bluuebunny/crossref_metadata_2025 huggingface dataset:
Electrodeposition of Tribological Molybdenum Disulfide Coatings on Stainless Steel
Authors: Robinson Donald "Donny" A , Reed Christopher L , Babuska Thomas F , Sugar Josh D , Vitale Suzy M , Larson Steven R , Curry John F , Dugger Michael T
Published: December 2024

MoS2 is an excellent solid-state lubricant for applications in space systems. Among various methods for MoS2 deposition, electrodeposition has the potential advantage over vapor deposition methods in achieving coatings on parts with complex geometries. This presentation will describe methods to electrodeposit smooth, crack-free, low-friction, and wear-resistant coatings of MoS2 on stainless steel at room temperature. The MoS2 films can be directly deposited on stainless steel without the need for anodic pretreatments or an adhesion layer, giving a low surface roughness comparable to that of the polished steel surface. The incorporation of stabilizing additives to the deposition bath not only enables the long-term stability of the solution under ambient environment, but also improves the uniformity of the coating over the substrate surface while maintaining a consistent S:Mo ratio of 2:1 across the thickness of the film. Additionally, coatings deposited from additive-free baths are amorphous, whereas those produced with additives are a composite of both amorphous and crystalline MoS2 regions. Coatings deposited with or without bath additives both display initially high friction and long run-in times but achieve low steady-state coefficients of friction and wear rates comparable to MoS2 coatings prepared by physical vapor deposition. Post-deposition mild annealing of the electrodeposited films under inert gas substantially reduces the initial friction and run-in times. Ongoing efforts to adopt the electrodeposition method for coating small parts with complex geometries such as pins and bearings will also be presented, as well as detailed information about the chemical composition and mechanistic roles of the additives in the improved deposition bath, methods to prevent film cracking during drying, and the role of mild thermal annealing.
Controlled Texture of Metal Electroforming through Pulse Electrodeposition
Authors: Mirabal Alex , Hooks Daniel E , Fensin Saryu Jindal , Stull Jamie A
Published: December 2024

Impact physics provide equation of state information for material performance in extreme environments. There is some evidence that the underlying microsctructure impacts the response at some velocities1. One way to probe the microstructure is through controlled electrodeposition. Both pulse plating and chemical additives are known to modify the grain structure during electrodeposition. However, additives can be incorporated in the coating and influence the resulting properties such as hardness and mechanical properties. Therefore, we aim to control electroformed coatings through exclusively using square wave pulses.

There are some preliminary studies indicating control of grain size of electroplated coatings, however, process control has, so far, only been studied by post characterization analysis on often limited subsets2–5. A methodical approach leads to a deeper mechanistic understanding of isolating plating parameters to control the grain structure.

In this work, we explore the impact of current density, duty cycle, frequency and pulse widths/heights and their impacts on the grain structure. We show uniform grain structure through thick films (>3mm), and control over the texture and orientation of grains (Fig. 1).

(1) Escobedo, J. P.; Dennis-Koller, D.; Cerreta, E. K.; Patterson, B. M.; Bronkhorst, C. A.; Hansen, B. L.; Tonks, D.; Lebensohn, R. A. Effects of Grain Size and Boundary Structure on the Dynamic Tensile Response of Copper. J. Appl. Phys.
2011, 110 (3), 033513. https://doi.org/10.1063/1.3607294.

(2) Marro, J. B.; Darroudi, T.; Okoro, C. A.; Obeng, Y. S.; Richardson, K. C. The Influence of Pulse Plating Frequency and Duty Cycle on the Microstructure and Stress State of Electroplated Copper Films. Thin Solid Films
2017, 621, 91–97. https://doi.org/10.1016/j.tsf.2016.11.047.

(3) Chan, K. C.; Qu, N. S.; Zhu, D. Crystallographic Textures and Magnetic Properties of Electroformed Nickel. J. Appl. Electrochem.
1998, 28 (10), 1095–1099. https://doi.org/10.1023/A:1003452615814.

(4) Sivasakthi, P.; Sekar, R.; Bapu, G. N. K. R. Pulse Electrodeposited Nickel Using Sulphamate Electrolyte for Hardness and Corrosion Resistance. Mater. Res. Bull.
2015, 70, 832–839. https://doi.org/10.1016/j.materresbull.2015.06.019.

(5) El-Sherik, A. M.; Erb, U.; Page, J. Microstructural Evolution in Pulse Plated Nickel Electrodeposits. Surf. Coat. Technol.
1997, 88 (1), 70–78. https://doi.org/10.1016/S0257-8972(96)02928-3.

Figure 1
Nanocomposite Engineering of Heterogeneous Mn-Based Cation-Disordered Cathodes for High-Performance and Low-Cost Lithium-Ion Batteries
Authors: Lee Eunryeol , Park Sang-Wook , Lee Dae-Hyung , Malik Rahul , Lee Hyun-Wook , Lee Jinhyuk , Seo Dong-Hwa
Published: December 2024

High-capacity cathodes for Li-ion batteries without Co and Ni are critical for lower $/kWh. Mn-rich cathode compounds are cost-effective alternatives. Partially cation-disordered cathodes are promising due to their high energy densities and fast rate capability. However, they have a poor cycle life, requiring an understanding of the structure-property relationship. This study shows these cathodes have a multi-phase heterogeneous nature and presents a nanocomposite engineering strategy to modify the phase heterogeneity and enhance cycling stability. Additionally, we demonstrated that these engineered cathodes can achieve high energy densities at the electrode level with over 95% weight-active material. These findings expand cation-disordered cathode materials and offer insights into developing low-cost Li-ion cathodes."
Effect of Nanoparticles As Additives on Lithium-Ion Transport in Composite Polymer Electrolytes
Authors: Burns Meghan , Counihan Michael , Cabana Jordi , Tepavcevic Sanja
Published: December 2024

Advancing solid-state battery technology holds immense promise in the context of climate change, providing a sustainable path toward efficient energy storage and electric vehicles. Li metal batteries are an ideal candidate for this need due to the high theoretical specific capacity of Li metal (3860 mA h g-1). Composite polymer electrolytes (CPEs) are being explored for lithium-metal solid state batteries (SSBs) due to their potentially high ionic conductivity, ease of processing, and ideal mechanical properties. In this work, we looked at poly(ethylene oxide) and lithium bis(trifluoromethanesulfonyl)imide (PEO-LiTFSI) as a polymer matrix due to its superb mechanical properties, low material cost, and ideal interfacial contact with the Li anode. The addition of 20 wt % tetraethylene glycol dimethyl ether (TEGDME) plasticizer to the PEO-LiTFSI matrix had a significant increase in conductivity at room temperature compared to neat PEO-LiTFSI. Furthermore, the incorporation of TEGDME resulted in enhanced flexibility, strength, and workability. This clearly illustrates the positive impact of the plasticizer on both conductivity and mechanical properties. To further improve the CPE performance, we added 20 wt % of different 500 nm nanoparticles to the PEO-LiTFSI-20 wt % TEGDME matrix. In CPEs with added neat aluminum oxide (Al2O3) nanoparticles the conductivity, transference number, limiting current, and interfacial resistance were all unchanged compared to the plasticizer mixture. Since the addition of the Li-inactive, neat Al2O3 nanoparticles had no impact on cell performance, we then tested the addition of ionically conductive, silane-functionalized Li7La3Zr2O12 nanoparticles (s@LLZO) but observed no significant change in ionic conductivity. However, there was a large decrease in interfacial resistance and an increase in transference number. As a result, the limiting current with s@LLZO nanoparticles was tripled as compared to the addition of the same size neat Al2O3 nanoparticles. To see if the addition of the silane to LLZO interface was the main reason behind the improved cell performance, we also tested silanized aluminum oxide nanoparticles (s@ Al2O3) but observed no significant changes when compared to neat Al2O3. These results confirmed that the addition of the lithium containing s@LLZO nanoparticles is beneficial to the overall cell performance of CPE, and we are currently investigating the mechanism of the improved Li-transport. Further optimization of these systems holds the potential to significantly enhance the charging rates of SSBs using composite polymer electrolytes.
Effect of Fast-Charging and Cycling Window on Lithium-Ion Battery Performance and Aging
Authors: Venkatakrishnan Sankaranarayanan , Ramasamy Ramaraja
Published: December 2024

Aggressive charging practices and extreme usage patterns of electric vehicle batteries pose safety risks, including fire hazards. Beyond fast charging, battery health is influenced by dynamic factors like temperature, state-of-charge (SoC) window of operation, and driving conditions relative to charging events1,2. Given that electric vehicles (EVs) rarely operate in their full SoC range (0–100%)3, understanding battery cell degradation across different SoC swing ranges and fast-charging effects becomes critical. This understanding not only optimizes battery usage and extends cell lifespan but also enhances lifetime economics and mitigates environmental consequences tied to raw material extraction and manufacturing2.

This study explores the impact of SoC swing ranges and fast charging on the performance and aging of commercially available 18650 cells equipped with graphite-NCA electrodes. Departing from the conventional constant-current constant-voltage (CC-CV) fast charging protocol, we adopted a scaled-down version of the 150-kW real-world battery electric vehicle (BEV) fast charging profile. Unlike the broader SoC range of high current charging typical in CC-CV protocol, the real-world BEV fast-charging profile charges the battery at peak power or peak current only in a narrow SoC range between 10% and 40% SoC and then tapers down. Cycling experiments were conducted for two sets of SoC ranges: 0%-50% and 0%-100%. Both cycling experiments exhibited similar trends in overall capacity fade, yet the underlying causes differed. The DV-IC analysis revealed that the loss of active negative electrode material (LAMNE) was pivotal in capacity fade for both cycling experiments. Notably, during 0%-100% SoC cycling, loss of positive electrode material was observed alongside LAMNE. Additionally, variations in the homogeneity of lithium distribution within the negative electrode and kinetic rate degradation of the negative electrode were evident.

This research underscores the critical role of SoC swing ranges and fast charging protocols in battery degradation, with differential voltage and incremental capacity analysis revealing distinct degradation pathways. It highlights the need for optimized battery usage strategies to extend cell lifespan, enhance lifetime economics, and mitigate environmental impact, thereby contributing to the sustainable growth of the EV market.

References:

C. R. Birkl, M. R. Roberts, E. McTurk, P. G. Bruce, and D. A. Howey, Journal of Power Sources, 341, 373–386 (2017).

J. S. Edge et al., Physical Chemistry Chemical Physics, 23, 8200–8221 (2021).

G. Luo, Y. Zhang, and A. Tang, Energies, 16, 4232 (2023).
(Invited) Probing the Functionality of Lithium Carbonate in Lithium Metal Interphases through Model and Native SEI
Authors: Gallant Betar M.
Published: December 2024

The lithium (Li) metal anode promises significantly higher capacity than graphite and is central to strategies to develop advanced Li-ion batteries with improved energy, lifetime and performance. Yet, the Coulombic efficiency (CE) of Li anodes in liquid electrolytes still falls well below the >99.9% targeted for electric vehicles. Efficiency and capacity loss arise from uncontrolled reactivity at the solid electrolyte interphase (SEI) and its resulting physicochemical, ionic and electronic properties, which couple to inhomogeneous plating/stripping, SEI breakage, electrolyte infiltration and additional consumption, and ultimately to loss of active Li inventory as stranded Li0 or SEI Li+. Despite empirical insights into electrolyte design guidelines, quantitative understanding of SEI functionality is underdeveloped, hindering attempts to control and improve its properties through tailoring of its materials chemistry.

This talk will discuss ongoing efforts to improve understanding of phase-specific functionality in the SEI, with an objective of identifying compositional design principles to minimize active Li inventory loss. We developed approaches to isolate and synthesize SEI-relevant ionic and organic phases, including lithium fluoride (LiF)1, lithium oxide (Li2O),2and recently lithium carbonate (Li2CO3), at representative nanometer-scale thicknesses directly on Li metal. These interfaces are interrogated via targeted electrochemical techniques to reveal their Li+ conductivity, providing a framework to assess which phases bolster, or hinder, ion transport in the SEI. Here we examine in detail the role of Li2CO3, a pervasive yet metastable SEI component that has long been asserted to improve CE in conventional carbonate electrolytes.3-5 By synthesizing model Li2CO3 interphases, we measure the ionic conductivity, probe reaction pathways in contact with specific electrolyte constituents, and interpret its properties against other key ionic SEI phases. We further examine the role of carbonate on the native SEI through re-examination of CO2 gas as a cell additive in a wider range of electrolytes—including modern formulations like ethers and localized high-concentration electrolytes (LHCEs)—than those studied previously. In combination with titration methods,6,7 we finally reveal how Li2CO3 relates to capacity loss at the anode and conditions in which enhancing Li2CO3 translates into improved CE.

He, R. Guo, G. Hobold, H. Gao and B.M. Gallant, PNAS 2020, 117, 73-79.

Guo and B.M. Gallant, Chemistry of Materials 2020, 32, 13, 5525-5533.

Plichta, S. Slane, M. Uchiyama, M. Salomon, D. Chua, W. B. Ebner and H. W. Lin, J. Electrochem. Soc. 1989, 136, 1865.

Aurbach, Y. Gofer, M. Ben-Zion and P. Aped, J. Electroanal. Chem 1992, 339, 451.

D. Aurbach, I. Weissman, A. Zaban and O. Chusid, Electrochimica Acta 1994, 39, 51.

Fang, J. Li, M. Zhang et al., Nature 2019,572, 511–515.

M. Hobold and B. M. Gallant, ACS Energy Letters 2022, 7, 3458-3466.
(Invited) Electrochemical Deposition for Microelectronic Interconnects
Authors: Moffat Thomas P , Raciti David , Kim Hyunki , Braun Trevor , Josell Daniel
Published: December 2024

Since the beginning of the microelectronics era, ongoing miniaturization of transistors has been accompanied by the development of ever more intricate multilevel Cu interconnects. Presently these range from nanoscale on-chip wiring to 3D TSV for chip stacking along with related structures for advanced packaging and printed circuit board applications. Electrodeposition has been a key process for void-free Cu filling of recessed patterned features by virtue of surfactant-mediated superconformal growth. This lecture will detail how the combination of electroanalytical kinetics, metallurgical analysis, and in situ electrochemical surface science measurements can be used to reveal the mechanisms associated with this unusual deposition mode. Going forward, significant challenges loom as surface and grain boundary scattering threaten to curtail Cu interconnect scaling at the finest dimensions and thus the search for new materials and alternative processing schemes is underway. Accordingly, the extension of insights gained from Cu superfilling to the processing of other materials will be discussed.

Figure 1
(Invited) Metallization for Advanced Semiconductor Technology Nodes: Wet-Chemical Deposition and Etching, Characterization, and (Semi) Damascene Approaches
Authors: Philipsen Harold
Published: December 2024

To ensure semiconductor technology scaling to continue for the decades to come, the industry focuses on identifying alternative metals (elemental or alloys), that can replace copper in the back end of line (BEOL) integration scheme, for which the metal is used as main conductor for most of the metallization levels. Recently, the semi-damascene process is being developed, in which the interconnect metal is first deposited and then patterned using a dry etching process (‘direct metal etch’), in a fashion closely resembling the traditional Al metallization. One of the advantages is that any metal that can be deposited as a blanket thin film (either by physical vapor deposition (PVD), electrochemical deposition (ECD), electroless deposition (ELD), chemical vapour deposition (CVD), or atomic layer deposition (ALD)) can subsequently be patterned, provided that the critical requirement for dry etching of ‘volatilization’ of the metal is fulfilled. Furthermore, it allows the integration of materials for which no ECD, ELD, CVD or ALD process is available to fill damascene trenches.

In this contribution, intrinsic material properties (bulk resistivity, electromigration, ...) and composition (surface versus bulk composition as well as surface oxide) of a wide range of metals and alloys of interest to the BEOL will be compared. An overview of wet-chemical deposition approaches of a few selected metals (Cu and Rh) will be given. For ELD, the focus will be on discussing the mechanistic understanding of the intrinsically complex process, for which the stability and reactivity of the reducing agent is affected by solution pH and composition as well as the presence of oxygen. For ECD, results will be discussed for Rh and Ni, for which an electrochemical quartz crystal microbalance (EQCM) was used to quantify the amount of material deposited and interpret the various features detected in cyclic voltammograms. Metal ion solution speciation as well as stability, of importance for both deposition methods, has been studied using UV-vis spectroscopy and electrochemical characterization (linear sweep and cyclic voltammetry). Deposits were analysed morphologically using transmission electron microscopy and the chemical composition was assessed by elemental mapping.

During process integration, the surface-chemical composition of metals / alloys needs to be carefully controlled, as this can, for instance, critically impact metal line resistance or result in wet etching or corrosion. A few example cases in which this is relevant will be presented, e.g. the reversible surface oxidation and reduction of Cu was studied using EQCM, the surface chemistry of NiAl was characterized using electrochemical measurements, and the reversible surface nitridation of a model metal (Mo) is demonstrated as a method to protect against unwanted metal dissolution.
A Combined Aerosol Jet Printing and Electrodeposition Process for Fabrication of Multi-Layer Inductors and Transformers on Iron-Nitride Substrates
Authors: Tsui Lok-kun , Manzi Jacob , Hartmann Thomas Michael , Dye Joshua , Lavin Judith Maria
Published: December 2024

The manufacturing of planar spiral transformers and inductors by direct write additive manufacturing is an attractive approach because they are lighter, less brittle, and have the added customizability of a digital design process compared with conventional wire-wound inductors. Aerosol jet printing (AJP) is a direct write process capable of printing structures with less than 10 µm lateral resolution. However, the nanoparticle Ag inks used in AJP of conductive parts typically only have 35-40% of bulk conductivity. A hybrid electroless deposition of Cu and electrodeposition of Cu and Ni process can decrease the resistance of AJP printed silver spiral inductors by a factor of 45x while maintaining linewidths of 50 µm.[1] We have recently demonstrated the use of this hybrid method to manufacture a coreless flyback transformer with a primary inductance of 206-208 nH and a secondary inductance of 19.4-23.1 µH. This inductor converted an input of 17 V at 400 kHz to an output of 1250 V.[2]

Forming the transformer on a magnetic layer of Fe4N can increase the inductance of the primary and secondary inductors, and ultimately the output of the transformer. Transformers (Figure 1) were manufactured on polyimide covered Fe4N substrates by aerosol jet printing of Ag seed layers, electrodeposition of Cu and Ni, and ultrasonic spraying or aerosol jetting of dielectric polymer separation layers. A new plating fixture which contacts both the interior and exterior of the secondary inductors enables the electrodeposition of Cu without the need for an intermediate electroless deposition step. For the same inductor configuration, the inductance increased to 561-809 nH for the primary and 63-82 µH for the secondary when sandwiched between Fe4N layers. Finally, a flyback transformer of this design converted an input voltage of 15V to an output voltage of greater than 2100V.

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. SAND2024-04161A.

References

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

[2] L. Tsui, T. M. Hartmann, J. Dye, J. M. Lavin. 2023 IEEE Transactions on Components, Packaging and Manufacturing Technol., 13, 8, 1302-1309.

Figure 1. Construction of a multi-layer transformer on an Fe4N substrate. (a) Primary Layer 1. (b) Primary Layer 2. (c) Secondary Layer 1. (d) Secondary Layer 2.

Figure 1
Application of Single Ion Conductive Polymers in High Voltage Solid-State Batteries
Authors: Dominko Robert , Guerrero Mejía Luis Miguel , Vargas Ordaz Mariana , Kosir Urban , Wang Aiping , Talian Sara Drvarič
Published: December 2024

All solid-state batteries are considered a future technology that can further increase energy density, improve safety, and extend the life of battery packs in various devices. The biggest challenge with solid-state batteries is the chemical and mechanical stability of the interfaces. Continuous volumetric changes and thermodynamic instability of high-voltage cathodes and metallic lithium with electrolyte require innovative approaches to interface design. Conductive single-ion polymers are considered as possible solutions, but cannot be used as a single component due to various limitations.

In this presentation, we focus on the development of protective coatings based on conductive single-ion polymer. The coating is applied to NCM811 particles. The aim is to create a homogeneous, thin coating that acts both as a channel for the transport of lithium and as an electronic conductor that promotes good contact between the NCM811 particles, the binder, and the carbon black particles. The stability and reversibility of the Li metal anode are achieved by the protective coating based on cellulose and the P(LiMTFSI) single-ion conductor polymer, including different fillers. The applied strategy involves the physical blending of the polymer and fillers with cellulose to improve the electrochemical performance by homogenizing the Li-ion flux at the Li metal surface and promoting the formation of a dense coating.

Acknowledgment: The authors would like to acknowledge funding from the Slovenian Research Agency (ARIS) under research programs P2-0423 and from the European Union Horizon 2020 research and innovation programme under grant agreements No. 945367 (Destiny) and No. 101069703 (PSIONIC).
Ultrafast Lithium-Ion Diffusion in Oxyhalides
Authors: Wei Grace , Jun KyuJung , Ceder Gerbrand
Published: December 2024

All solid-state batteries are a promising technology due to their employment of inorganic solid electrolytes (SEs), which are safer compared to their flammable, liquid counterparts. Recently, halide SEs have gained significant attention due to their relatively high ionic conductivity (> 1 mS/cm), wide electrochemical stability window, and compatibility with various electrode materials. However, prior to 2023, no known halide materials could reach the conductivities of the state-of-the-art sulfide SEs (> 10 mS/cm). This can be attributed to the close-packed anion arrangement of existing halide conductors, which confines lithium ions to narrow and high-energy conduction pathways. Recently, a new Li oxyhalide superionic conductor LiMOCl4 (M=Nb/Ta) was reported with extremely high ionic conductivities greater than 10 mS/cm [1]. Unlike previously found halide conductors, LiMOCl4 has a non-close-packed anion framework that provides a large conduction pathway. We present a first-principles investigation of the phase stability, electrochemical stability, and Li-ion conductivity in the LiMXCl4 (M = Ta, Nb, Sb, Ti, Zr, Hf, Sn, and X = O, F, Cl) family of superionic conductors. We identify a mixed-anion framework as key to stabilizing the oxyhalide structure and demonstrate the impact of aliovalent anion and cation substitutions on material properties. Long ab-initio molecular dynamics simulations spanning 10’s of ns confirm room temperature superionic conductivity in all systems. Probabilistic analysis of the rotational dynamics at the picosecond timescale contributes direct, quantitative evidence correlating the high Li-ion conductivity in oxyhalide systems with the soft tilting motion of MO2Cl4 octahedral groups present in the material. Our findings supply the theoretical underpinnings for the effectiveness of LiMXCl4 family of superionic conductors as catholytes compatible with 4-V-class layered cathodes and provide essential design criteria for constructing new Li halide superionic conductors with conductivity greater than 10 mS/cm.

[1] Y. Tanaka, K. Ueno, K. Mizuno, K. Takeuchi, T. Asano, A. Sakai, Angew. Chem. Int. Ed. 2023, 62, e202217581; Angew. Chem.
2023, 135, e202217581.
(Invited) Borohydride-Substituted Li Argyrodite Solid Electrolytes for All-Solid-State Batteries
Authors: Kim Jae-Hun
Published: December 2024

In recent times, there has been a notable increase in the worldwide adoption of electric vehicles, with lithum-ion batteries (LIBs) maintaining their dominant position in the market for electrochemical power sources. However, this expansion has generated a greater demand for LIBs with higher energy density, which has consequently raised concerns about their safety during usage. One significant method for addressing these concerns and satisfying the need for increased energy density involves replacing flammable and volatile liquid electrolytes with solid alternatives in current LIB designs. Inorganic solid electrolytes, characterized by a broad electrochemical stability range of up to 5 V, offer promising solutions by facilitating the use of high-capacity lithium metal anodes or anode-free systems, all while preventing the formation of dendritic lithium growth. Additionally, solid electrolytes substantially improve the safety profile of LIBs, as they exhibit greater stability compared to organic liquid electrolytes, especially in cases of thermal runaway. This presentation demonstrates the development of solid lithium argyrodite electrolytes containing BH4
– and halide anions. The resultant materials exhibit a notable ionic conductivity exceeding 10 mS cm–1 at room temperature. It has been noted that adjustments to the local structure of thiophosphate can be achieved by varying the quantities of BH4
– and halogen ions, leading to significant impacts on ionic conductivity. The all-solid-state battery employing the synthesized solid electrolyte exhibits superior performance in terms of cycle life and charging/discharging rates.
High Entropy Stabilized Porous Metallic Glass Nanosheet for Proton Exchange Membrane Water Electrolysis
Authors: Jo Seunghwan , Shin Ki Hoon , Sohn Jung Inn
Published: December 2024

Acid-stable oxygen evolution electrocatalyst is paramount for practical proton exchange membrane water electrolysis. Owing to the sluggish diffusion kinetics, the nonprecious high entropy materials that comprise more than five principle elements are considered promising candidates to alternate the noble metals by overcoming oxidative elution in acidic media. Herein, nonprecious high entropy material consisting of Co, Fe, Ni, Mo, and W has been prepared by electrochemical deposition and following Te-mediated glassification for acidic oxygen evolution electrocatalyst. The hybrid approach of electrochemical deposition combined with glassification enables porous nanosheet morphology with expanded surface area and increased valence states of metal cations, outperforming the non-glassified high entropy material (CoFeNiMoW). The glassified CoFeNiMoWTe exhibits a lower cell voltage of 1.81 mV than the CoFeNiMoW (1.87 V) and a low voltage increase of 30 mV for 100 h at the current density of 1 A cm-2 in the proton exchange membrane water electrolyzer.
Formation Efficiency of Anodic Alumina in Acidic Electrolyte Containing Amino Acid
Authors: Kusuyama Shota , Hagiwara Kenta , Asoh Hidetaka
Published: December 2024

Anodic porous alumina films, which are formed by anodization in acidic solution, provide hardness, wear resistance and corrosion resistance for the surface of aluminum used for automobile and aircraft parts. For instance, to increase the hardness of anodic films on aluminum, the anodization is industrially carried out at low temperature to avoid chemical dissolution of the film during anodization. From a perspective of energy conservation and decarbonization, an important objective are to reduce energy costs and improve work efficiency. Our group has reported that the addition of alcohol (e.g., methanol, ethanol, and ethylene glycol) to an electrolyte improves the formation efficiency and hardness of the film at 20 °C 1, 2). In this study, we focused on amino acids that having inhibitability of aluminum corrosion by adsorbing on the surface of aluminum in a mixed acid containing chloride ion 3). The effects of types and concentrations of amino acids on the anodization voltage, formation efficiency (coating ratio) and structure of the porous alumina were investigated. The sulfuric acid and oxalic acid were used as electrolytes, each containing various amino acids (e.g., glycine, α-alanine, and β-alanine). The electrolyte was maintained at a constant temperature of 20 °C using a thermostat and gently stirred at 300 rpm using a magnetic stirrer to accelerate the diﬀusion of the heat evolved during the anodization.

For example, anodization was conducted in 1.5 mol dm–3 sulfuric acid at 100 A m–2. After anodization for 60 min, the final voltage was 15 V. Even when 100 mmol glycine was added to sulfuric acid, the final voltage was almost the same as sulfuric acid alone. For sulfuric acid containing 800 mmol glycine, however, the final voltage (22 V) was higher than that for sulfuric acid alone. When the concentration of amino acid became high, the viscosity of the electrolyte increased, while the conductivity decreased. Even in the oxalic acid-based electrolyte, the tendency of amino acid concentration dependence of voltage was the same as that of sulfuric acid-based electrolyte. These results indicate that the increased final voltage can be attributed to the high solution resistance of the electrolyte used for anodization. The formation efficiency (coating ratio) and hardness of anodic film formed in acidic electrolyte containing amino acids will also be discussed.

1) Matsumoto, H. Hashimoto, H. Asoh, J. Electrochem. Soc., 167, 041504 (2020).

2) Asoh, T. Sano, J. Electrochem. Soc., 168, 103506 (2021).

3) Ashassi-Sorkhabi, Z. Ghasemi, D. Seifzadeh, Appl. Surf. Sci., 249, 408–418 (2005).
Direct Extraction of Lithium from α-Phase Spodumene By Electrochemical Leaching
Authors: Zhang Hanrui , Shi Feifei
Published: December 2024

With the rapid increase in lithium consumption for electric vehicle applications, its price soared during the past decade. To secure a reliable and cost-effective supply chain, it's critical to unlock alternative resources for lithium extraction, beyond conventional brine. In this study, we developed an electrochemical method to directly leach lithium from solid-state α-phase spodumene. We found the H2O2 promoter can significantly reduce the leaching potential by facilitating the electron transfer and changing the reaction path. Upon leaching, β-phase spodumene shows a typical phase transformation to HAlSi2O6, while leached α-phase remains its original phase with a lattice shrinkage. To demonstrate scale-up capability, we designed a high-throughput current collector for suspended spodumene feedstock, achieving a leaching current of 18 mA and a leaching efficiency of 92.2%. By minimizing the environmental footprint and reducing energy consumption, electrochemical leaching will revolutionize traditional mining and recycling processes for more sustainable energy applications.

Acknowledgments: H.Z. and F.S. thank the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research Program. F.S. thanks the support from the U.S. Department of Energy under contract DE-NE0009286. F.S. thanks the support from the National Science Foundation under Grant No. 2239690.
Coal-Derived Nanoscale Materials for Energy Storage Applications
Authors: Salimi Nanadegani Fereshteh , Khan Nadeem , Smith Natasha , Olson Rudolph , Sleppy Joe , Oladeji Isaiah , Silverstein Alisa , Wolfe Kody D , Trembly Jason , Staser John A.
Published: December 2024

The demand for carbon-based energy storage materials is growing as renewable energy production and electrification expand worldwide. The types of carbon-based energy storage materials are as diverse as the systems in which they operate. The source of these materials is also of interest. Some carbon-based energy storage materials are naturally occurring (i.e., graphite) while others are synthesized from other carbon precursors (i.e., synthetic graphite, activated carbon, graphene, etc.). This presentation will focus on this group's efforts to synthesize, by electrochemical methods, nanoscale carbon materials from an abundant natural resource, coal. The electrochemical synthesis procedure and physical characterization of the nanoscale materials will be discussed. The nanoscale material's performance in energy storage systems will be presented and compared to other commercially available carbon-based energy storage materials.
Investigating Crude Glycerol Electrooxidation
Authors: Gaines Rachel N , Sibal Adam P , Friel Bridget E , Shah Vijay M , Stillwell Ashlynn S , Kenis Paul J.A
Published: December 2024

Decarbonization of chemical manufacturing requires a range of strategies, including the utilization of process waste. This waste can then be used in processes powered by renewable electricity, such as electrocatalysis, to synthesize other useful chemicals. In doing so, process waste is reduced and industrially-relevant chemicals are produced without the use of fossil fuel-based feeds.

One intriguing candidate feedstock for electrocatalytic conversion to relevant chemicals is glycerol, produced as a byproduct of biodiesel production at ~10% by mass. Glycerol electrooxidation can produce up to 12 different compounds, all with relevant industrial uses. Prior work has studied glycerol electrooxidation extensively to understand the mechanisms by which these compounds are produced on a variety of different catalysts.1,2

However, most of these studies utilize 99+% pure glycerol to investigate these mechanisms. There is very limited information on the electrooxidation of impure, or “crude,” glycerol – the glycerol that will exit the biodiesel production process in an industrial setting. This crude glycerol is made up of a mixture of glycerol, methanol, sodium hydroxide, and water, and its composition varies dramatically depending on the manufacturer. It is critical to understand the electrooxidation of crude glycerol to effectively scale the reaction.

In this work, we investigate the electrooxidation of crude glycerol in scalable flow electrolyzers on precious3 and nonprecious metal catalysts. Using a multifaceted approach that includes system design, reaction engineering, and technoeconomic analysis, we explore the electrochemical performance of relevant compositions of crude glycerol and identify approaches to improve and augment that performance in terms of chemical production and cost efficiency.

(1) Fleischmann, M.; Korinek, K.; Pletcher, D. The Oxidation of Organic Compounds at a Nickel Anode in Alkaline Solution. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1971.

(2) Houache, M. S. E.; Hughes, K.; Baranova, E. A. Study on Catalyst Selection for Electrochemical Valorization of Glycerol. Sustainable Energy and Fuels, 2019.

(3) Gaines, R. N.; Kleimenhagen, B. A.; Griebler, J. J.; Harris, L. C.; Gewirth, A. A.; Rogers, S. A.; Kenis, P. J. A. Optimizing the Flow Electrooxidation of Glycerol Using Statistical Design of Experiments. Journal of the Electrochemical Society, 2024.
Quantifying the Temperature Dependence of the Multi-Species, Multi-Reaction Model
Authors: Paul Abigail , Magee Regan , Baca Isabel , Wilczewski Warren , Wichert Nathan , Wolfe Kody D , Lowe Jeffrey , Trembly Jason , Staser John A. , Garrick Taylor R.
Published: December 2024

The Multi-Species, Multi-Reaction (MSMR) model utilizes slow-rate lithiation and delithiation data to estimate parameters such as total fraction of available host sites, reference potential, and deviation from Nernstian behavior.1 The MSMR model has successfully been applied to a variety of common lithium-ion materials such as lithated silicon2, graphite, iron phosphate and spinel manganese oxide.3-5

In this presentation, the temperature impact on MSMR gallery parameters will be presented for coal-derived and commercially available graphite. The temperature dependent trends observed and their impact on a system will be discussed. A comparison of the MSMR parameters for each material will be provided. The commonalities and differences in the trends will be discussed and linked back to the differences observed in the graphite material properties.

References:

Baker D. R. and Verbrugge M. W. 2018 Electrochem. Soc.
165 A3952

Verbrugge M., Baker D. and Xiao X. 2015 Electrochem. Soc.
163 A262

Paul et al., Journal of The Electrochemical Society, 171, 039001 (2024)

Verbrugge M., Baker D., Koch B., Xiao X. and Gu W. 2017 Electrochem. Soc.
164 E3243

Baker D. R., Verbrugge M. W. and Gu W. 2019 Electrochem. Soc.
166 A521
Deconstructing the Onsager-Stefan-Maxwell Framework
Authors: Rungta Rohit , Monroe Charles W.
Published: December 2024

The increasing drive for enhanced electrochemical energy storage underscores the importance of understanding and predicting concentrated electrolyte transport behavior. The most popular frameworks for understanding ion transport in concentrated electrolytes are the Stefan-Maxwell and Onsager frameworks. The Stefan–Maxwell equations relate the electrochemical potential’s gradient in terms of the flux driving forces [1]. On the other hand, the Onsager framework inverts this to relate the species flux in terms of the thermodynamic driving forces [2]. Both are thermodynamically consistent, but each framework requires different transport properties which are often experimentally and computationally obtained with varying simplifying assumptions.

This study utilizes a ‘salt–charge basis’ developed by Van-Brunt and Monroe to relate the transport properties from the Stefan–Maxwell to Onsager framework [3]. One-by-one, each assumption within the Stefan–Maxwell framework is relaxed and compared to the equivalent Onsager framework. The three independent assumptions are electroneutrality, thermodynamic ideality (no mixing energies), and no ion-ion drag. Varying combinations of these assumptions relate to different models utilized throughout literature. The most ubiquitous of these in the battery community is the Doyle, Fuller, and Newman’s physics-based model [4] which accounts for ion-ion drag and nonideal thermodynamics in the binary salt.

This systematic deconstruction allows for an overview of the variety of sub-models used in battery and electrolyte modelling.

References

[1] J. Newman and K. E. Thomas-Alyea, Electrochemical Systems, 3rd ed. New Jersey: John Wiley & Sons, Inc., 2004.

[2] L. Onsager, The Collected Works of Lars Onsager, vol. 17. Trondheim: World Scientific Publishing Co., 1996.

[3] A. Van-Brunt, P. E. Farrell, and C. W. Monroe, ‘Structural electroneutrality in Onsager–Stefan–Maxwell transport with charged species’, Electrochim Acta, vol. 441, Feb. 2023, doi: 10.1016/j.electacta.2022.141769.

[4] M. Doyle, T. F. Fuller, and J. Newman, ‘Modeling of Galvanostatic Charge and Discharge of the Lithium/Polymer/Insertion Cell’, J Electrochem Soc, vol. 140, no. 6, pp. 1526–1533, Jun. 1993, doi: 10.1149/1.2221597.
(Invited) High-Frequency Impedance Measurements on Cement Paste Loaded with Steel Fibres
Authors: Díaz B. , Diéguez A. , Gil C. , Novoa X. Ramon , Paz C. , Pérez C.
Published: December 2024

Good mechanical performance and a multifunctional character make conducting fibre-reinforced cement-based materials of great technological interest. In addition to their excellent structural performance, the non-destructive damage and strain detection ability or the inherent electrical conductivity have expanded the range of applications of these composites [1].

The composite's properties depend mainly on the fibre's concentration. But, for a given nominal concentration, the critical practical aspect is the degree of dispersibility achieved during the mixing process. This is an unsolved problem that greatly conditions the reproducibility of mixes in terms of their properties. No non-destructive method for examining the fibre's orientation and dispersibility is currently available to investigate the dispersibility degree.

Recent studies [2] have shown that the high-frequency part of the impedance spectra obtained from fibre-reinforced composites is sensitive to the presence of fibres, and the time constants present in that frequency domain allow information about the material's microstructure and conductivity. The present contribution will discuss new experimental results and numerical simulations to provide a step forward in assessing the fibre's orientation and dispersibility degree based on impedance spectroscopy measurements.

References

[1] D.D.L. Chung, Cement reinforced with short carbon fibers: a multifunctional material, Compos. Part B Eng. 31 (2000) 511–526. https://doi.org/10.1016/S1359-8368(99)00071-2.

[2] B. Díaz, B. Guitián, X. Ramón Nóvoa, C. Pérez, Conductivity assessment of multifunctional cement pastes by impedance spectroscopy, Corros. Sci. 185 (2021) 109441 (9pp). https://doi.org/10.1016/j.corsci.2021.109441.
Matching Operating Parameters and Catalysts for the Sulphur Depolarized Electrolysis
Authors: Roessler Escudero Lukas Fernando , Hacker Viktor , Bodner Merit
Published: December 2024

Sulphur depolarized electrolysers (SDE) represent an important alternative for green and economic hydrogen production in places where SO2 and energy are available, such as mining, refineries, pulp and paper industry, among others. The SDE reaction relies on the oxidation of the SO2 into sulphuric acid on the anode side, while forming H2 on the cathode. Through the depolarization of the anode, the theoretical voltage of the overall reaction is decreased to 0.158 V, allowing a less energy intensive process and the utilization of different, non-CRM catalysts [1]. SDE technology was first studied on the late 70s but was mostly abandoned until the mid-2000s. Therefore, these electrolysers are in an early stage of development and the ideal operation requirements are still not clear. The operation of an SDE has been approached utilizing aqueous SO2 dissolved in H2SO4 feed, resulting in short term promising results but fast degradation and excessive SO2 crossover [2]. In our previous study, the operating parameters of the anodic SO2 flow, Pt catalyst loading and applied voltage were assessed [3]. In the present study, the effects on temperature, water management on Pt as well as alternative non-CRM-based catalysts were studied. By the modification of these parameters it is possible to fully determine the sensitivity of catalyst systems towards operating parameters, prioritizing a stable operation without SO2 crossover, the main issue regarding SDE. To evaluate the results, boundary experiments are carried out as well as continuous operation of up to 5 h. The products are characterized utilizing SEM/EDX for the solid components such as GDL, membrane and catalyst layer, while the products are analysed using titration and GC-MS to determine the purity of the products as well as the efficiency of the process.

[1] J. L. Steimke, T. Steeper, H. Cólon-Mercado y M. B. Gorensek, «Development and testing of a PEM SO2-depolarized electrolyser and an operating method that prevents sulfur accumulation, » International Journal of Hydrogen Energy, pp. 13281-13294, 2 September 2015.

[2] R. J. Kriek, J. Rossmeisl, S. Siahrostami y M. E. Björketun, «H2 production through electro-oxidation of SO2: identifying the fundamental limitations, » Physical Chemistry Chemical Physics, 2014.

[3] L. Roessler Escudero, V. Hacker y M. Bodner, «Operating boundaries for the mitigation of SO2 crossover in sulphur depolarised electrolyser cells, » Journal of Power Sources, (Submitted).

Figure 1
Li-Mediated Electrochemical NH3 Synthesis Utilizing H2o As a Proton Source
Authors: Kim Jae Hyung , Shim Joonmok , Kim Sun Hyung , Lee Kyungho , Yoon Hyung Chul
Published: December 2024

Electrochemical ammonia (NH3) synthesis is a promising technology for sustainable NH3 production that does not require H2 extraction from natural gas or coal which results in significant amounts of CO2 emissions. However, in aqueous electrolytes, the kinetics of H2O reduction (or proton coupling) into H2 is much faster than that of N2 reduction, leading to the dominance of the H2 evolution reaction. To address these challenges, the Li-mediated electrochemical N2 reduction reaction (Li-NRR) has been investigated in polar aprotic organic solvents, and a high NH3 production rate and faradaic efficiency (F.E.) have been obtained. Although significant progress has been made in the Li-NRR, the sustainability of the reaction system remains questionable. As an anode reaction, sacrificial oxidation of the THF-based electrolyte is exploited and the electrolyte undergoes oxidative chemical transformations. To prevent electrolyte degradation at the anode, the H2 oxidation reaction has been derived by supplying additional H2. However, such a methodology is a paradoxical approach to the original purpose of electrochemical NH3 synthesis to replace the proton source for NH3 with H2O from H2. Nevertheless, the absence of H2O (or a low concentration of H2O) is a prerequisite for the Li-NRR; thus, attempts to provide H2O as a proton source for NH3 have not yet been made. In this presentation, we show a biphasic hybrid electrolyte system consisting of an organic solvent catholyte and aqueous anolyte to supply the proton from H2O oxidation (O2 evolution reaction) for electrochemical NH3 synthesis. A comparable NH3 production rate and F.E. could be achieved in the hybrid system using H2O as the proton source, similar to those of the conventional one-compartment Li-NRR system. The hybrid electrolyte system maintains ~60% of NH3 F.E. for 50 h without the electrolyte degradations at a current density of −5 mA cm−2. We expect that this hybrid electrolyte system holds the potential to extend the applications of electrochemical conversion reactions beyond the Li-NRR system.