS acknowledges interactions with Dr. Srikanth Vedantam from IIT Madras, India and Dr. Daniel Wheeler from National Institute of Standards and Technology for early discussions on phase-field and level-set methods. VS also acknowledges Richard Braatz from Massachusetts Institute of Technology for pointing out the poor results from standard algorithms because of the convective nature of the models.

References

1. Q. Wang, G. Zhang, Y. Li, Z. Hong, D. Wang and S. Shi, NPJ Comput. Mater., 6, 176 (2020).
2. Z. Hong and V. Viswanathan, ACS Energy Lett., 3, 1737 (2018).
3. L. Liang and L.-Q. Chen, Appl. Phys. Lett., 105, 263903 (2014).
4. D. A. Cogswell and M. Z. Bazant, ACS Nano, 6, 2215 (2012).
5. Y. Zeng and M. Z. Bazant, SIAM J. Appl. Math., 74, 980 (2014).

Figure 1