bluuebunny/crossref_metadata_2025 huggingface dataset:
A Flexible Aptasensor Based on Silver–Modified PVC Membrane Electrode Detection of Chikungunya Virus in Human Serum
Authors: Sharma Pradakshina , Hasan mohd Rahil , Narang Jagriti
Published: February 2024

Electronic devices have advanced from their heavy, bulky origins to become smart appliances. Nevertheless, they remain rigid, which precludes their intimate integration into everyday life. Flexible, textile and stretchable electronics are emerging research areas and may yield mainstream technologies. The design and development of a screen-printed carbon electrode on a polyvinyl chloride substrate as a disposable sensor is described. The SPCEs were printed with two inks: carbon ink as the working and counter electrodes, silver/silver chloride ink as the reference electrode. Selection of the best configuration was done by comparing slopes from the calibration plots generated by the cyclic voltammograms for each configuration. Modifying the configuration for use as a biosensor, aptamer was selected as a biomaterial bound with silver nanoparticles (AgNP). Biosensors of Aptamer/AgNP/PCE, were used in the voltammetric detection of chikungunya virus antigen (CHIKV-Ag) in a solution of 0.5 mM ferro/ferri cyanide as a redox couple by applying a potential of 50mV/s at the working electrode yielded the highest performance. The voltammetric response of Aptamer/AgNP/PCE retained over 95% of the initial current of the 1st day up to 30 days of storage at 4 ◦C. The biosensor showed a linear range of 0.1ng/ml-1µg/ml, with a detection limit of 0.1ng/ml of CHIKV-Ag (S/N = 5). The low detection limit, long storage life and wide linear range of this biosensor make it advantageous in variety of quick diagnostic procedures for the detection of Chikungunya virus infection.
Solid Reservoir Reference Electrode
Authors: Tran Minh Ngoc Anh , Capilli Gabriele , Szkopek Thomas
Published: February 2024

Potentiometric sensing requires a stable sensing electrode that is selectively responsive to an analyte, and a reference electrode (RE) that provides a stable and well-defined reference potential in a liquid electrolytic environment. In sensor applications where compactness and ease of integration are essential characteristics, pseudo-REs in the form of doped polymer semiconductors, bare metal films, or a bare chlorinated silver film are typically used. Bulk glass electrodes, such as the Ag/AgCl electrode, are incompatible with sensor integration.

We report here a solid reservoir reference electrode (SRRE) that achieves the performance of traditional immersed wire Ag/AgCl REs in a compact, layered structure. The SRRE is a solid, layered analogue of the Ag/AgCl RE, with a chlorinated silver film as metallic electrode, a solid KCl layer serving as a saturated reservoir of chloride, and a porous polydimethylsiloxane (PDMS) layer acting as membrane for exchange of water and ions. We demonstrate two different method to fabricate the porous PDMS in figure A and B. The characteristics of the SRRE, including impedance, noise, and long-term drift, can be tuned by adjustment of the PDMS membrane permeance and KCl solid reservoir size.

We have demonstrated temporal stability of the RE open circuit potential (OCP), with drift less than 0.37 mV over 17 hours in deionized water. When compared against bare chlorinated silver, the SRRE exhibits superior stability of OCP versus changes in electrolyte ion-concentration, including solutions of potassium chloride, sodium chloride and pH buffers. The ease of fabrication enables SRRE integration with graphene ion-sensitive field effect transistors (ISFETs) to achieve entirely solid-contact micro ion sensors. The solid-contact micro ion sensor can simultaneously measure pH and Na+, in volumes as low as 20 μL. Using the same layered structure, we further demonstrated fabricated electrocardiogram (ECG) and electroencephalogram (EEG) electrodes with significantly lower impedance and noise when compared to disposable gel electrodes. Finally, we have shown that the SRRE can function in non-aqueous solventssuch as acetonitrile, demonstrating the wide range of SRRE applications.

Figure 1
Detection of VOCs Using Doped ZnO Nanorods
Authors: Amoah Papa Kojo , Baumgart Helmut , Obeng Yaw , Abdel-Fattah Tarek M , Quach Qui
Published: February 2024

Metal-oxides, such as ZnO, have been popular materials of choice for the detection of VOCs because they show a relatively quick response. In this study, ZnO nanorods were prepared, first, by depositing a seed layer via atomic layer deposition (ALD) on top of a silicon substrate, and then immersing that seed layer in a chemical bath solution to facilitate growth of the rods. To enhance the gas sensing properties of the rods, some of the nanorods were doped with metals such as Au and Co. The gas sensing materials were then probed with microwaves, using Broad band dielectric Spectroscopy (BDS), to observe their changing characteristics in the presence of a VOC analyte. BDS provides and advantage in that it avoids the need for physical electrical connections which lead to errors into the measurement. Additionally, we use Raman spectroscopy to not only confirm the presence of the dopants in the nanorods, but also to help explain the behavior of the materials under microwave interrogation.
Modulating Charge Percolation in Biocompatible Norbornene Redox-Active Polymers Obtained Via ROMP
Authors: Ibrahim Nafisa Aden , Romo Adolfo I.B. , Zimmerman Steven , Rodriguez Lopez Joaquin
Published: February 2024

Organic redox-active materials are actively being developed as next-generation energy storage systems. These materials have multiple advantages, including superior chemical and physical properties, and excellent electrochemical storage performance compared to metal-based inorganic materials. Specifically, redox-active and conductive polymers have been used over organic single molecules due to the advantages that polymeric materials offer such as good stability, excellent processability, and simple device fabrication. Furthermore, we can adjust the synthetic process to obtain a wide range of desirable properties and can incorporate conductive and redox-active polymers into biological entities to carry out bio-inspired functions such as shuttling electrons through wastewater mediated processes or sensing of heavy metals in wastewater. By leveraging natural processes, our goal is to engineer resistant and sustainable energy storage technologies using conductive and redox-active polymers. To that end, we present the synthesis and characterization, including material and electrochemical characterizations, of biocompatible norbornene redox-active polymers in which we modulated charge percolation by copolymerizing with a water-soluble polymer for potential applications in bio-inspired redox-flow batteries.
Synthesis and Characterization of Responsive Antimicrobial Materials for Chronic Wound Management
Authors: Sheets Katey M , Hurd Chiara M , Kamuda Heather M , Havens Mallory A , Keleher Jason J.
Published: February 2024

Chronic wound treatment requires the ability to regulate the wound healing process and mitigate the propagation of bacterial infection with constant monitoring, in real-time. The need for multi-functional wound management materials has emerged as a significant research area with promise shown in the incorporation of antimicrobial agents within responsive polymeric materials to elicit signals providing dynamic information about the healing process. Traditional wound dressings provide a barrier between the outside environment and the wound; however, these methods are increasingly becoming less effective. Hydrogels synthesized from natural biopolymers have emerged due to their intrinsic properties such as biodegradability and non-cytotoxicity and enhanced from their well-defined, three-dimensional, non-covalent networks ideal for modification and functionalization to create “micro-reactors.” Previous work focused on the strategic design of an alginate-based hydrogel containing dual functional additives (i.e., amino acids) paired with photochemically prepared Ag- and Cu-TiO2 nanoparticles (Ag/Cu-NPs) to understand the synergistic interactions of the polymer chains, cross-linkers, and additives. The antimicrobial effectiveness of the composite was examined using an epi-fluorescent optical tweezer to measure the rates of bacterial cell death. Results showed that with the incorporation of the NPs there is a decrease in green signal (live cells) within 1 hour of exposure. Furthermore, the healing rates of simulated wounds using human dermal fibroblasts were explored along with changes in the expression of growth factors that promote wound healing, such as collagen and TGF-b. This work focuses on a two-layer responsive material with a wound-healing layer and a conductive layer formed through the secondary functionalization of the composite system through a metal-coordination-assisted photopolymerization of conductive polymers (i.e. aniline). Preliminary results show there is uniform polymeric chain growth seen in enhanced charge transfer through the matrix upon an applied voltage. Studies have also been conducted to measure the impact of saturation of the bandage through simulated wound exudate that revealed once saturation occurs, the passing of electricity between the ions found in wound exudate carried current through the composite, increasing the conductivity, leading to the signaling of an LED prompting replacement. The resulting two-layer nanocomposite system then functions as a responsive, antimicrobial wound healing material capable of eliminating constant monitoring with application in healthcare and home settings.
Quantifying the Thermochemistry of Kinetic Transitions in a Li/Llzo/Layered Metal Oxide Cathode Solid-State Battery with Varying Cathode States of Charge
Authors: Bhargava Bhuvsmita , Johnson Nathan B , Zaman Samaa , Albertus Paul
Published: February 2024

The safety of solid-state battery is multifaceted and requires analysis of the thermal runaway onset temperature, total heat released, maximum heat release rate, the amount and toxicity of any gases released, and other factors1. The onset temperature of strong self-heating is particularly important, and hence quantitative analysis of exothermic reactions as a function of temperature is required. We use differential scanning calorimetry to measure heat flow for solid-state cells with a Li metal anode, an LLZO separator, and both LiCoO2 and NMC cathode sheets (which also contain a conductive additive and a binder), and quantitatively analyze the data to develop a thermochemical reaction map consisting of all major reactions that take place upon heating. This quantitative thermochemistry map can serve as a basis to assess cell safety, and in particular the rate and extent of temperature rise. We find that primary reaction that determines the total heat released is lithium reaction with oxygen from delithiated cathode decomposition (i.e., 4Li+O2→2Li2O), but other components in the cell such as conductive carbon, PVDF binder and current collectors also have significant participation in the reaction pathway. As previous studies for graphite/liquid electrolyte/metal oxide cathode cells have shown, reducing the state of charge also reduces the amount of heat released upon heating2, with implications for safe storage and operation of future cells.

References:

(1) Johnson, N.; Albertus, P. Modeling Thermal Behavior and Safety of Large Format All-Solid-State Lithium Metal Batteries under Thermal Ramp and Short Circuit Conditions. J. Electrochem. Soc.
2022, 169 (6), 060546. https://doi.org/10.1149/1945-7111/ac79cf.

(2) Barkholtz, H. M.; Preger, Y.; Ivanov, S.; Langendorf, J.; Torres-Castro, L.; Lamb, J.; Chalamala, B.; Ferreira, S. R. Multi-Scale Thermal Stability Study of Commercial Lithium-Ion Batteries as a Function of Cathode Chemistry and State-of-Charge. Journal of Power Sources
2019, 435, 226777. https://doi.org/10.1016/j.jpowsour.2019.226777.
Innovative High-Voltage Cathode Architectures for Doped Ammonium Vanadium Oxide: Overcoming Limitations and Boosting Energy Density
Authors: Khan Zarrin , Ahuja Aakash , Adil Md. , Mitra Sagar
Published: February 2024

Sodium-ion batteries are emerging as a feasible substitute to lithium-ion batteries due to natural abundance and cost of their raw materials. Cathode materials with high operating voltage window are highly investigated in order to attain a high specific capacity and energy density. Because of its larger ionic size and lower standard electrochemical potential of Na, research on suitable cathodes with rich electrochemistry and high energy density is of utmost importance. NH4V4O10 (Ammonium Vanadium Oxide) is one such cathode with rich electrochemistry in terms of high sodium-ion storage along with a low-cost proposition. It is synthesized feasibly using a one-step hydrothermal process at lower temperatures (160o). However, the low conductivity and structural distortion during extended cycling pose a significant challenge. In this study, we present a high-rate cathode based on NH4V4O10, which employs a doping strategy to address the structural changes that cause distortion, while simultaneously improving ionic conductivity and electrochemical performance. By introducing dopants into NH4V4O10, the mobility of carriers is increased as the lattice spacing is expanded. This modification facilitates easier movement of Na-ions within the crystal lattice during electrochemical cycling, ultimately leading to enhanced Na-ion diffusion. As a result, the doped NH4V4O10 electrode exhibits superior high-rate performance compared to the pristine NH4V4O10. Furthermore, this doped NH4V4O10 cathode can be operated effectively at High voltage (1 V to 4.2 V ) and thus increasing the energy density. In addition to enhancing the ionic conductivity and Na-ion diffusion coefficient, the incorporation of dopants into NH4V4O10 also results in improved morphology, which contributes to the maintenance of a stable structure. As a result, the doped- NH4V4O10 cathode exhibits a specific capacity of 250 mAh/g with 0.1 A/g after 100 cycles, along with a Coulombic efficiency of 98%, whereas NH4V4O10 only achieves a 70% efficiency and within a restricted working potential window. With its unique properties, including superior conductivity, high Na-ion diffusion coefficient, and stable capacity over extended cycling, this newly modified doped NH4V4O10 material holds promise as a novel class of cathode for next-generation high-performance sodium-ion batteries.

References:

Sarkar, S. Sarkar, Journal of Materials Chemistry, 2017, 24929

Sarkar, S. Mitra, Journal of Power Sources, 2020, 452, 227832.

Muthuraj, Divyamahalakshmi, et al, Batteries & Supercaps11 (2021): 1757-1770.

Adil, Md, et al. Journal of Power Sources541 (2022): 231669.

Chen, Long, et al, Chem4 (2019): 896-912.
Troubleshooting CNT Bundling with Electrospray Method in LiFePO4 Cathode Material
Authors: Kim Ilgyu , Jung Ji-Won
Published: February 2024

CNT, a nanomaterial with a 1D structure providing efficient electron transport, is well known as an excellent electron-conducting material and a key element for realizing thick electrodes. However, due to its high aspect ratio, there is significant Van der Waals force present; therefore, when used at a certain level or higher, it aggregates, which causes performance degradation, limiting its use.

In this work, we solve the bundling problem by applying a feasible electrospray method. This approach achieves a LiFePO4/CNT composite with uniform morphology, even with high CNT content, and is confirmed with Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) analysis. In addition, we found out that it shows enhanced capacity retention and longer battery life compared to the conventional mixing-only method.
Elastic Interfacial Layer Enabled the High-Temperature Performance of Lithium-Ion Batteries Via Utilization of Synthetic Fluorosulfate Additive
Authors: Moon Hyeongyu , Nam Huibeom , Kim Min Pyeong , Lee Seung , Kim Hyeongjun , Jeon Min Ho , Lee Yoon-Sung , Kim Koeun , Chun Joong-Hyun , Kwak Sang Kyu , Hong Sung You , Choi Nam-Soon
Published: February 2024

The key to producing high-energy Li-ion cells is ensuring the interfacial stability of Si-containing anodes and Ni-rich cathodes. Herein, 4-(allyloxy) phenyl fluorosulfate (APFS), a multi-functional electrolyte additive that forms a mechanical strain-adaptive solid electrolyte interphase (SEI) comprising LiF and polymeric species, and a thermally stable cathode–electrolyte interface containing S–O and S–F species. The radical copolymerization of vinylene carbonate (VC) with APFS via electrochemical initiation creates a spatially deformable polymeric SEI on the SiG-C (30 wt.% graphite + 70 wt.% SiC composite) anode, with large volume changes during cycling. Moreover, the APFS-promoted interfacial layers reduce Ni dissolution and deposition. Furthermore, APFS deactivates the Lewis acid PF5, thereby inhibiting hydrolyses that produce unwanted HF. These results indicate that the combined use of VC with APFS allows capacity retentions of 72.5% with a high capacity of 143.5 mAh g−1 in SiG-C/LiNi0.8Co0.1Mn0.1O2 full cells after 300 cycles at 45 °C.
Multivariate Analysis of Synchrotron X-Ray Data for Battery Research
Authors: North Erlend Tiberg , Koposov Alexey , Wragg David Stephen
Published: February 2024

By utilizing multivariate analysis of x-ray operando data from working batteries one can separate and enhance scattering signals from specific components of the battery, identifying the critical responses that are connected to its performance and failure. This can enable faster and easier analysis of operando data, especially from complex materials that are difficult to analyze manually.

In this poster I will present the preliminary results that we have obtained so far, focusing mainly on comparing analysis methods on simulated data sets, along with the current plan of the research project in my PhD.
Pair Distribution Function Analysis of Local Structural Rearrangement in Spinel Vanadium Oxide Cathodes
Authors: Samanta Anwesa , Cabana Jordi
Published: February 2024

Being a divalent cation with the lowest mass, Mg2+ has garnered quite attention in recent times due to the high volumetric capacity of it’s batteries. Theoretical studies reveal that the combination of a Mg anode and a spinel oxide cathode would be able to surpass the current limits found in widely used Li-ion batteries Therefore, to design materials with high diffusion and reversible insertion capacity, a conclusive demonstration of the intercalation mechanism of Mg2+ into metal oxides, is required.

Among the numerous options for cathodes, vanadium oxides show evidence of the largest capability toward reversible intercalation of Mg ions. In particular, spinel-type MgV2O4 shows a capacity of 200 mAh/g, corresponding to the cycling of ~0.7 mol Mg2+ per mol of oxide, and layered α-V2O5 reaches 300 mAhg-1, intercalating 1 mol Mg2+ per mol of oxide. The extent and reversibility of these reactions were confirmed by elemental, redox and structural characterization in recent work [1,2]. This high capacity is only observed at 110°C and it is accompanied by a large hysteresis in potential during the electrochemical cycling. The push to overcome these bottlenecks demands a more comprehensive definition of the underlying mechanisms of reaction than is currently available.

Previous X-ray Diffraction (XRD) measurements conducted on the oxide indicated a loss of reflection intensity due to a loss in their crystallinity which makes structural characterization using typical diffraction techniques difficult. Through this work, we mainly make use of pair distribution function techniques to study the changes in the local structures of these oxides in both their pristine and charged state, and the effect of annealing for longer hours with the goal of further pushing the efficiency of multivalent battery materials.

Reference:

Hu, L., Jokisaari, J.R., Kwon, B.J., Yin, L., Kim, S., Park, H., Lapidus, S.H., Klie, R.F., Key, B., Zapol, P. and Ingram, B.J., 2020. High capacity for Mg2+ deintercalation in spinel vanadium oxide nanocrystals. ACS Energy Letters, 5(8), pp.2721-2727.

Yoo, H.D., Jokisaari, J.R., Yu, Y.S., Kwon, B.J., Hu, L., Kim, S., Han, S.D., Lopez, M., Lapidus, S.H., Nolis, G.M. and Ingram, B.J., 2019. Intercalation of magnesium into a layered vanadium oxide with high capacity. ACS Energy Letters, 4(7), pp.1528-1534.
Visualising Chemical Transformations in Si-Based Electrodes through Operando Tomography
Authors: Skautvedt Casper , Brennhagen Anders , Checchia Stefano , Wragg David Stephen , Koposov Alexey
Published: February 2024

The development of the modern Li-ion batteries requires new materials which will be capable of delivering high energy storage capacities. In such quest, anode materials operating under alloying mechanism have been recognised among the others as a potential replacement for conventional graphite-based anodes in Li-ion batteries. Among those, Si has long been viewed as the main candidate for such a role, as the Li storage capacity of Si is ten times higher than that of graphite. While more than a decade of research was dedicated to improve poor cycling stability of Si-based anodes, the progress in stabilisation of Si cyclability is still partially impeded by the lack of complete fundamental understanding of the chemical transformations taking place during cycling. Despite the relative simplicity of the electrochemical processes underlying the cycling mechanism of Si, the true atomistic and morphological changes are not fully understood. Furthermore, the formation of amorphous Li-Si phases during lithiation and delithiation substantially restricts the set of characterisation techniques, which could be applied to reveal the details of the cycling mechanism. In general, the materials operating under allowing mechanism in LIBs and other battery chemistries share the similar level of complexity. This calls for new experimental and computational methods for characterisation of Si and other alloying materials with use of operando mode, which will help to link the chemical transformations at different scales to the electrochemical performance. In this presentation, we will demonstrate a characterisation methodology, which illustrates the possibility of retrieving new insights into the cycling mechanism by conducting operando pair distribution function computed tomography (PDF-CT) measurements using electrodes based on amorphous silicon (Si) as an example. The amorphous nature of Si and its lithiated forms complicates the analysis of this material system and, thus, Si-based anodes represent a perfect platform for evaluation of the new characterisation methods. The PDF-CT methodology demonstrated herein allows spatially resolved analysis of amorphous materials such as Si and detect the structural changes during lithiation/delithiation in a specially designed battery cell. Furthermore, this method could be utilised for creating a 3D structural map of electrodes fabricated from amorphous active materials (or materials which can form amorphous phases during cycling) and for understanding of structural and morphological changes during cycling.
Incorporation of PEDOT:PSS to Reduce Iridium Loading at Anode Catalyst Layer for Proton Exchange Membrane Water Electrolysis
Authors: Sun Yujiao , Xu Shaoyi , Li Hui
Published: February 2024

Proton exchange membrane water electrolysis (PEMWE) is one of the most promising technologies to produce green hydrogen with high efficiency. However, its commercialization is hindered by the large usage of expensive iridium as anode electrocatalyst [1-3] . Incorporation of cheap conductive materials into the catalyst ink, e.g., titanium powder [4], is a straightforward and efficient method to reduce noble metal loading of membrane electrode assembly (MEA). In this study, we aimed to use a conductive polymer PEDOT:PSS to build the low Ir loading catalyst layer for PEMWE.

The MEAs at 0.3 mgIr cm-2 loading were fabricated with different PEDOT:PSS contents. In practice, the dispersion of IrO2 particles is difficult in catalyst ink, leading to the formation of big IrO2 agglomerates. We found that the zeta potential of the anode catalyst ink gained obvious enhancement after the addition of PEDOT:PSS. This indicated that PEDOT:PSS as dispersant could increase the stability of the catalyst ink. The morphology of anode catalyst layers was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface and cross-sectional images of morphology exhibited small IrO2 particles and porous structure in the catalyst layer with the addition of PEDOT:PSS, which would contribute to the water/gas movement in triple-phase boundaries. Electrochemical measurements such as polarization curves, electrochemical impedance spectroscopy (EIS), cyclic voltammogram (CV) and durability tests were conducted in a PEMWE single cell. The MEA using PEDOT:PSS as binder displayed better electrochemical performance (3.4 A cm-2@2.0 V) than other references with Nafion only (2.4 A cm-2@2.0 V). Moreover, the addition of PEDOT:PSS improved the high-frequency resistance due to its excellent electronic conductivity. In consideration of the conductive binder and dispersant effect of PEDOT:PSS, future research will focus on reducing Ir loading below 0.1 mg cm-2 through designing novel structure of anode catalyst layer with PEDOT:PSS.

Keywords:

PEM water electrolysis, low iridium loading, PEDOT:PSS

References:

[1] Carmo, M., et al., A comprehensive review on PEM water electrolysis. International Journal of Hydrogen Energy, 2013. 38(12): p. 4901-4934.

[2] Chen, Y., et al., Key Components and Design Strategy for a Proton Exchange Membrane Water Electrolyzer. Small Structures, 2022.

[3] Shiva Kumar, S. and V. Himabindu, Hydrogen production by PEM water electrolysis – A review. Materials Science for Energy Technologies, 2019. 2(3): p. 442-454.

[4] Rozain, C., et al., Influence of iridium oxide loadings on the performance of PEM water electrolysis cells: Part II – Advanced oxygen electrodes. Applied Catalysis B: Environmental, 2016. 182: p. 123-131.

Fig 1. Polarization curves for MEAs. Anode and cathode catalyst loading were 0.3 mgIr cm-2 and 0.3 mgPt cm-2, respectively; Nafion 115 membrane and 80℃.

Figure 1
Three-Dimensional Microstructure-Based Deformation Predictions in Battery Electrodes
Authors: Teel Hunter , Lopata Joseph Steven , Garrick Taylor R. , Wang Fengkun , Zhang Han , Zeng Yangbing , Shimpalee Sirivatch
Published: February 2024

To give insight on the deformation behavior of the porous electrodes for a lithium-ion battery induced by mechanical stresses, a three-dimensional microstructure-based modeling method (3DMS) is developed [1,2]. The 3DMS simulation applies a Finite Element Analysis (FEA) based solid-stress model to track the composite (active material (AM) and binder) porous electrodes response to compression (external forces), reversible expansion (intercalation dependent), and irreversible expansion (aging dependent).

The microstructures used for the electrodes were generated using a modified version of the opensource program MATBOX, developed by NREL, in conjunction with in-house code to create a cutout section of a representative lithium-ion cell. Both anode and cathode structures are stochastically generated and applied with an advanced volume element generation technique to resolve small interface and boundary domains created by binder generation. The applied solid-stress model couples different stresses from local mechanical behavior for the different materials present in the system, considering the individual materials respective mechanical properties. The coupled stresses are used to predict deformation in the microstructure domain. Further analysis on the behavior of the deformation is enacted to gain insights on the design of the porous electrodes.

Predictions of the electrodes’ deformation will be validated using experimental work at various length scales and compared to continuum porous electrode models from previous works. Furthermore, development of techniques using the FEA solid stress-model platform will be implemented to predict full cell-level deformation for various macro cell designs including jell-roll, pouch cells, and full module assemblies [3-8]. Ultimately, insights gained from the simulations will be used to understand irreversible deformation in electrodes after cycling and inform microstructure design- particularly for automotive-relevant applications [9].

J. S. Lopata, T. R. Garrick, F. Wang, H. Zhang, Y. Zeng and S. Shimpalee, ECSarXiv (2022).

J. S. Lopata, T. R. Garrick, F. Wang, H. Zhang, Y. Zeng and S. Shimpalee, J Electrochem Soc, 170, 020530 (2023).

D. J. Pereira, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 166, A1251 (2019).

D. J. Pereira, M. A. Fernandez, K. C. Streng, X. X. Hou, X. Gao, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 167, 080515 (2020).

D. J. Pereira, A. M. Aleman, J. W. Weidner and T. R. Garrick, J Electrochem Soc, 169, 020577 (2022).

T. R. Garrick, K. Kanneganti, X. Y. Huang and J. W. Weidner, J Electrochem Soc, 161, E3297 (2014).

T. R. Garrick, K. Higa, S.-L. Wu, Y. Dai, X. Huang, V. Srinivasan and J. W. Weidner, J Electrochem Soc, 164, E3592 (2017).

T. R. Garrick, X. Huang, V. Srinivasan and J. W. Weidner, J Electrochem Soc, 164, E3552 (2017).

T. R. Garrick and J. W. Weidner, in Electrochemical Society Meeting Abstracts 233, p. 1345 (2018).
Surface Modification of NaCrO2 Positive Electrode Material for Sodium-Ion-Batteries
Authors: Wortelkamp Fritz , Hwang Jingkwang , Matsumoto Kazuhiko , Hagiwara Rika , Krossing Ingo
Published: February 2024

Sodium-ion batteries are potential successors of lithium-ion batteries, due to the abundance of sodium resources, which leads to up to 30% cost reduction when the two systems are compared directly[1]. While the cost advantage is high the performance of sodium ion batteries still needs improvement if they are to replace their lithium counterparts in many areas. Stability and performance are big areas which need to be improved.

The volatile (H2AlOtBu)2-precursor can be used to create a coating of HAlO on metal surfaces at 270°C from the gas phase via chemical vapor deposition. It has also been used to coat Li1+x(Ni0.85Co0.10Mn0.05)1-x positive electrode material for lithium ion batteries in an autoclave at 180°C, resulting in a LiAlO2 layer and improving cycling stability.[2],[3]

In this work the same coating procedure was applied to the NaCrO2 positive electrode material resulting in a similar coating and improving the performance of the material in electrochemical tests in half cells. The coating received has been shown to be a mix of different aluminium compounds resulting in an artificial cathode electrolyte interface. Electrochemical testing shows that the capacity of the treated material is higher than the capacity of the pristine one from the first cycle and it shows increased cycling stability. These improvements can be attributed to a lower resistance of the coated compared to the pristine material as shown by electrochemical impedance spectroscopy.

Overall the coating procedure is simple and the required amount of 0.3 weight percent of precursor material compared to the positive electrode material is very small for a big effect on electrochemical performance.

[1] D.Larcher, J-M. Tarascon, Nat. Chem, 2014, 7, 19-25

[2] M. Veith, S. Faber, H. Wolfanger, V. Huch, Chem. Ber. 1996, 129, 381.

[3] A. Martens, C. Bolli, A. Hoffmann, C. Erk, T. Ludwig, M. El Kazzi, U. Bredde-mann, P. Novák, I. Krossing, J. Electrochem. Soc. 2020, 167, 70510.
Filiform Corrosion on Polyester Powder-Coated Aluminum
Authors: Petrecca Michael J. , Kotb Yosra , Prout Jonathan , Basu Abhirup , Velev Orlin D. , Fedkiw Peter S.
Published: February 2024

Filiform corrosion initiates and grows locally at macroscopic defects in coatings on metal substrates. While typically not detrimental to the bulk metal properties, the filiform corrosion results in threadlike filaments that propagate parallel to the surface underneath the coating. Herein, we present a study correlating the electrochemical and structural properties of polyester powder coatings onto 6022 aluminum to their associated resistance to filiform corrosion. Filiforms are propagated using a modified EN 3665 method and tracked temporally via bright field microscopy. Results including electrochemical impedance spectroscopy, open-circuit potential tracking, and potentiostatic experiments were used to evaluate coating barrier properties. Coating morphologies of pre- and post-corrosion samples are evaluated using SEM and EDX. Mechanical properties of free-standing polyester films are also characterized. The combined electrochemical and mechanical data are used to derive polyester coating design criterion to maximize resistance to filiform corrosion.
Investigation of Antibacterial Efficacy of CuCrO2 Delafossite Thin Films Against E. coli
Authors: Sundaresh Sreeram , Sundaram Kalpathy B.
Published: February 2024

Terminals used in hospitals, information systems displaying patient information, and smartphones use touch panels that incorporate n and p transparent conducting oxide (TCO) layers [1]. There are a lot of pre-existing research present on n-type TCO while at the same time similar research interest related to p-type TCOs has been lacking. This is due to the inherently high electrical resistivity or low optical transparency of p-type TCOs. Recently, there has been a spike in research related to p-type delafossite thin films, owing to their excellent electrical and optical properties as compared to the other p-type counterparts. Cu-based p-type delafossite materials exhibit low resistivity and at the same time good optical transparency in the visible region. Among the Cu-based delafossites, copper chromium oxide (CuCrO2) exhibits the lowest electrical resistivity reported yet. Use of CuCrO2 as the p-type TCO along with a suitable n-type TCO might demonstrates significant potential to be used for optoelectronic applications.

In this work, CuCrO2 thin films have been deposited on quartz substrates using dual target RF magnetron sputtering technique. This involved dual sputtering of 3- inch Cu2O and Cr2O3 targets. The substrate temperature was maintained at 400 °C during the deposition with Ar used as the sputtering gas. This was followed by post deposition annealing. Previous research carried out by our group has indicated that single-phase CuCrO2 was obtained at an annealing temperature of 650 °C in N2 ambiance for 4 hours [2, 3]. Successful synthesis of single-phase CuCrO2 has been confirmed using XPS and XRD study. The resistivity of CuCrO2 was obtained as 0.652 Ω-cm, which is the lowest reported so far. The optical study denoted an average optical transmission of > 60% in the visible wavelength spectrum and a high optical bandgap of 3.2 eV. The antibacterial efficacy of different thickness of CuCrO2 thin films was tested against E. coli bacterial strain and compared against the efficacy of plain quartz in this research work. Results showed that with an increase in the thickness of CuCrO2 thin films, the efficacy against E. coli increases. The highest antibacterial efficacy of 78.07 % was shown by 2000 A° CuCrO2 thin film.

[1] Chiu T-W, Yang Y-C, Yeh A-C, Wang Y-P, Feng Y-W. Antibacterial property of CuCrO2 thin films prepared by RF magnetron sputtering deposition. Vacuum. 2013;87:174-177.

[2] Sundaresh S, Bharath AH, Sundaram KB. Effect of Annealing Temperature on Radio Frequency Sputtered p-Type Delafossite Copper Chromium Oxide (CuCrO2) Thin Films and Investigation of Diode Characteristics Forming Transparent pn-Heterojunction. Coatings2023.

[3] Sundaresh S, Bharath AH, Sundaram KB. Effect of Cu2O Sputtering Power Variation on the Characteristics of Radio Frequency Sputtered p-Type Delafossite CuCrO2 Thin Films. Coatings2023.
CO2 Separation Using Electrochemical Hydrogen Pumping
Authors: Kanazawa Sota , Matsushima Hisayoshi , Ueda Mikito
Published: February 2024

Introduction

Carbon dioxide (CO2) separation and capture technologies are necessary for a decarbonized society. The chemical absorption method using an amine solvent has been demonstrated in steel and power industry. However, the separation process has some drawbacks such as material corrosion. In this study, we examined CO2 separation by electrochemical approach using hydrogen pumping.

Experimental

The JARI fuel standard cell was employed and modified. It was divided in anode and cathode compartment by a cation exchange membrane. KHCO3 solution and KCl solution were circulated in the anode and cathode compartment, respectively. H2 gas was supplied to the anode at a constant flow rate by mass flow controller. Electrolysis was carried out at various cell voltages using a DC power supply unit. The gas from the anode was introduced into a quadrupole mass spectrometer (QMS). The volume rate of CO2 gas was measured by a mass flow meter.

Results and discussion

Figure 1 shows the current-voltage curve when H2 gas was supplied, and constant voltage electrolysis was carried out. The current was detected below the theoretical decomposition voltage of water (1.23 V). This supported that the reversible reaction of hydrogen pumping (H2 ⇆ 2H+ + 2e-) was occurred as expected. The Pt catalyst was contributed to the small overvoltage.

During electrolysis, gas was generated in the anode solution. It was separated by a gas-liquid separator, and then introduced to QMS. Figure 2 shows the relationship between the ratio of CO2 gas and cell voltage. In our experiment, the CO2 purity was over 90% at all voltages. This suggested that water electrolysis with O2 evolution did not occur. That is, by controlling the cell voltage, the hydrogen pumping reaction take place preferentially, and H+ is effectively supplied to the anode compartment. This archive high CO2 gas separation. In poster session, results on energy consumption will also be presented.

Figure 1
Effect of Structure to Promote Organic Residue Removal during Cu Post-Chemical Mechanical Planarization (p-CMP) Cleaning
Authors: Dudek Abigail L. , Caridi Adam T. , Reyes Kevin R , Keleher Jason J.
Published: February 2024

The extension of Moore’s law remains a focal point as semiconductor manufacturers drive to advance Integrated Circuit (IC) technology by implementing new materials. Chemical Mechanical Planarization (CMP) has emerged as a critical processing step in device fabrication to keep up with these demands. However, one drawback to this process is the generation of killer defects that result from residual contamination (i.e., organic residues, abrasive particles, pad remnants, etc.) that are reliant on post-CMP (p-CMP) cleaning methods. Current Cu p-CMP cleaning methods implement the use of an industry standard polymer brush coupled with cleaning chemistries to remove residual contamination. It has been well established that shear and compressive forces coupled with surface active cleaning chemistries have proven to be efficient albeit with the potential for secondary defectivity (i.e., pitting, etching, scratching). Additionally, current cleaning formulations rely on additives that promote aggressive redox conditions to remove residues through an undercutting mechanism, which leads to the propagation of the aforementioned defect modes. This work focuses on the development of a “softer” approach to Cu p-CMP cleaning by surveying various additives (i.e., -unsaturated carboxylic acids, carboxylic acids, and unsaturated benzaldehydes) to exploit an “overcutting” mode of organic residue removal. By implementing additional modes of interaction (i.e., p-stacking, H-bonding, conformational relationships, etc.), the mode of residue removal can be finely tuned to achieve desired surface-active conditions. This work employs a suite of techniques (i.e., Tafel analysis, OCP vs. time, time-resolved contact angle, shear force analysis) to correlate structure-activity to organic residue removal efficiency and the effects on the coefficient of friction (COF), particle removal efficiency, and the generation of secondary defectivity. Initial results have shown that implementing an “overcutting” mechanism will decrease the overall shear force and significantly reduce the proliferation of p-CMP cleaning defects. Furthermore, adding ancillary structure activity aids in additional modes of residue interaction to alter removal at the liquid-brush interface. Additionally, increased structure-activity has promoted residue-chemistry interactions to form a second passivation layer. Moreover, conformational changes that result in limited accessibility to the a,b-unsaturated double bond promote an “undercutting” mode of removal to become the predominant mode of organic residue mediation.
The Active Interface of Iron-Decorated Cobalt (Oxy)Hydroxide for Oxygen Evolution Reaction
Authors: Jiang Qu , Song Fang
Published: February 2024

Iron can significantly enhance the activity of Co (oxy)hydroxide. However, the nature of active sites is currently under debate for Fe-Co (oxy)hydroxide. Here, we use well-define crystalline cobalt hydroxide nanosheets and nanorods as model catalysts to investigate the role of Fe on different crystal planes. The electrochemical reactivity and morphology-dependent analysis suggest that the lateral facets of Co(OH)2 are active sites and the enhancement effect of iron incorporation only occurs on lateral facets rather than basal facets. Furthermore, by introducing tetramethylammonium cation (TMA+) as a chemical probe in KOH solution, we demonstrate the Fe species can interact strongly with the “active species” on the lateral facets and promote the improvement of OER activity. This work identifies the active site of cobalt hydroxides in the presence and absence of iron and elucidates the interaction of Fe species with “active oxygen” species on the lateral facets of cobalt hydroxide, which has a fundamental implication on the design of efficient OER catalysts.
Development of a Robust Electrochemical Ammonia Electrolysis Protocol Using in Operando Quantitative Analysis
Authors: Kim Jeongwon
Published: February 2024

Ammonia electrolysis is an eco-friendly technology that shows promise for producing clean hydrogen. Compared to water electrolysis, ammonia electrolysis only requires a low external voltage of 0.06 V to produce hydrogen. This research proposes a simple protocol for evaluating the practical properties of electrocatalysts for ammonia electrolysis using in-operando gas chromatography. The protocol allows for reliable and efficient comparison and evaluation of new ammonia oxidation catalysts, including distinguishing between competitive oxidation reactions and monitoring them in real-time. Additionally, the author investigated the correlation between physical or electrochemical surface areas and stability performances to estimate practical stability based on half-cell analysis. The use of this rigorous protocol should aid in evaluating the practical performance of ammonia oxidation and contribute to identifying viable pathways for the practical electrochemical oxidation of ammonia to hydrogen.
Development of Durable Pt/CoWO4 Nanofiber Catalyst-Support Hybrid Material Using Ex-Solution for Zn-Air Batteries
Authors: Lee Chang Ho , Lee Caroline sunyoung , Yoon Ki Ro
Published: February 2024

The zinc-air batteries (ZABs) has been regarded as a next-generation energy storage device due to its high energy density, cost competitiveness, and excellent safety [1]. However, several challenges must still be overcome to commercialize the ZABs, including poor cycle properties and low coulombic efficiency. These problems are due to oxygen-base reaction which has sluggish kinetics and a high overpotential. Generally, noble metals (Pt) and metal oxides (IrO2, RuO2) have been employed as oxygen-based electrocatalysts for oxygen reduction reaction and oxygen evolution reaction respectively. However, these materials suffer from poor durability during the reaction and high material costs. Therefore more durable and economical catalyst materials designed for ZABs should be developed.

In this study, we developed Pt/CoWO4 nanofiber hybrid material with excellent stability to overcome the limitations of the commercial catalyst. First, the ceramic nanofibers with a high specific surface area were fabricated by the electrospinning method. Pt and Co catalysts were strongly bonded to a WO3 support using an Ex-solution technique in which metal ions within the solid solution were exposed as metal nanoparticles on the surface [2]. We have modulated a stepwise thermal treatment that controls the crystallinity and oxygen deficiency of support material, and the exposure behavior of Pt, and Co nanoparticles such as particle size and alloy formation. Finally, the optimized hybrid material exhibited high catalytic activity, reaction stability, and material durability in the half-cell tests in alkaline media. Furthermore, a container-type zinc-air cell was fabricated and the Pt/CoWO4 catalyst successfully operated for over 240 h at 2mA∙cm-2. We believe this study guides a strategy for the development of more efficient catalyst materials for feasible not only the ZABs but also various metal catalyst–ceramic supports

[1] J. Fu, R. Liang, G. Liu, A. Yu, Z. Bai, L. Yang, and Z. Chen, "Recent Progress in Electrically Rechargeable Zinc – Air Batteries," Adv. Mater., vol. 31, no. 31, p. 1805230, 2019

[2] Js Jang, BJ Kim, JW HAN, WC Jung and Id Kim, “Dopant-Driven Positive Reinforcement in Ex-Solution Process: New Strategy to Develop Highly Capable and Durable Catalytic Materials,” Adv. Mater. Vol. 32, issue 46, p. 2003983, 2020

Figure 1
Computational Design of Durable and Selective Double Atom Catalysts Toward the Electrochemical NH3 Production: Role of Carbon Defects
Authors: Lee HyunJu , Han Junghyeon , Ham Hyung Chul
Published: February 2024

Electrochemical NH3 production through nitrogen reduction reaction (N2RR) has received much attention as an energy-efficient way to produce ammonia, which is one of CO2-free hydrogen carriers. Note that electrochemical N2RR is carried out under mild temperature and pressure conditions, unlike the conventional Haber-Bosch process for chemical NH3 production, which requires a lot of energy due to the high temperature and pressure conditions. In recent years, the concept of double atom catalysts (indicated DAC) has been proposed to improve the reactivity of catalyst owing to the maximized utilization and 100% dispersion of active sites. The main problems in the development of DACs are the poor stability [the dissolution of double atoms into electrolyte and agglomeration of double atoms] and the low selectivity [lower onset potential for N2RR than HER (hydrogen evolution reaction)]. In this study, by using density functional theory (DFT) calculations, we examined the role of carbon defects (di, tri, quad vacancies) in graphene in enhancing the stability and selectivity in single and double atom catalysts (Ru, RuRu, and RuFe) and screened the novel double atom catalysts which have high selectivity to NH3 and durability at reaction conditions by ligand and support engineering. First, we found the optimal carbon defect structure to suppress the dissolution and agglomeration of double atoms and unraveled the factors to enhance the selectivity to N2RR over HER. Second, we developed the multiscale model to design the selective and durable double atom catalysts by identifying the descriptors to represent the durability and selectivity of double atoms catalysts. Next, we computationally screened the novel DACs (consisting of transition metals) by using the developed multiscale model. Finally, through the electronic structure calculation, we elucidated the underlying mechanism of defect in determining the durability and selectivity of double atom catalyst. Our study can provide the design factors to efficiently engineer the carbon defect and double atom in the development of NH3 production catalyst.