bluuebunny/crossref_metadata_2025 huggingface dataset:
Additive Manufacturing of Inductors and Transformers by Hybrid Aerosol Jet Printing and Electrochemical Deposition
Authors: Tsui Lok-kun , Sui Yongkun , Hartmann Thomas Michael , Dye Joshua , Lavin Judith Maria
Published: September 2023

Aerosol jet printing (AJP) is an attractive additive manufacturing process for printed electronic applications due to its high resolution (< 10 µm), flexible stand-off distance, and support of both metal and dielectric materials. A slow deposition rate (< 1 µm per layer) and the relatively low conductivity achievable with commercially available nanoparticle inks (~40% bulk) present some of the current limitations associated with AJP. Electrochemical deposition methods including both electrodeposition and electroless deposition are widely used in the microelectronics industry. Dense, high conductivity layers several 10s of µm can be deposited with well-established plating processes. Metals including Cu and Ni which are challenging to deposit by AJP, can be easily/readily deposited using commercially available plating baths. A hybrid approach of seed layer deposition using AJP and electrochemical deposition of highly conductive copper is used to improve the overall conductance of the printed structures. [1] Here, we apply this combined approach to the manufacturing of transformer and inductor devices.

We have successfully prepared a two-layer secondary inductor on top of a two-layer primary inductor to form a coreless flyback transformer (Figure 1(a)). These inductors were fabricated by AJP of an Ag seed layer, followed by electroless deposition and electrodeposition of Cu and Ni. UV-curable dielectric polymer layers were deposited by AJP to separate each inductor layer. The flyback transformer produced a gain of 75.3x with an input voltage of 17 V at 400 kHz resulting in an output voltage of 1250 V (Figure 1(b)). We also demonstrated the repeated stacking of 8 coil layers by AJP of Ag seed layers and electrodeposition of Cu and Ni (Figure 1(c)). These inductors had an average equivalent series resistance of 0.6 Ω and a 1.7 µH inductance at 100 kHz (Figure 1(d)). Finally, we will study the deposition of these inductor and transformer devices on magnetic substrates, characterizing changes in inductance and gain.

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. SAND2022-17001 A

References:

[1] L. Tsui, S.C. Kayser, S.A. Strong, J.M. Lavin. ECS J. Solid State Sci. Technol. 10 (2021) 047001.

Figure 1. (a) Additively manufactured coreless flyback transformer fabricated by combined aerosol jet printing, electroless deposition, and electrodeposition. (b) Output voltage vs. input voltage at 400 kHz resulting in a gain of 73.5x. (c) 8-layer inductor fabricated by combined aerosol jet printing and electrodeposition. (d) Inductance at 100 kHz as a function of number of layers for the multi-layer inductor up to 8 layers.

Figure 1
An Electrochemical and Spectroscopic Characterization of Chiral MIL-53(Fe) Metal-Organic Framework
Authors: Bonechi Marco , Bettoni Diana , Maccioni Irene , Biffoli Fabio , Giurlani Walter , Salzillo Tommaso , Kawondera Rufaro , Mtangi Wilbert , Fontanesi Claudio , Innocenti Massimo
Published: September 2023

Metal-organic frameworks (MOFs) have attracted increasing scientific interest due to unique features including high specific surface areas, exceptional porosity, high crystallinity and tuneable pore size [1]. In fact, the opportunity to achieve porous materials with high modularity and diverse functionality make MOFs suitable candidate for solid-state materials. In recent years, scientists conducted intense research in the production of chiral MOFs (CMOFs). The attractiveness of chiral MOFs is due to their specific application including chiral enantioselective recognition, enantioselective separation, asymmetric catalysis, and sensing. Chirality within MOFs can occur in each of the components, whether linker, metal node, or even guest molecules [2]. MIL-53(Fe) is the most common iron-based MOF. This class of compound is obtained by a combination between iron(III) cations and 1,4-dicarboxylic acid consists of three-dimensional networks which contain FeO6 hexagonal chains and dicarboxylate anions. MIL-53(Fe) shows significant advantages compared with other MOFs, which include chemical stability, the presence of nontoxic and widely available metals [3]. MIL-53(Fe) derivatives containing chiral molecules (cysteine and camphorsulfonic acid) were characterized by IR, XRD and Electron Spectroscopy. The electrochemical behaviour of the synthesized MOFs was characterized on solid state using a glassy carbon (GC) electrode and by making a paste with graphite powder. Cyclic voltammetry (CV) measurements show different redox behaviour depending on the type of molecules present inside the framework. The experimental results were integrated and related to the properties obtained using DFT based quantum mechanical calculations.

References

[1] Q. Wang, D. Astruc, Chem. Rev.
2020, 120, 1438–1511

[2] Z. Sharifzadeh, K. Berijani, A. Morsali, Coordination Chemistry Reviews
2021, 445, 214083

[3] F. Millange, R. I. Walton, Israel Journal of Chemistry
2018, 58, 1019–1035
Cathodic Deposition of Thickness-Controllable ZIF-62 Film and Its Vitrification
Authors: Xie Sijie , Zhang Xuan , Fransaer Jan
Published: September 2023

Glass metal-organic framework (MOF) membrane is a newly developed material that is promising for separation works like ionic sieving and gas separation. Compared with its crystalline counterpart, the glass MOF membrane takes the advantage of its grain-boundary-free nature that greatly benefits the separation performance. However, the fabrication of the glass MOF membrane requires the pre-preparation of the mother crystalline MOF film, which remains a challenge. Taking the deposition of the iconic ZIF-62 (Zn-imidazole, melting point: 711 K) film as an example, this area remained silent until Jiang et al. reported the first example in 2018.1,2 They achieved the ZIF-62 deposition on anodic aluminum oxide (AAO) membrane by a solvothermal method. Nevertheless, this approach is limited by the low yield of the generated MOF crystals on the substrate and the time/energy-consuming process. To mitigate the existing dilemma, here we show an economic cathodic deposition approach to the preparation of ZIF-62 film with a controllable thickness. Thanks to the addition of hydrogen peroxide as a probase, the pure ZIF-62 film can be deposited without the co-deposition of metallic Zn. In the proposed deposition, a nucleation-Ostwald ripening-crystallization ternary process can be observed, which is different from the cathodic deposition of other MOF species like MOF-5. Also, it is found that the crystallinity of the deposited ZIF-62 film improves with the deposition temperature and the thickness of it can be well-tuned by the deposition time from a range of ~1 µm to ~15 µm. The cathodically deposited ZIF-62 film can be directly used as the mother material for the preparation of glass MOF membrane via a vitrification process. Systematic annealing experiments indicate that the heating temperature and dwelling time are crucial to the quality of the glass MOF membrane. At the optimized conditions (713 K, 4 hours), the dense and bulb-free glass MOF membrane with a flat surface can be obtained, which is ideal for separation works.

Wang, Y.; Jin, H.; Ma, Q.; Mo, K.; Mao, H.; Feldhoff, A.; Cao, X.; Li, Y.; Pan, F.; Jiang, Z., A MOF glass membrane for gas separation. Angewandte Chemie
2020,
132 (11), 4395-4399.

Bennett, T. D.; Yue, Y. Z.; Li, P.; Qiao, A.; Tao, H. Z.; Greaves, N. G.; Richards, T.; Lampronti, G. I.; Redfern, S. A. T.; Blanc, F.; Farha, O. K.; Hupp, J. T.; Cheetharm, A. K.; Keen, D. A., Melt-Quenched Glasses of Metal-Organic Frameworks. Journal of the American Chemical Society
2016,
138 (10), 3484-3492.
Porous Copper Layer Development by Dynamic Hydrogen Bubble Template for Power Modules Assembling by Thermocompression
Authors: Schoenleber Jonathan , Chachay Lucas , Janod Goulven , Gigandet Marie-Pierre , Hihn Jean-Yves , Daudin Remi , Missiaen Jean-Michel , Bouvard Didier , Avenas Yvan , Khazaka Rabih
Published: September 2023

Copper is the most widely used materials for microelectronics applications due to their electrical and thermal conduction properties, and in several applications, thick and porous layers are requested. With increased aircraft electrification, there is a need of extremely high-power converters in the power electric chain, interfacing the bus and the electric motor. The COPERPACK project (COPPER based PACKaging for direct cooled power module ANR-19-CE05-0011) aims to module assembling by thermocompression, which requested the elaboration of thin nanoporous copper film to be placed between chips and metallized ceramic substrates.

Different possibilities still exists such as copper-zinc or copper-manganese electrodeposition followed by an anodic dissolution, but the faster and simpler way resides in electroforming deposition made by Dynamic Hydrogen Bubble Template (DHBT) [1]. This process works in unusual potentials and current densities where the competition between hydrogen discharge (commonly avoided) and copper reduction is very high. In this case, this method achieves thick deposits in very short time (few seconds) with high currents allowing a very fast growth of copper around hydrogen bubbles. Pores and ligaments sizes can be controlled by several operating parameters i.e. current densities, temperature, deposit time, chemical additives [2] as well by pulsed currents. Films were tested for chips assembling by thermocompression, and present excellent behavior’s.

[1] Abdel-Karim, R.; El-Raghy, S. Chap 4 in Advanced materials and their applications - micro to nano scale. One Central Press, United Kingdom, pp 69–91, 2017

[2] Shin, H.-C.; Liu, M. Chem. Mater. 2004, 16, 25, 5460–5464 doi.org/10.1021/cm048887b

Figure 1
Understanding Li Nucleation and Growth
Authors: Meng Shirley
Published: September 2023

Lithium metal anode has been widely studied for next generation lithium metal batteries. Its chemical, electrochemical and mechanical properties are unique as lithium is the lightest metal in the planet earth. In this talk, I will use some of the advanced modeling and characterization methods to probe and understand the lithium metal anode in a rechargeable battery. The tools we developed here will be also useful for other reactive metal anodes such as sodium and zinc.
Controlling Electrodeposition Via Electrokinetic Phenomena and Phase Separation
Authors: Bazant Martin Z.
Published: September 2023

This talk will review the basic physics of dendritic instabilities in electrodeposition and how they may be suppressed, in some cases, by controlling electrokinetic phenomena in the electrolyte or phase separation in the electrode: 1) It is shown both theoretically and experimentally that, if electrodeposition occurs in charged porous media above the diffusion-limited current, then dendritic growth can be suppressed by surface conduction and electro-osmotic flows through the phenomenon of “shock electrodeposition”, as in many examples with copper. 2) It is also shown theoretically and experimentally that dendritic electrodeposition on a multiphase electrode can be avoided by avoiding the separation of a resistive phase, as illustrated by lithium plating on graphite. Examples include composite metal materials manufacturing, metal nanotube growth in templates, rechargeable metal batteries, and conductive-bridge random access memory (CB-RAM). These phenomena may also be leveraged to enhance the selectivity of electrodeposition for metal separations.
In-Situ Li Plating Reactions on Inorganic Solid Electrolytes for Advanced All-Solid-State Batteries
Authors: Iriyama Yasutoshi
Published: September 2023

All-solid-state batteries (SSBs) using lithium metal anode are expected to realize SSBs with high energy density. This is because lithium metal anode has the lowest redox potential and the theoretical capacity of 3861 mA h g-1 is ca. ten times larger than that of commonly-used graphite anode (372 mA h g-1). In fact, lithium metal anode has been successfully used in thin-film-type SSBs and stable charge-discharge reactions are reported [1]. In SSBs, both positive and negative electrode materials are combined with solid electrolytes, and they are assembled from the initial state in general. On the other hand, conventional SSBs apply lithium transition metal oxides (LiCoO2, etc.) as the positive electrode material, and lithium metal is electrochemically plated during the charging process. Appling electrochemically-plated lithium as a anode material can simplify the battery manufacturing process and will be an effective way to form pure lithium metal anode. Such “Li-free” SSBs has been successfully prepared in thin-film-type SSBs [2]. Also, this anode-less idea has been applied to develop large-sized SSBs in recent years [3].

In this presentation, the author will talk about the factors for lithium plating morphology on inorganic solid electrolytes, such as current collector species, current densities, temperature, etc. [4]. The model solid electrolytes are LiPON-coated LATP or garnet-structured Ta-doped LLZ. Also, several problems for applying electrochemically-plated lithium anode and the issues arising during the stripping processes will be discussed.

References

[1] J. B. Bates, N. J. Dudney, B. Neudecker et al., Solid State Ionics
135 (2000) 33.

[2] B. J. Neudecker, N. J. Dudney, and J. B. Bates, J. Electrochem. Soc.
147 (2000) 517.

[3] a) Y-G. Lee, S. Fujiki, C. Jung, et al., Nature Energy
5 (2020) 299. b) https://www.quantumscape.com/ 2020/12/16

[4] a) F. Sagane, K-I. Ikeda, Y. Iriyama et al., J. Power Sources
233 (2013) 34. b) F. Sagane, R. Shimokawa, Y. Iriyama et al., J. Power Sources
225 (2013) 245. c) M. Motoyama, M. Ejiri, and Y. Iriyama, J. Electrochem. Soc.
162 (2015) A7067. d) F. Yonemoto, A. Nishimura, Y. Iriyama et al., J. Power Sources
343 (2017) 207. e) M. Motoyama, M. Ejiri, Y. Iriyama et al., J. Electrochem. Soc.
165 (2018) A1338. f) T. Yamamoto, H. Iwasaki, Y. Iriyama et al., Electrochem. Comm.
105 (2019) 106494.
Peroxynitrite Sensing Using Electrode Interfaces Decorated with Grafted Diaryl Selenides
Authors: Ibrahim Magdy , Kalil Haitham , Fouad Farid , Bayachou Mekki
Published: September 2023

Peroxynitrite is a highly reactive species that is known to cause damage to cells, and it is challenging to measure its concentration accurately. Electrochemical methods for detecting peroxynitrite are limited, and there is ongoing research to develop effective electrochemical probes or catalytic materials that can serve as interfaces for efficient detection of peroxynitrite. In our previous work we developed and characterized a thin film material based on 4,4’ diaminodiphenyl selenide grafted onto glassy carbon electrodes to create a functional interface for peroxynitrite detection. This selenide-based peroxynitrite sensors demonstrated remarkable sensitivity and a low limit of detection, and we postulated an electrocatalytic catalytic mechanism whereby the grafted selenide moieties act as electroactive mediators that ultimately lead to the catalytic oxidation of peroxynitrite. The positive charge developed on the selenium atom of the diarylselenide upon electrochemical oxidation is crucial for a such electrocatalytic mechanism. To test the validity of the postulated mechanism, we designed other other diarylselenides with different functional groups in the para position of the selenium atom. In this study, we decorated electrodes with diarylselenide moieties bearing various functional groups in the para position of the selenium atom of the diaryl selenide (See Scheme1; R=-H, -OMe, -CF3).We show that the electron-withdrawing -CF3 group significantly improves the sensitivity of the corresponding electrode towards PON. The opposite is observed with the methoxy group, which almost abolishes the mediated electrocatalytic oxidation of PON. We will present the results and analyze these findings in light of the electron-donating or withdrawing ability of the substituents placed in the para position from the selenium atom in the context of the postulated electrocatalytic mechanism mediated by the selenide moiety.
Combining 1D and 3D Multi-Physics Modeling Methodologies for Thermal Runaway Propagation Analysis
Authors: Pisharodi Vivek , Artukovic Dominik , Holcomb Brad , Gundlapally Santhosh , Biju Nikhil , Luo Gang , Wimmer Joe
Published: September 2023

Battery pack designers must ensure that all battery packs are designed to withstand a single cell entering thermal runaway without the heat from this cell causing thermal runaway to occur in neighboring cells, leading to thermal runaway propagation. Pack designers must be confident that no matter which cell enters thermal runaway, and no matter how the cell enters thermal runaway, that thermal runaway will not propagate into a pack-level fire.

Studying thermal runaway events at the pack-level has historically relied heavily on expensive pack-level experimental tests using prototype batteries or computationally-expensive 3D CAE analyses. Because the cost of a single test in either scenario (real cost or computational cost) is very high, both options allow for only a handful of scenarios to be realistically studied.

Additionally, when reduced-order models of pack-level thermal runaway are employed, they have historically relied on empirically-driven models for the heat generation of cells entering thermal runaway. These models often rely on knowing the heat ejected from a cell ahead of time and often ignores the history of cells leading up to their thermal runaway events.

This presentation will demonstrate the benefits of a physics-driven approach to reduced-order modelling of pack-level thermal runaway propagation. By combining 1D/3D thermal structure modelling of cell temperature, 1D flow simulation of flow paths between cells, pseudo-2D electrochemical modelling of cells leading up to thermal runaway, and generalized chemical modelling for thermal runaway reactions inside the cell, this presentation demonstrates a computationally efficient approach to modeling thermal runaway propagation that also has high model fidelity and accuracy.

With an accurate and fast-running model, more virtual experiments can be setup to enable more what-if scenarios to be tested. This includes robust case sweeps and even multi-factor design of experiments (DoE) tests to be done.
Characterization of Emerging Porous Electrode Designs with High-Fidelity Pore-Scale Models
Authors: Fu Yucheng , Bao Jie , Feng Shuo , Singh Rajesh K. , Zeng Chao , Chen Yunxiang , Lu Dongping , Xu Zhijie
Published: September 2023

Porous electrodes have been widely adopted in battery applications due to their favorable properties of large surface area, abundant active reaction sites, and high permeability. Constrained by high computational costs, the porous electrodes are generally described by their established macroscopic properties in the device-scale battery models without explicitly reconstructing their geometries. This practice limited the model capability to analyze the recently developed porous electrodes with revised structures, whose macroscopic properties, such as permeability, mass transfer rate and reaction kinetics are not fully understood. Those knowledge gaps could result in uncertainties for battery performance assessment using the device-scale models. In response to such challenges, we have developed new pore-scale models to analyze those emerging porous electrodes by resolving their geometries with high fidelity. By incorporating hydrodynamics and electrochemical reaction physics, the pore-scale model can assess the battery performance without simplifying the electrode geometries. Two novel electrodes adopted recently in the redox flow battery and Li-S battery have been analyzed with the proposed method. For the redox-flow battery, the biporous electrode etched secondary pores on the carbon fibers to provide additional surface area and faster reaction kinetics. The pore-scale model resolves the secondary pore structures to the micrometer-scale and quantified the effects of those secondary pores on the electrode permeability, species transport and reaction kinetics. On the other hand, the low porosity electrodes are actively developed for the Li-S batteries, due to its reduced electrolyte intake and parasitic weight. The proposed pore-scale model has been used to analyze and optimize the electrolyte wetting behavior in those low-porosity electrodes to improve the Li-S battery efficiency. It is envisioned that the novel porous electrode design and development can be accelerated with well-characterized electrode macroscopic properties informed by our high-fidelity pore-scale models.
Electrochemical and NMR Characterization of ZIF-67
Authors: Hangarter Carlos M , Bovee Mark O , Swift Michael W , Miller Joel , Lyons JOHN L , Laskoski Matthew , Klug Christopher
Published: September 2023

Metal Organic Frameworks (MOFs) are attractive materials for their tunable porosities and chemistries. Zeolitic Imidazolate Frameworks (ZIF) are a class of MOFs recognized for their relative ease in synthesis and stability. In this work we study ZIF-67 for energy storage applications. We use a host of characterization techniques, including XRD, BET, EDS and 1H and 13C nuclear magnetic resonance (NMR), to better understand the neat ZIF-67. The ZIF-67 particle size is shown to be 150-300 nm, exhibiting good crystallinity with specific surface area of 850 m2/g. NMR reveals hyperfine interactions of the paramagnetic cobalt with 1H and 13C that are in good agreement with calculated values from first principles. Additionally, high resolution NMR spectra of “guest” molecules within the pores of the MOF are demonstrated. Composite electrodes based on ZIF-67 are characterized for their energy storage capacity in KOH electrolytes using cyclic voltammetry and electrochemical impedance spectroscopy. These electrodes are shown to display capacities greater than traditional carbons. Cyclic voltammetry is used to distinguish redox contributions from double layer capacity. Finally, in-situ NMR spectra of two electrode devices are presented to understand charging and discharging mechanisms.
Gold Electropolishing Using Cyanide-Free Electrolytes
Authors: Rodriguez Julymar del Carmen , Doche Marie-Laure , Hihn Jean-Yves
Published: September 2023

Electropolishing or electrochemical polishing (EP), is an ultrafinishing process that improves the aesthetic, technical and functional properties of surfaces by reducing their roughness. This process is based on the anodic dissolution of the workpiece through an oxidation reaction. The polishing effect is due to the formation of a viscous layer that induces a preferential dissolution of the peaks of the surface profile at the expense of the valley. This results in the surface leveling and in brightness improvement. Compared to conventional mechanical finishing techniques, EP is a non-contact process that does not disturb the metallurgy of the surface layer. In addition, it allows the treatment of relatively complex geometries as well as the obtention of reproducible results.

Regarding the electrolyte composition, it often includes oxidizing agents to activate the anodic dissolution (strong acids, hydrogen peroxide, ...) as well as depassivating agents to prevent the oxide film from becoming too stable (halides, alcohols, ...) and viscous layer promoting agents (glycerol, organic acids, ...). In the case of gold, the presence of a complexing agent lowers the oxidation potential and facilitates dissolution. However, most of the electrolytes used for EP of precious metals are toxic due to the presence of cyanides or thiourea. Furthermore, each alloy requires a specific electrolyte formulation and therefore suitable operating parameters. The complexity of the mechanisms involved and the associated environmental risks make it difficult to deploy this technique in the luxury and jewelry industry. Another concern is the lack of literature regarding the role of each component.

A better understanding of the process could lead to an improvement of the electrolyte formulation and to the proposal of other options with a lower environmental impact. The aim of this work is to study the effect of various non-toxic and ecofriendly electrolytes on the electropolishing mechanisms of gold and gold alloys. Their efficiency will be evaluated in terms of the surface properties obtained after the treatment: roughness reduction (macro/micro) and gloss. Moreover, the effect of each component of the electrolytes is investigated using electrochemical measurements, in the perspective of describing EP mechanism and its consequences on surface properties.

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Electrochemically Modulated Separation of Olefin-Paraffin Gas Mixtures in Membrane Electrode Assemblies
Authors: Akashige Toshihiro , Katzenberg Adlai , Frey Daniel , Merkhaji Debdyuti , Urbina-Blanco Cesar , Chen Brian , Okamoto Yoshiyuki , Modestino Miguel A
Published: September 2023

Olefin-Paraffin separations are ubiquitous chemical processes used in purifying monomers for the manufacture of a large variety of polymers and chemical intermediates. Some of the highly demanded olefin-made products include polyethylene, ethylene oxide, vinyl acetate, polypropylene, acrylonitrile, propylene oxide, and acrylic acid. Olefin-paraffin mixtures are relatively difficult to separate because of the similarity in physical properties of each component. Currently, olefins are typically purified via cryogenic distillations, a highly energy-intensive process that liquifies the hydrocarbon gas mixture and re-vaporizes them repeatedly, requiring approximately 3.6 MJ per kg of olefin purified. Because of the large energy-intensive of the process, olefin separations are responsible for approximately 0.3% of the global energy consumption, to produce 200 and 130 million metric tons per year of ethylene and propylene respectively (2020).

Alternative non-thermal olefin-paraffin separation methods have the potential to increase the efficiency of this separation, and thus increase its sustainability. In this presentation we will discuss an alternative separation method based on an electrochemically modulated swing absorption system. In this system, Nickel(II) maleonitriledithiolate, an electrochemically active organometallic complex, is dispersed in an ionogel and integrated in a membrane electrode assembly (MEA). The oxidation state of Nickel(II) maleonitriledithiolate can be electrochemically modulated based on potential. At its oxidized state [i.e., Ni (IV)], the complex has a strong affinity towards the olefin’s pi-bond, while at its reduced state [i.e., Ni (II)] the complex loses this affinity. Our results show that when exposed to propylene-propane gas mixtures, propylene was selectively captured by the organometallic species during oxidative phase, and then released or decoupled during reductive phase. Its paraffin counterpart, propane, behaved as spectator molecules throughout the whole process, demonstrating consistent olefin separation through this selective capture-and-release mechanism. I will discuss how varying the composition of the MEA exposed potential mass transport limitations that play an important role in the separation efficiency and throughput. Experiments conducted under varying potentials exhibited operational robustness of the MEA in gas separations if electric potentials are carefully tuned between 1-3V in the oxidative cycle, and at approximately -2V in the reductive cycle. This proof-of-concept demonstration represents an important step towards achieving high-performing electrochemically-modulated olefin-paraffin separations that can integrate renewable electricity sources directly and help decarbonize the chemical manufacturing industry.

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Tailored Deep Eutectic Solvents for Effective Leaching and Electrochemical Recovery of Spent Li-Ion Battery Cathode Materials
Authors: Usen Nazreen Mohamed Shahid , Ashoka Sahadevan Suchithra Ashoka , Ramani Vijay K , Sankarasubramanian Shrihari
Published: September 2023

The increase in demand for Lithium-ion battery (LIB) raw materials such as cobalt, nickel and lithium are expected to exacerbate exploitative resource extraction and have negative geopolitical implications. A solution to ameliorate this issue is to recycle LIBs. Unfortunately, the existing LIB recycling market is dominated by energy inefficient and environmentally harmful processes such as pyrometallurgy and hydrometallurgy which produce products that require further processing before downstream use. Deep Eutectic Solvents (DESes) are a class of compounds that are formed by mixing hydrogen bond donors and acceptors and exhibit high capability for dissolving metal oxides. In this work, we tailored the electrochemical stability window of selected, high leaching efficiency DESes by incorporating additives (such as ammonium salts and glymes), thereby expanding their electrochemical window and gaining the ability to electrochemical plate out dissolved metals from the DES in addition to facilitating leaching at high recovery rates. The electrochemical window of our baseline DES, the extensively studied system consisting of choline chloride and ethylene glycol (ChCl: EG), is ca 1-3 V (vs AgCl). This system can be tailored with additives to yield DESes with extended electrochemical stability window of ca 4-5 V (vs AgCl) while retaining its excellent leaching. The ability of this class of DESes to efficiently leach metals from LiCoO2 (LCO) and LiMnxNiyCo(1-x+y)O2 (LMNCO) cathodes and corresponding leaching efficiencies for Li, Co, Mn and Ni was examined over a range of temperatures and by subjecting the mixture to microwave or sonication in addition to (or in lieu of) heating. Selective tailored DES were shortlisted depending on the high leaching efficiency and leached elements were electrochemically recovered. The microstructure of the electrodeposited material was examined using x-ray diffraction and scanning electron microscopy for phase identification, purity, and stability of the individual elements.

Keywords: LIB, Cathode, Electrodeposition, Leaching, Sonication, DES

Figure 1. Effect of additives on the electrochemical window of a ChCl:EG DES (left); Photograph of leach liquors of different cathode materials (LCO, LNO, LMO and LNMCO from left to right) dissolved in selected DES (right)

Figure 1
Sustainable Iron Production by Low Temperature Electrolysis of Fe2O3 Colloidal Electrode
Authors: Thanwisai Panya , Wang Yan
Published: September 2023

Fe is one of the most important metals that has been used in nearly every construction of man. Currently, Fe is manufactured by a carbothermic reduction by which Fe2O3 ores and carbon are reduced at >2000°C in a blast furnace. This conventional method is environmentally hazardous as it emits almost 2 tons of CO2 per every ton of crude iron produced, accounting for 5% of global CO2 emission. With the goal of zero CO2 emission and sustainable development, more advanced technologies of Fe manufacturing are urgently required. Herein, we introduce a novel and sustainable Fe production using a low temperature electrolysis (100°C) of Fe2O3 colloidal electrode. The Fe2O3 colloid with an electronic-ionic conductive network was successfully fabricated which contains Fe2O3 electrochemically active species, carbon and NaOH solution. Carbon acts as an electronic conductor while NaOH solution serves as an ionic conductor. This electrode design helps increase reactive areas for the Fe2O3 reduction process resulting in fast reaction rate. In addition, some organic and inorganic additives were added to enhance an electrolysis efficiency via promoting the reaction and suppressing H2 evolution parasitic reaction. This method can produce high purity Fe powder with a high current efficiency of 95%. Our zero CO2 emission method is much greener, and less energy consumptive than the conventional carbothermic process, which potentially revolutionizes the iron and steel industry that has a history of environmental consciousness for many decades.
Electrode Design for Effective Electrochemical Regeneration of an Alkaline CO2 Capture Solution
Authors: Muroyama Alexander , Masiello Davide , Gubler Lorenz
Published: September 2023

The use of a membrane electrochemical cell to drive carbon capture has the potential to exceed the performance of conventional, thermally driven methods. KOH is a common solvent for CO2 capture, as it spontaneously reacts with CO2 to form carbonates (K2CO3 or KHCO3) at ambient conditions. Previous work has shown the use of an anion exchange membrane electrochemical cell to simultaneously regenerate an alkaline carbon capture solution on the cathode (feed) side and concentrate CO2 on the permeate (anode) side of the cell. Supplying H2 to the anode side of the cell allows hydrogen oxidation to be the dominant reaction, which reduces cell overpotentials compared with oxygen evolution. The CO2-enriched H2 stream can be used for methanol synthesis as a versatile energy carrier. Through experimental optimization and modeling work, we demonstrate the use of rational design to reduce cell overpotentials and improve faradaic efficiency. The balance of operating parameters such as current density and specific energy consumption have important implications for the overall cost and scalability of the process.
Synthesis and Morphological Control of Fe Metal Particles By Controlling the Metal Complex Condition in Basic Solution
Authors: Takahashi Hideyuki , Yokoyama Koji , Araya Yuma , Asakura Tomokazu , Kumon Shoichi , Sato Kimitaka , Yokoyama Shun
Published: September 2023

Coronavirus outbreaks have recently necessitated rapid virus recovery and vaccine developments. Magnetic beads are essential components to recover virus in an immunoprecipitation process. Pure iron particles with a diameter of 1 µm can be used as core materials of high-performance magnetic beads.

Thus, the development of effective and green synthesis method of Fe nanoparticles is important. However, Fe nanoparticles were synthesized only in acidic solution by using strong reducing reagent, such as NaBH4, while it cannot be achieved in the basic solution since iron hydroxide, which is easily formed in this condition, cannot be reduced into metals. However, former is not suitable for commercial synthesis method because of its intense reducing process. Thus, the reducing rout of Fe species under basic condition should be developed.

Here, until now, we tried to synthesis the various metal/alloy nanoparticles, such as Pd20Te7 nanoparticles and uniform Cu-In (CI) alloy nanoparticles, by utilizing the restrict metallic complexes controlling method in an aqueous solution under room temperature. In this method, reduction potential of the metal species can be controlled under the room temperature, consequently metal/alloy nanomaterials with uniform and well crystallized structure can be successfully synthesized.

So, in this study, we proposed the synthesis method of iron particles under basic conditions, and morphological conditions control of iron particles by utilizing the “gel-sol” method using gel networks, which is a safe and simple approach to suppress the chain crystallization.

Calculation results indicated that Fe complex can be restricted into one species as the function of pH, complexing reagent species and/also concentration. For example, Fe complex can be restricted into single complex in the basic condition (for example 8<pH<11).

By using this homogeneous condition, metal Fe nanoparticles were successfully synthesized. The addition of gel networks into the synthesis system can effectively suppress the chain crystallization of iron particles. Furthermore, in order to obtain iron particles with organic-free surface, we proposed a novel method to decompose and remove the gel networks.

Other results will present in our presentation. This work was supported by JSPS KAKENHI Grant Number 21H03628 and DOWA holdings.

[1] H. Takahashi et.,al, Applied Catalysis A: General 392 (2011) 80–85
Combinatorial Screening of Nb1-x-YTixWyOz Materials for Li-Ion Battery Anodes
Authors: Sieffert James Michael , Lang Christopher , Rehman Sarish , McCalla Eric
Published: September 2023

While much attention in recent years has been given to high performance Li-ion batteries for electrical vehicles, other applications require properties that demand a different set of material considerations such as long lifetimes and extremely high safety and reliability. Anodes for such batteries must be carefully selected to properly achieve these goals. The most commonly industrially utilized anode material, graphite, is not ideal for such applications due to particle fracture and Li dendrite growth at high rates. The current state of the art for high power anode materials is Li4Ti5O12 (LTO) where energy density is sacrificed (theoretical capacity of about 170 mAh/g) in order to operate at potentials where the electrolytes are highly stable.

Nb-based oxides have been of interest recently in this regard, with materials such as Nb2TiO7 being considered as industrially relevant for applications where LTO currently dominates. To date in the literature, only 3 compositions have been considered.[1-2] Herein, a wide array of Nb based materials are explored for use as anodes by way of high-throughput experimentation. Over 128 different compositions in the Nb-Ti-W-O pseudoternary space are prepared and characterized with both X-ray diffraction and cyclic voltammetry. Of note, this system features a number of promising solid-solutions that extend well into the ternary system. These compositions derive from crystal structures that are found on both the Nb2O5-WO3 and Nb2O5-TiO2 pseudobinaries, but wide substitutions of the third metal are found to be feasible. This dramatically increases the candidate list for potential anodes. Importantly, the electrochemical performance varies dramatically across the solid solutions. Some ternary compositions feature high discharge capacities of up to 300 mAh/g and high reversibility with 98% capacity retention after 10 cycles. It should be noted that the pseudobinaries have been previously studied in our group with a far lower capacity retention than those found here for some pseudoternary compositions. The rate performance is also found to be outstanding.

The improved specific capacity at a comparable potential as LTO makes Nb-W-Ti-O materials highly promising for applications where high rates and safety are paramount. Results presented here will guide further exploration of the rich chemistry available for Nb-based anodes.

References:

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Structure and Lithium Insertion in Oxides of Molybdenum
Authors: Vincent Rebecca , Cheetham Anthony K. , Seshadri Ram
Published: September 2023

Oxides MoOx of molybdenum have a rich structural chemistry arising from the accommodation of oxygen deficiency as MoO3 is reduced, and varied redox behavior arising from the ability of Mo to take on several different oxidation states. We have reviewed MoO3, MoO2, and all the reduced Mo oxides with intermediate compositions for their performance as Li-ion battery electrode materials. These reduced oxides are perhaps the most structurally diverse in the field of energy storage materials, taking on structures ranging from ones with crystallographic shear to bronze-like structures and distorted rutile. Crystal structure can have a significant impact on the performance of battery materials, which makes the reduced Mo oxides a promising domain of study. Electrochemical studies of these oxides from as early as 1971 to as recently as 2022 have been compiled, and characteristics of capacity, capacity retention, and rate performance have been compared. We found that certain oxides indeed display promising and highly reversible capacities for Li+ storage. Typical redox voltages for Mo oxides lie in a regime that hinders maximizing energy density when they are paired with higher-voltage cathodes or lower-voltage anodes. The possibility of decreasing the redox voltage in the future will expand the promise of these materials, while offering an alternative to more critical elements such as Nb.

Figure 1
Electrochemical and Microstructural Characterization of Lithium-Ion Battery Anodes Based on C/SiC and C/SiOC Ceramic Matrix Nanocomposites Prepared Via Xenon Flash Lamp Photothermal Pyrolysis of Organosilicon Preceramic Polymers
Authors: Okoroanyanwu Uzodinma , Bhardwaj Ayush , Pande Varun , Watkins James J.
Published: September 2023

Ceramic matrix nanocomposites of carbon/silicon oxycarbide (C/SiOC) and carbon/silicon carbide (C/SiC) are prepared via photothermal pyrolysis of crosslinked polycarbosilane and polysiloxane preceramic polymers (PCPs), using a high-intensity pulsed xenon flash lamp in air at room temperature. The millisecond duration of the radiation pulse is shorter than the thermal equilibrium time of the PCPs, enabling pyrolysis of the precursor phase and crystallization of the product before significant energy transfer to the substrate, making this process uniquely amenable to ceramic processing on or adjacent to thermally sensitive materials. Rapid precursor pyrolysis and product crystallization during flash lamp processing, even in air, limits oxidation of the resulting ceramics. To prepare the nanocomposites, PCPs are coated onto woven carbon fiber fabrics, thermally crosslinked and then flash-lamp pyrolyzed. The resulting nanocomposites are thermally and oxidatively stable at extremely high temperatures. Microstructural characterization of the composites carried out by means of XRD, Raman spectroscopy, and TEM analysis reveal the composites to be composed of three major phases: (1) an amorphous Si-O-C phase, (2) a segregated carbon phase containing a mixture of disordered carbon, graphite, and few layer graphene, and (3) a crystalline silicon carbide phase. This advantageous composition offers a large variety of Li-ion storage sites, providing these materials with properties such as high areal lithiation capacity when used as anode materials in Li-ion batteries. Their electrochemical properties are strongly correlated to their microstructure and phase composition and are dependent on their pyrolysis conditions. The Li-ion diffusivity within the materials is evaluated with three independent electroanalytical methods: potentiostatic and galvanostatic intermittent titration techniques, and electrochemical impedance spectroscopy.
Quantifying the Open-Circuit Voltage (OCV) Hysteresis in Ternary Li-Rich Mn-Ni Layered Oxides
Authors: Kipfer Tim , Berk Rafael Benjamin , Piana Michele , Gasteiger Hubert A.
Published: September 2023

To achieve the high energy densities needed for automotive applications while keeping the cathode active material (CAM) cost as low as possible, lithium- and manganese-rich NCMs (LMR-NCMs), e. g., Li1.14(Ni0.26Co0.14Mn0.60)0.86O2, are considered as possible candidates. Furthermore, in the past years there was a tendency for replacing expensive and supply-limited cobalt from cathode active materials, resulting in cobalt-free LMR-NMs with the general composition x Li2MnO3 · (1-x) LiMO2 (M = Ni, Mn; 0.33 ≤ x ≤ 0.5) or alternatively expressed as Li1+δ[NiyMnz]1-δO2(y+z= 1, 0.14 ≤ δ ≤ 0.20).1 Even though these materials are able to reversibly provide capacities of ≈ 250 mAh/g, there are numerous challenges to overcome, like extensive gas evolution, capacity and voltage fading over extended charge/discharge cycling, and the substantial open-circuit voltage (OCV) hysteresis, which hamper the implementation of LMR-NCMs in the automotive sector.2–5

It was shown in previous publications that the OCV hysteresis, an intrinsic property of LMR-NCMs, significantly lowers the charge/discharge energy efficiency and thus increases heat generation.2, 6, 7 Furthermore, it was qualitatively shown that the voltage fading as well as the OCV hysteresis is dependent on x in x Li2MnO3 · (1-x) LiMO2 (M = Ni, Mn, Co).5, 6

In order to investigate the relation between composition and OCV hysteresis for Co-free overlithiated layered oxides, we synthesized CAMs with various compositions with the general formula x Li2MnO3 · (1-x) LiMO2 (M = Ni, Mn; 0.33 ≤ x ≤ 0.5), proving the presence of the layered structure of the materials with Rietveld refinements on the collected X-ray diffraction data. The OCV hysteresis of the synthesized and electrochemically activated LMR-NMs is determined from slow charge/discharge cycles with intermittent OCV holds. Based on these data, the OCV hysteresis of LMR-NMs can be correlated with their specific composition.

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Acknowledgement

This work is financially supported by the BASF SE Network on Electrochemistry and Battery Research.