bluuebunny/crossref_metadata_2025 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+.
Operando FTIR Measurements of Li-Ion Concentration in a Graphite/NMC Battery During Fast Charging
Authors: Meyer Lydia , Brow Ryan , Weddle Peter J , Porter Jason Morgan , Colclasure Andrew M.
Published: December 2024

When cycled at high charging rates, Li-ion batteries can suffer from poor performance and cell degradation, especially for thicker batteries intended for electric vehicles (> 4 mAh/cm2). Such degradation in these energy-dense cells can be attributed to heterogeneous electrode utilization due to Li-ion concentration gradients in thick electrodes. Researchers have used pseudo-2D (P2D) models to predict concentration polarization phenomena during fast charging, but experimental measurements have been minimal. In the present research, we developed an optically accessible operando cell for FTIR (Fourier transform infrared spectroscopy) and ATR (attenuated total reflection) to measure Li-ion concentration at the back of the graphite anode during fast charging (> 2C). The graphite/NMC811 full cells with 1.2M LiPF6 in 3/7 EC/EMC (ethylene carbonate/ethyl methyl carbonate) (wt./wt.). had cathode loadings ranging from 2.6 mAh/cm2 to 3.9 mAh/cm2 and N/P ratios of ≈1.1. Changes in Li-ion concentration are measured and compared with a P2D model at C-rates of C/2, 1C, 2C, 3C, 4C, and 5C. Large salt-depletion events were observed at the back of the anode in both the model and experiment, especially at charging rates greater than 2C. The model and experiments agreed most closely for thinner electrodes and at lower charging rates. However, at higher rates and for thicker loadings model/experiment disparities existed during periods in which the P2D model predicted minimal salt concentrations at the back of the anode. The disparity between measured and predicted Li-ion concentrations suggests a gap in understanding of electrolyte physics under extreme polarization.
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.

Figure 1
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.

Figure 1
Unraveling the Catalytic Graphitization Mechanism of Ni–P Electroless Plated Cokes Via in Situ Analytical Approaches
Authors: Lee Sangwon
Published: December 2024

We have unraveled the mechanism of catalytic graphitization by employing in-situ analytical methods. The process involves the use of a Ni–P electroless plating technique at a modest 1600 °C, ensuring high crystallinity of the produced coke material. Furthermore, we have incorporated ultrasonic waves during the Ni–P electroless plating process to enhance the formation of metallic layers on the carbon material, leading to improved surface characteristics and adhesion . The impact of ultrasonic treatment on the electroless plating process has been confirmed by field emission scanning electron microscopy images and elemental composition analysis. Additionally, our structural analysis using X-ray diffraction and Raman spectroscopy demonstrates that the Ni–P electroless plating significantly accelerates the graphitization process . Lastly, the behavior of graphitization has been illuminated through in situ transmission electron microscopy and XRD analysis . The presence of nickel layers on the surface of the coke material aids in graphite formation by promoting the dissolution and precipitation of amorphous carbons, resulting in effective graphitization at a relatively low temperature.

Figure 1
Role of 'pi-Stacked Self-Assembly' in Governing the Dynamics of Photoinduced Electron Transfer Events in Nanocarbon-Derived Donor-Acceptor Conjugates and Hybrids
Authors: D'Souza Francis , Kazemi Shahrzad , Caballero Ruben , de la Cruz Pilar , Alsaleh Ajyal , Karr Paul , Langa Fernando
Published: December 2024

Supramolecular donor-acceptor nanostructures formed from the intermolecular association of either repeated units of redox- and photo-active molecular monomers or with the association of components of the same molecule are of greater significance due to their importance in understanding the complex photo- and electrochemical events occurring in biology. One such supramolecular organization is the ‘photosynthetic antenna-reaction center’ found in green plants and bacteria which is involved in converting sunlight into chemical energy that drives life as we know it on our planet. Several attempts have been made to mimic aspects of this complex photo-active machinery.1-4

In the present contribution, we discuss our latest work on self-assembled, multi-modular systems. Two key examples will be highlighted, viz., (i) covalently linked fullerene-bisstyrylBODIPY-(zinc porphyrin)2 binding to single-wall carbon nanotubes and (ii) fullerene-(zinc porphyrin)2 self-assembling to form supramolecular donut structures.5 Photodynamics of these complex structures about stabilizing the charge-separated states through sequential electron transfer will be highlighted in this presentation.

D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ Phys.
Chem. Letts. 2010, 1. 2586-2593.

B. KC, G. N. Lim, and F. D’Souza, ‘Accelerated Charge Separation in Graphene Decorated Multi-Modular Tripyrene-Subphthalocyanine-Fullerene Donor-Acceptor Hybrids,’ Angew.
Chem. Int. Ed.
2015, 54, 5088-5092.

Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992.

Kazemi, Y. Jang, A. Liyanage, P. A. Karr, and F. D’Souza, A Carbon Nanotube Binding Bis(pyrenylstyryl)BODIPY-C60 Nano Tweezer: Charge Stabilization through Sequential Electron Transfer, Angew. Chem. Int. Ed.
2022, 61, e202212474 (1-7).

Caballero, M. Barrejón, J. Cerdá, J. Aragó, S. Seetharaman, P. de la Cruz, E. Ortí, F. D’Souza, and F. Langa, Self-Assembly-Directed Organization of a Fullerene−Bisporphyrin into Supramolecular Giant Donut Structures for Excited-State Charge Stabilization, J. Am. Chem. Soc. 2021, 143, 11199−11208.

Figure 1
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) Multiplexed Cytokine Detection Via Fluorescent Single-Walled Carbon Nanotube Sensors
Authors: Williams Ryan M. , Gaikwad Pooja Vinod , Ryan Amelia K. , Israel Atara R , Cohen Zachary , Rahman Syeda
Published: December 2024

Single-walled carbon nanotubes (SWCNT) are uniquely able to serve as sensor transducers for multiple analytes at once. This is in part due to their highly sensitive detection and functionality in complex biological environments, including in cells, serum, and animals. In our work, we developed SWCNT-based nanosensors that selectively and sensitively detect several inflammatory cytokines, including interleukin-6 (IL-6), IL-8, IL-1β, and tumor necrosis factor α (TNFα). We implemented aqueous two-phase extraction (ATPE) to obtain separate chiral sensors for these cytokines. We have found that these sensors demonstrate analyte quantification in vitro, in human serum, ex vivo, and in vivo. Our work has developed a non-invasive injectable hydrogel system for direct injection and in situ gelation for sensor stability. We anticipate that long-term translation of this fluorescent SWCNT-based cytokine sensor array will provide early-stage diagnostics for the development and progression of acute infection and chronic inflammatory diseases in patients.
(Invited) Spatial Quantification of Nitric Oxide Via DNA Wrapped Single Wall Carbon Nanotubes to Demonstrate Extracellular Interactions between Cells
Authors: Iverson Nicole M , Acosta Ramirez Ivon
Published: December 2024

It is known that cells communicate through release of small molecules, but the precise communication mechanisms are not well understood. Through the use of single wall carbon nanotube sensor platforms, we can now quantify the gradients of nitric oxide that are release by each cell within an in vitro colony. To achieve this level of detail, a system was created to locate and identify cells, including differentiating between live and dead cells. The system then needed to identify changing fluorescence intensity values in relation to each cell and quantify these levels to allow for analysis and comparison. This new technology will allow researchers to understand how cells alter the release of active species during disease and healthy states, and potentially improve medical treatment through small molecule interactions.
(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.
Electrochemical Preparation of Multifunctional Fabrics Using Graphene Materials
Authors: Jafari Behnaz , Botte Gerardine G
Published: December 2024

Multifunctional or smart textiles have demonstrated great potential in various fields such as health monitoring devices, antimicrobial applications, and thermotherapy. These fabrics can be created by integrating advanced materials such as graphene into traditional textile substrates. Graphene-related materials offer unique characteristics, including exceptional electrical and thermal conductivity, substantial surface area, and other notable features [1]. Therefore, they stand out as an ideal additive for producing smart fabrics. A facile electrochemical process was developed for the in-situ integration of graphene materials into the textile matrix [2]. The method involved the spray coating of graphene oxide on the substrate, followed by the electrochemical reduction of the graphene oxide to convert it to reduced graphene oxide. This approach aims to overcome the limitations of the current methods for coating graphene on fabrics, such as the use of toxic chemicals, elevated temperatures, and complicated lengthy steps. The incorporation of reduced graphene oxide into initially electrically insulating textiles transformed them into electroconductive materials with Joule heating and sensing capabilities. Furthermore, the graphene-modified fabrics demonstrated antibacterial activity under an electric field [3]. The findings regarding the capabilities of our multifunctional fabric will be presented.

References

Zhang, F., et al., Recent advances on graphene: Synthesis, properties and applications. Composites Part A: Applied Science and Manufacturing, 2022. 160: p. 107051.

Jafari, B., C.M. Lacerda, and G.G. Botte, Facile electrochemical preparation of hydrophobic antibacterial fabrics using reduced graphene oxide/silver nanoparticles. ChemElectroChem, 2023. 10(6): p. e202201111.

Jafari, B. and G.G. Botte, Reduced Graphene Oxide-Coated Fabrics for Joule-Heating and Antibacterial Applications. ACS Applied Nano Materials, 2023.
Novel Electrolyte Applications in Lithium-Sulfur Batteries Containing MOF-Modified Cathodes
Authors: Smolinski Maciej , Ossowska Aleksandra , Marczewski Maciej , Łaszcz Adam , Marcinek Marek
Published: December 2024

For many years now it can be observed that along with the developing world, human demand for energy is increasing. When in the second half of the 20th century the number of portable electronic devices was increasing constantly, it could have been easy to predict that the research on the battery development will be something crucial for the future. Now, in the early twenties of 21st century, having electric (EV) and hybrid (HEV) vehicles, computers, cell phones or even portable speakers – a good performing battery is the thing that everybody expects. That is why in last years the research for new batteries materials is speeding up permanently. Lithium sulfur batteries are in rapidly growing interest as a promising successor of the commercial cells that are produced now. Due to their high theoretical specific capacity (1675 mAh g-1) and high energy density (2000 Wh kg-1) they seem to be a good successor of commercial and wildly spread now lithium-ion batteries. Also, elementary sulfur used in the cathode is more environmentally friendly and much easier to acquire than transition metal oxides used in lithium-ion technology. The reason, why lithium-sulfur batteries are not in commercial use is because of the problem with the application and stability of the sulfur cathode. The expansion of the sulfur when charging, its insulation and dissolution in organic solvents of the electrolyte, resulting the creation of polysulfides chains, are the remaining problems to solve before lithium-sulfur batteries could be spread in the commerce devices. To solve these issues many additives and compounds have been examined. It’s possible to modify the cathode, like in this research, with metal-organic frameworks (MOFs) as a sulfur host on the electrode. Because of the porosity of the structure and the presence of metal cation they are able to interact with polysulfides and reduce the dissolution of the sulfur. Another way of possible modification of the lithium-sulfur batteries is to change the electrolyte salt, solvents or introduce the additives that will be able to reduce the sulfur dissolution and shuttle effect. In our research we are focused on introducing the Hückel-anion based salts and non-fluorine salts to lithium-sulfur technology. The aim of the research is to combine the effect of the cathode modification and new salts application on order to obtain the high-power density lithium-sulfur battery.
Thermodynamics of LixNa1-XCoO2 Layered Oxide: A Sodium Stabilized and Lithium Saving Battery Cathode Material
Authors: Geraci Tullio Salvatore , Navrotsky Alexandra
Published: December 2024

A path toward more sustainable battery cathodes is using LixNa1-xCoO2 layered oxides, which reduces the Li needed by traditional battery cathodes. During battery cycling, around 28 % of the Li within the structure of LiCoO2 cathodes goes unused and a portion of it could be replaced by Na. In this work, we show how sodium substitution serves not only to reduce the Li needed to produce these cathodes, but also to stabilize the structure of these battery materials by making the enthalpy of formation more exothermic. An enthalpic minimum has been found at around 10 % substitution with Na without major changes to the LiCoO2 layered oxide structure. Additionally, the positioning of the Na ions within the structure of the cathode appears to be concentration dependent. We present results from high temperature oxide melt drop solution calorimetry (AlexSYS), electron probe microanalysis (EMPA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder x-ray diffraction (PXRD), and bulk elemental analysis. This work lays the groundwork to extend Li reduction to more complex systems, such as nickel manganese cobalt (NMC) cathodes.
Enhancing Electrocatalytic Activity through Tailored Charge and Spin Polarization in Molecules and Frameworks
Authors: Sreenivasan Sreeprasad T
Published: December 2024

Single-molecule and framework-based electrocatalysts are increasingly attractive in the field of electrocatalysis due to their precise atomic-level control and highly tunable properties, enabling the development of highly efficient and selective energy conversion processes. Tailoring charge and spin polarization within these structures presents a unique opportunity to significantly enhance catalytic activity, opening new avenues in developing efficient electrocatalytic systems. This presentation will outline methods our group has developed to synthesize and adjust charge and spin configurations in molecular and framework catalysts. We will explore a variety of pathways, including the design of single molecular catalysts with optimized spin states, the application of mesomeric and inductive effects for charge regulation, and the use of external magnetic fields and chirality to modulate spin polarization at the molecular level. Our findings indicate that such customization can accelerate the kinetics of spin-sensitive electrochemical reactions like oxygen electrocatalytic reactions. Furthermore, we will discuss how the inherent properties of the catalysts, particularly magnetic moments and spin-orbit interactions, play a crucial role in influencing catalytic performance in the presence of spin potentials. Hence, this presentation aims to provide an overview of our advanced strategies to reconfigure charge and spin states in framework and molecular catalysts, underscoring their potential to revolutionize electrochemical energy conversion 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.

Figure 1
Fabrication and Modeling of Battery Yarns for e-Textiles
Authors: Gao Wei , He Nanfei , Zhang Xi , Mills Amanda , Bagnell Marcus , Crouch-Baker Steve
Published: December 2024

Yarn-shaped energy-storage devices (YSEs), including supercapacitors and batteries, are becoming promising energy-supply units with decent mechanical flexibility to be integrated into e-textiles, in various shapes and locations with the possibility of hiding among regular textile yarns without being noticed or detected. However, a robust YSE configuration, which can provide long-term and reliable power output after rigorous weaving/knitting processes and upon all kinds of end-use scenarios, is yet to be established. Most YSEs today still suffer from performance decay and short-circuiting risks, primarily due to structural failures of active materials involved. Moreover, a prominent length-dependent output has been observed in many YSE samples, which exhibit a plateaued capacitance/capacity at extended yarn lengths. In this talk, we will give an overview of existing issues of the state-of-the-art YSEs, and their possible solutions or mitigation strategies. In detail, we will discuss the incorporation of separator threads in a twisted YSE, to withstand repetitive mechanical deformations. A detailed mathematical model for YSEs will also be discussed to clarify the length dependence of their performances.

REFERENCES

He, X. Zhang, J. Song, F. Zhao, W. Gao*, Modeling of yarn-shaped supercapacitors – Unraveling its length dependent output, Journal of Power Sources, 2024, 595, 234067

He, J. Song, J. Liao, F. Zhao, W. Gao*, Separator Threads in Yarn-Shaped Supercapacitors to Avoid Short-Circuiting Upon Length,
npj Flexible Electronics
, 2022, 6, article number 19.

He, N.; King, C.; Xie, Q.; Zhao, F.; Gao, W.* A Multidirectional Forearm Electromagnetic Generator Designed via Numerical Simulations. Actuators,2023, 12 (6), 225.

Wang, Y.; Shim, E.; He, N.; Pourdeyhimi, B.; Gao, W.* Modeling the Triboelectric Behaviors of Elastomeric Nonwoven Fabrics. Adv.
Mater. 2022, 34 (2), 2106429.

Subjalearndee, N. He, H. Cheng, P. Teastchabut, P. Eiamlamai, P. Limthongkul, V. Instasanta, W. Gao*, X. Zhang*, Gamma (ɣ)-MnO2/rGO Fibered Cathode Fabrication from Wet Spinning and Dip Coating Techniques for Cable-Shaped Zn-Ion Batteries,
Adv. Fiber. Mater.
, 2022, 1-18.

Mainka, W. Gao, N. He, J. Dillet, O. Lottin, A General Equipvalent Electrical Cuicuit Model for the Characterization of MXene/graphene oxide hybrid-fiber supercapacitors by electrochemical impedance spectroscopy-Impace of fiber length,
Electrochimica Acta
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N. He, J. Liao, F. Zhao, W. Gao*, Dual-Core Supercapacitor Yarns: An Enhanced Performance Consistency and Linear Power Density,
ACS Appl. Mater. Interfaces
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ACKNOWLEDGMENT This work has been financially supported by 1) United States Army Research Office under the contract number W911NF19C0074 and W911NF18C0086; 2) Intelligence Advanced Research Projects Activity (IARPA) under the SMART ePANTS program.

Figure 1
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.
Synergetic Effect of Nasicon Na3V2(PO4)2F3 and 2D MXene for High-Performance Symmetric Sodium-Ion Batteries.
Authors: Shakoor Abdul , Moossaa Buzaina , James Abraham Jeffin , Kahraman Ramazan , Al-Qaradawi Siham
Published: December 2024

NASICON-based sodium Fluorophosphate Na3V2(PO4)2F3 (NVPF) cathode materials have been widely analyzed in sodium-ion batteries (SIB) owing to their high energy density and high working voltages. However, the low electronic conductivity of NVPF is a factor hindering their efficient use. To enhance the electronic conductivity of NVPF, a porous Na3V2(PO4)2F3 with Ti3C2-based MXene nanostructures was synthesized using a facile sol-gel method. NVPF acts as a bipolar or symmetric battery material from the presence of two redox couples at a low voltage of 1.4V and another at a high voltage of 3.6~4.1V. The benefits of a symmetric cell are many, including ease of fabrication, low volume expansion leading to higher safety, reduced cost of production, and easy recycling costs. In this work, the MXene-incorporated NVPF are analyzed in a symmetric cell, and the effect of incorporation of various MXene wt. percentages on the structural, thermal, and electrochemical performance of Na3V2(PO4)2F3 in a sodium symmetric cell was thoroughly investigated. Structural analysis of the materials developed indicates that the MXene addition has not altered the crystal structure of the NVPF. The modification improved the electrochemical performance of NVPF in the sodium symmetric cell as indicated by its high specific discharge capacity of 92mAhg-1 at a high C rate of 1C for the MXene 5wt% incorporated composite structures. The GITT analysis confirmed the improved diffusion kinetics of the MXene-incorporated samples, as evident from the calculated Na+ diffusion coefficients. The DNa+ calculated was found to be 9.57x10-9 cm2s-1 for the 5wt% MXene incorporated sample and 4.14x10-9 cm2s-1 for pristine sample.
Porous Iron Anodes for High-Performance Hybrid Battery-Electrolyzer System
Authors: Pal Santosh K. , Mulder Fokko M.
Published: December 2024

The demand for clean and efficient energy storage solutions has driven research towards advanced electrochemical devices utilizing abundant, low-cost materials. Hybrid battery-electrolyzers, combining battery and electrolyzer functionalities, offer a promising path for improved energy conversion and storage. [1] Iron, with its high-capacity, wide availability, and low cost, emerges as a potential anode material for these systems. [2,3]

This study investigates the fabrication and performance of a novel, porous iron anode specifically designed for hybrid battery-electrolyzers. The optimized electrode exhibits superior capacity, enhanced mass transport properties, and increased surface area, leading to improved overall performance. The electrode's dual-porosity structure facilitates efficient electrolyte penetration and hydrogen bubble removal, addressing limitations of traditional electrodes.

Extensive characterization techniques (SEM, XRD, EIS, CV, and cycling tests) confirm superior electrochemical properties, including enhanced specific capacity, faster charge/discharge kinetics, and extended cycle life compared to conventional iron anodes. Incorporation of conducting nanocarbon and optimized sintering at 800 °C yields stable electrodes with exceptional capacity exceeding 500 mAh/g (Fe⁰ to Fe²⁺ discharge). Furthermore, the electrodes achieve high porosity (65 %) with two pore size ranges (50-100 μm and 2-5 μm), leading to excellent current rate performance (350 mAh/cm² at 35 mA/cm² and 245 mAh/cm² at 50 mA/cm²). Additionally, they demonstrate superior charge-rate performance with 98 % charging efficiency at 4C. Remarkably, the optimized iron electrodes showcase outstanding electrocatalytic hydrogen evolution performance at high current densities (HER potential of 1.25 V and 1.50 V at 200 mA/cm² and 1000 mA/cm², respectively).

These findings highlight the promise of porous iron electrodes as a key component for high-performance and cost-effective hybrid battery-electrolyzer systems. Integration of such advanced materials paves the way for advancements in energy storage and green hydrogen technology, promoting the development of efficient and sustainable energy solutions.

References:

[1] M. Mulder, et al., Energy Environ. Sci., 2017, 10, 756.

[2] K. Manohar et al., J. Electrochem. Soc. 2012, 159, A2148.

[3] Weinrich, et al., Batteries & Supercaps 2022, 5, e202100415.

Figure 1
Influence of Water Vapor on High Temperature Oxidation Behavior of Type 310 Stainless Steel
Authors: Tsai Wen-Ta , Ma Michael
Published: December 2024

Oxidation behavior of 310 stainless steel (SS) was investigated in both dry and water vapor-containing air, respectively, at 800 ~ 1000 °C . The roles of water vapor on oxidation rate and scale microstructure were explored. After the exposure test, the specimen was examined by X-ray diffraction (XRD) for corrosion product identification. The cross-section image of each specimen after oxidation test was examined using a scanning electron microscope (SEM), where the scale chemical composition was analyzed with the attached energy dispersive spectrometer (EDS). The experimental results showed that oxidation of 310 SS followed parabolic oxidation kinetics in dry air, while a higher weight gain was found in moisture air at the early stage of exposure test showing accelerated oxidation. However, a lower weight gain was measured in water vapor-containing air at 1000 °C as compared with that in dry air for a prolonged exposure. XRD and cross-section SEM examination revealed that the oxidation product mainly consisted of an outer compact Cr2O3 and an inner spinel when exposed in dry air. In moisture air at 1000 °C, however, degradation of the passive film occurred due to the change of point defect structure while the oxidation product was mainly spinel. Moreover, the reaction of Cr2O3 with H2O resulted in the formation of CrO2(OH)2 vapor species which subsequently led to the formation of a loose scale structure and caused an increased oxidation rate.