bluuebunny/crossref_metadata_2025_split huggingface dataset:
Understanding Shelf Life of Electrolytes with LiPF6 Under Commercially Relevant Storage Conditions
Authors: Garg Shipra , Hennek Matthew , Kerber Brian M , Guillot Sarah Lucienne , Giedd Michael , Sadowski Diana , Usrey Monica Lee 
Published: December 2024

Lithium hexafluorophosphate (LiPF6) salt is the most commonly used lithium salt in commercial Li-ion batteries due to its high conductivity, passivation of Al current collectors for positive electrodes, and participation in SEI layer formation at graphite anodes.1 However, LiPF6 suffers from poor thermal stability and poor stability toward protic species (like water) leading to decomposition that can significantly reduce Li-ion battery performance especially under the extreme conditions demanded by today’s industrial applications. Specifically, LiPF6 decomposition leads to HF generation, especially in the presence of water,2 which results in multiple negative outcomes in Li-ion cells including dissolution of cathode materials and gas generation.3 Conditions during electrolyte blending, transport, and/or storage often exacerbate LiPF6 instability and increase HF generation.
To date, efforts to replace LiPF6 have not proven to be commercially successful, therefore strategies to improve the stability of LiPF6 electrolytes under relevant storage conditions are critical to support the deployment of Li-ion batteries. Orbia Fluor and Energy Materials has extensively characterized the degradation of LiPF6 as a function of multiple conditions, including temperature, water content, electrolyte composition, and container materials to inform the design of strategies to improve stability.
This poster will illustrate the understanding of LiPF6 decomposition (and HF generation) under conditions relevant to the Li-ion electrolyte supply chain and will present data showing a series of fluorinated materials that improve the thermal stability of LiPF6 electrolyte through the elimination of existing HF and suppression of additional formation. In addition, Orbia Fluor and Energy Materials has launched a custom electrolyte blending business to provide high quality, domestically produced lithium-ion battery electrolytes to enable the clean energy transition.
References:

Sascha Nowak and Martin Winter 2015 J. Electrochem. Soc. 162 A2500

Hui Yang et al 2006 J. Power Sources 161 573

Weishan Li 2020 J. Electrochem. Soc. 167 090514
New Insights into the Crystal Structure of Fe0.5TiOPO4 Anode Material for Lithium-Ion Batteries Using Non-Ambient X-Ray Diffraction Measurements
Authors: Lasri Karima , Mahmoud Abdelfattah , Sougrati Moulay Tahar 
Published: December 2024

The search for alternative electrode materials for lithium and sodium ion batteries is an expanding field with a continuous effort of research. Among the various materials, polyanionic phosphate compounds M0.5TiOPO4 (M= Fe, Ni, Co, Cu) have been investigated as anode materials for Lithium-ion batteries due to their several advantages.
Our research group has been investigating the crystal and electronic structure changes of Fe0.5TiOPO4/C material that occur during the insertion/extraction of lithium ions. Hence, Operando X-ray diffraction (XRD) measurements on Fe0.5TiOPO4/C composite were conducted. The experiments were performed using special electrochemical coin cells with glass windows, which enabled us to conduct operando XRD measurements on the battery cell during operation. The coin cells were prepared in a glovebox under an Argon atmosphere. In-situ Iron-57 Mössbauer and in-situ X-ray Absorption Near Edge Spectroscopy (XANES) were also performed to reveal the electrochemical mechanisms of this material.
After analyzing all the results at high and low voltage cut-offs, we found that Fe0.5TiOPO4/C electrode materials maintain their structure crystallinity after cycling between [3.0-1.3V], showing the formation of a new phase at the end of the first discharge. At highly lithiated states, [3.0-0.02V] voltage range, a reduction–decomposition reaction highlights the Li-insertion/extraction behaviors, and low phase crystallinity is observed during cycling.
Furthermore, the Iron-57 Mössbauer analysis on the pristine material Fe0.5TiOPO4/C revealed the presence of two distinct Iron environments, which contradicts the previously reported structural observations. To gain more insights into the crystal structure of the pristine material, we conducted XRD measurements between 13 and 300 K conditions. From Rietveld refinements, we determined the newly found crystal structure of Fe0.5TiOPO4/C, which shows that the Fe2+ cations can be in two triangular-based antiprism crystallographic sites. This finding is further supported by DFT calculations, which demonstrate the possibility of the co-existence of several host sites for Fe2+.
Fullertubes: Current Progress and Latest Isolation of New Molecules
Authors: Stevenson Steven 
Published: December 2024

In 2020,1 it was experimentally demonstrated that [5,5] C100 fullertubes are finally found in carbon soot and are isolable. These new fullertube molecules have the benefit of defined structures, reproducible molar masses, and are soluble in aromatic organic solvents and carbon disulfide. Fullertubes exist as a series of family members whose length (aspect ratio) can be extended by adding belts of carbon to its tubular region. Since 2020, newly experimentally isolated [5,5] C120 (2022)2 and [5-5] C130 (2023)3 fullertubes are also now purified and characterized. Indeed, both fundamental science and application development are, in parallel, underway to explore their unique features. In this oral presentation, I will discuss the latest findings related to their synthesis, separation strategies, new fullertubes on the horizon, and early characterizations. I will also discuss the most up-to-date progress in fullertube application R&D.
(1) Koenig, R. M. et al, JACS,2020, 142 (36), 15614-15623.
(2) Liu, X. et al, JACS, 2022, 144 (36), 16287-16291.
(3) Bourret, E. et al., JACS,2023, 145 (48), 25942-25947.

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Sulfate Radical Oxidation for Enhancing Polishing-Rate Forhardmask-Film Chemical–Mechanical-Planarization
Authors: Park Jea-Gun , Han Manhyup , Kim Myung-Hae , Koh Hyun-Sung , Park Jin-Hyung 
Published: December 2024

Recently, to scale down semiconductor devices less than several nm (i.e.,m 5, 4, and 3 nm), lithography using a 193 nm ArF excimer laser, extreme ultraviolet lithography (EUVL), and 13.8 nm laser-produced plasma were applied. However, since photoresist patterns with a high aspect ratio could easily result in collapse of photoresist patterns, a carbon polymer hardmask between the photoresist and the substrate film has been introduced. The carbon polymer hardmask produces a high surface topography induced by pattern density, requiring chemical-mechanical planarization (CMP) for removing such surface topography. Although, the demand for hardmask-film CMP slurries performing high polishing-rate has been increased, the improving the carbon polymer hardmask-film polishing-rate has been considered difficult because of its hardenss caused by C-C sp3 and C-C sp2 covalant bonds.
In this study, as a solution, unlike conventional oxidizing agent such as hydrogen peroxide(H2O2), sulfate radical oxidant (i.e., Patassium persulfate) was used in the hardmask-film CMP slurry for acheiving high quality surface roughness and enhancing hardmask-film polishing-rate. The new designed CMP slurry evidently accomplished hardmask surface oxidation via transformation from C-C sp3 and C-C sp2 covalent bonds to C-O bond during CMP, resulting an extremely high polishing-rate (i.e., 300 Å/min) and high quality surface roughness (i.e., 0.36 nm at 5x5 um2) at the sulfate radical oxidant concentration of 1 wt%. In our presentation, we will prove the mechanism of the sulfate radical oxidation on the polished hardmask-film surface. In addition, we will present the dependencies of the chemical dominant polishing properties (i.e., OH radical, chemical oxidation degree of the Ag-film surfcae, chemical composition of chemical oxidation, and slurry adsortion degree) as well as the mechanical dominant polishing properties (i.e., electrostatic force between abrasives and hardmask-film surface) on the surfate oxidant concentration.

Acknowledgment

This research was supported by the MOTIE(Ministry of Trade, Industry & Energy (1415180388) and KSRC(Korea Semiconductor Research Consortium) (20019474) support program for the development of the future semiconductor device, and by the Brain Korea 21 PLUS Program and the Samsung Display Co. Ltd.

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Tailored 3D Porous N-Doped Carbon Nanospheres for Bottom-up Electrode Design - Independent Pore and Particle Size Control for the Use in Model Electrodes
Authors: Ortlieb Niklas , Berestok Taisiia , Elsäßer Patrick , Küspert Sven , Mutscher Jonas , Fischer Anna 
Published: December 2024

Design of porous carbon-based electrode materials and derived porous electrode structures is crucial for the performance of electrochemical energy storage and conversion devices. In that context carbon-based electrode material building blocks with well-defined properties are desired. Such properties include controlled morphology (preferably spherical), particle size, and intra-particle porosity along with controlled composition, surface chemistry, and processability. These factors influence the particle arrangement and electrode structure during processing, as well as electrolyte interaction, distribution, and mass transport phenomena within the electrode.
In this work, we introduce a hard-templating method for producing highly uniform meso- and macroporous N-doped carbon nanospheres with independently tuneable pore and particle sizes, serving as a versatile material platform for the bottom-up design of 3D porous carbon electrodes. We could thereby customize the pore sizes between approximately 10 to 100 nm at a constant particle size, while particle sizes between 50 and 300 nm could be achieved for a constant pore size. Other physicochemical parameters such as chemical composition, graphitization, and surface functionalization remained constant across all samples, allowing for the exclusive investigation of pore and particle size effects independently from each other.
We further used our different N-doped carbon nanospheres as building blocks for 3D porous electrodes and studied these in electrochemical double-layer capacitors with the aim to (i) showcase the versatility of our materials and (ii) examine pore and particle size effects on the performance. Indeed, electrochemical double-layer capacitors serve as an excellent model system for such investigations due to their sensitivity to carbon particle surface area, pore size, and mass transport phenomena within the 3D percolated structure of porous carbon electrodes.
(Invited) How to Make and Manipulate Carbonaceous Materials Using Liquid Metals
Authors: Kalantar-Zadeh Kourosh 
Published: December 2024

Liquid metal-based processes offer significant possibilities in the realm of carbon-based materials. Liquid metals are highly electrically conductive, making them suitable for electrochemical redox processes. They serve as atomically smooth templating substrates for creating planar structures. The absence of interfacial forces, owing to the non-polar nature of liquid metals, facilitates self-exfoliation of the synthesized two-dimensional (2D) layers from the surface of liquid metals. In addition, liquid metals can act as natural catalysts for promoting the formation of C-C bonds and are immiscible with non-metallic systems, including electrolytes, making them compatible with various electrochemical systems. Liquid metals can also engineer carbonaceous materials in contact with their interface. These properties facilitate the construction of carbonaceous materials from various organic precursors to CO2 and also tailoring of carbon based materials using liquid metals.
Room temperature synthesis and engineering of 2D graphitic materials (2D-GMs) remains an elusive goal, especially through electrochemical means. Here, it is demonstrated that liquid metals make this achievable by providing catalytic activity and an ultra-smooth templating interface conducive to Frank–van der Merwe regime growth. Moreover, they enable facile exfoliation due to the absence of interfacial forces as a non-polar liquid. The 2D-GMs is shown to be formed at a low onset potential and can be in situ doped based on the choice of organic precursors and the electrochemical setup. The synthesized materials can be tuned to exhibit porous or pinhole-free morphologies and engineered for their degree of oxidation and number of layers.
In another part of the talk, the interfacial interaction between eutectic gallium–indium (EGaIn) liquid metal and graphene oxide (GO) for reducing both substrate-based and free-standing GO will be discussed. NanoIR surface mapping confirms the successful removal of carbonyl groups. Building upon this knowledge, a composite comprising assembled reduced GO sheets on LM microdroplets (LM–rGO) is presented. The LM reinforces Ga3+ coordination within the rGO assembly, thereby modifying the electrochemical interface for selective dopamine sensing by separating the peaks of interfering biologicals. Subsequently, paper-based electrodes modified with LM–rGO is shown, demonstrating the compatibility of the assembly with low-cost commercial technologies.
(Energy Technology Division Walter van Schalkwijk Award in Sustainable Energy Technology) Ion-Pair Membranes for Advanced Electrochemical Devices
Authors: Kim Yu Seung 
Published: December 2024

Anhydrous proton-conducting materials offer significant advantages for electrochemical devices like fuel cells. Ion-pair membranes, first designed in 2016, emerged from studying of quaternized polymers where the cationic functional group tightly binds phosphate anions.1 In this talk, I will introduce the operational principles of ion-pair membranes and provide an in-depth discussion on their differences from traditional phosphoric acid-doped polybenzimidazole membranes. We will explore the benefits of using implementing ion-pair membranes, including improved acid retention, diverse membrane and ionomeric binder options, and membrane electrode assembly processing.2, 3 Recent advancements in the performance and durability of fuel cells and electrochemical hydrogen pumps utilizing ion-pair membranes will also be covered.4-6 Lastly, I will address the scale-up production and commercialization efforts for ion-pair membrane technology and discuss the remaining challenges in this field.
References

Lee, K. S., Spendelow, J. S., Choe, Y. K., Fujimoto, C. & Kim, Y. S. An operationally flexible fuel cell based on quaternary ammonium-biphosphate ion pairs. Energy
1, 16120 (2016).

Lee, A. S., Choe, Y. K., Matanovic, I. & Kim, Y. S. The energetics of phosphoric acid interactions reveals a new acid loss mechanism. Mater. Chem. A
7, 9867-9876 (2019).

Lim, K. H., Matanovic, I., Maurya, S., Kim, Y., De Castro, E. S., Jang, J.-H., Park, H., Kim, Y. S., High Temperature Polymer Electrolyte Membrane Fuel Cells with High Phosphoric Acid Retention. ACS Energy Letters, 8, 529-536 (2023).

Atanasov, V., Lee, A.S., Park, E.J. et al. Synergistically integrated phosphonated poly(pentafluorostyrene) for fuel cells. Mater.
20, 370–377 (2021).

Lim, K., Lee, A., Atanasov, V., Kerres, J., Adhikari, S., Maurya, S., Park, E. J., Delfin, L., Jung, J., Fujimoto, C., Matanovic, I., Jankovic, J., Jia, H., Kim, Y. S. Protonated phosphoric acid electrodes for high power heavy-duty vehicle fuel cells. Energy 7, 248-259 (2022).

Chhetri, M., Leonard, D. P., Maurya, S., Sharan, P., Kim, Y., Kozhushner, A., Elbaz, L., Ghorbani, N., Rafiee, M., Kreller, C., Kim, Y. S. Scalable tandem electrochemical pumps achieving >99.999% hydrogen from 10% feed for purification and compression. submitted for publication (2024).
A Simple Electrochemical Way to Probe the Surface Area of Zinc Electro-Deposition
Authors: Freville Mathieu Ben-Aouda , Abdeldhani-Idrissi Soufiane , Tregouet Corentin , Colin Annie 
Published: December 2024

In this work, we are interested in flowing batteries and mainly in flowing zinc air batteries. The current lack of understanding of metallic Zn deposition mechanisms during charging phase contributes to prevent them from being competitive in industry. Currently, literature seems to converge to give the optimized parameters for flat zinc deposition, and avoiding dendrites or boulder-like structures. However, these conditions are often obtained at microscale level, and the scaling up for more macroscopic applications is not trivial. We seek to understand and develop strategies to analyze the evolution of large electrodes.
Beyond the results of the literature, in our work we propose a non-intrusive method to qualify the evolution of the electrode structure through electrochemical measurements based on Tafel analysis. A strong correlation has been identified between the evolution of exchange current density, i0, and the type of morphology that zinc adopts depending on injected current density, electrolyte concentration or electrolyte flow velocity. When zinc deposits in mossy way, its active surface area is higher than when it deposits under a flat way. By choosing cautiously the configuration of electrodes, the gap between them and the initial active surface area, we are able to determine under which type of morphology zinc is depositing inside the cell, without to have to open it or to use x-ray method. This reproducible technique allows also an early detection of defects, thanks to variations which can be compared to reference curves. The exchange current density increases exponentially when zinc deposits in a mossy way while it varies slightly when zinc is flat. This approach is confirmed by direct surface measurements using X-ray tomography.
We establish a complete phase diagram that gives the nature of the deposited structure at zinc electrode surface depending on parameters such as current intensity or electrolyte flow rate. Charge and discharge cycles are performed. Based on these analyses, we propose more appropriate charging and discharging strategies to increase battery life.

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Pressure-Electrochemistry at Gigapascal Pressures: Model Study in the Y-H System
Authors: Sugano Karen , Phuthi Mgcini Keith , Guan Pinwen , Viswanathan Venkat , Chiang Yet-Ming 
Published: December 2024

High pressure electrochemistry, while originating out of necessity from fields like deep marine science and geology to study reactions under extreme conditions, has become a tool for chemists to understand fundamental reaction properties, such as reaction volumes and ion-solvent interactions. More recently, researchers have begun utilizing pressure as a knob to increase selectivity of redox reactions, from the production of formate from the electrochemical reduction of CO2 [1] or ammonia from the electrochemical reduction of N2 [2]. We have designed a pressure-electrochemical cell apparatus capable of applying a voltage at pressures of 1GPa by adapting a traditional piston-cylinder pressure apparatus. In this talk, we will review how pressure affects electrical properties such as conductivity, open circuit potential of redox reactions, and reaction rates, followed by experimental data supplementing the expected trends. We use the apparatus to measure the conductivity of electrolytes and verify that the conductivity follows what would be expected of the Stokes relationship. We measure the equilibrium potential of water electrolysis and compare against the calculated equilibrium potential derived from modeling the nonideality of gaseous species at high pressure with a virial equation of state. We demonstrate enhanced selectivity at higher pressures by demonstrating enhanced electrochemical hydrogenation of yttrium foil. We find that by increasing the pressure to 1GPa, we suppress hydrogen evolution and instead promote hydrogen absorption, increasing the current efficiency from 35% to 74%. Lastly, we discuss the potential of utilizing pressure-electrochemistry to synthesize novel materials, presenting a pressure-potential Pourbaix diagram for the yttrium system generated from density functional theory calculations. We discuss the challenges in realizing higher stoichiometry hydrides and strategies to synthesize the predicted phases.
[1] T. Li, E. W. Lees, Z. Zhang, C. P. Berlinguette, ACS Energy Lett.
5, 2624–2630 (2020).
[2] A. Tsuneto, A. Kudo, T. Sakata, Journal of Electroanalytical Chemistry. 367, 183–188 (1994).

Figure 1
A Planar Sodium Nickel Chloride Battery Running at Intermediate Temperatures for Mid-Range Energy Storage
Authors: Jung Keeyoung , Choi Hanul , Lee Seungmi , Kim Hayoung , Heo Jeongheon , Yang Choongmo , Dirksen Cornelius , Schulz Matthias , Lee Younki , Sprenkle Vincent , Li Guosheng 
Published: December 2024

Sodium nickel chloride (Na-NiCl2) battery is one of the most promising candidates for grid scale electricity storage due to its high safety, long lifetime and demonstrated performance. The battery comprises molten Na and NiCl2 as negative and positive electrodes, respectively, in its charged state, separating them by a β”-Al2O3 solid electrolyte (BASE). In order to facilitate fast sodium ion transport in the cathode compartment, molten catholyte (NaAlCl4) is infiltrated into the cathode granule made of Ni and NaCl powders. The battery typically operates at 250-300oC so as to maximize the ionic flux in the cathode and through the solid electrolyte, and to minimize the dissolution of NiCl2 into the catholyte. However, this efficient battery is yet to be widely used in grid scale energy storage applications since it is still expensive mainly due to its use of expensive sealing technologies.
The presentation introduces international collaborative efforts to develop a lower temperature operating planar Na-NiCl2 battery towards commercialization for the mid-range energy storage. Since the novel battery runs at 180oC, it can be fabricated at an ultra low manufacturing cost by adopting simpler and inexpensive polymer sealing and by introducing a planar cell design that can eliminate a number of unnecessary cell components. Starting with stating problems in traditional sodium beta-alumina batteries, their possible corresponding solutions are described. Challenges and progress in materializing the 6Ah class proto-type unit cell and its serially stacked cells will be discussed with related core technologies, including a cell design, highly toughened planar solid electrolyte, enhanced wetting, and semi-automated cell manufacturing platform.