bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) A Three-Biomarker Strategy for Diagnosis of Acute Myocardial Infarction Via a Multiplex Electrochemiluminescence Immunoarray
Authors: Cui Hua , Guo Mingquan , Smith Zachary J.
Published: February 2024

Acute myocardial infarction (AMI) is a cardiovascular diseases characterized by myocardial necrosis resulting from acute and persistent obstruction of a coronary artery. AMI accounts for one third of overall cardiovascular diseases deaths, exceeding the mortality of any single tumor, and shows an increasing trend year by year1-2. Cardiac troponin T is the gold standard for diagnosis of AMI but has insufficient specificity at early times3-4. Herein, we report a three-biomarker strategy (cardiac troponin I, heart type fatty acid binding protein, and copeptin) for rapid, accurate and early diagnosis of AMI via a multiplex electrochemiluminescence immunoarray coupled with robust machine learning. In a >200 subject pilot trial, the three-biomarker joint model achieved 100% sensitivity and specificity across a broad patient population with chest pain, including those patients within three hours of symptom onset. This study is very important for the diagnosis, medical treatment and prognoses of AMI, which holds the potential to minimize AMI mortality as well as to lower medical expenditure.
Stretchable Electrodes for Medical Devices
Authors: Saini Matteo , Andreula Stefania , Taveggia Chiara , Groppi Chiara , Trezzi Marco , Spreafico Laura , Gussoni Luca
Published: February 2024

[Key topics:

Electrodes

Electrodeposition techniques

Electrochemical properties

Structure – physical properties relationships]

The fabrication of electrodes on polymers, and especially on elastomers, is relevant in several fields. Among them, the medical field can benefit a lot from these kinds of electrodes. The human body uses electrical signaling in the muscles as well as in the nervous system to transfer energy and information between the brain and the rest of the body. Cardiac pacemakers, neuromodulation systems, neuromonitoring systems, brain machine interfaces are all examples where electrodes play a key role. Most of the body tissues are soft with unique shapes. When it is required to transfer electrical signals between the soft tissues and hard electronic systems, having soft and conformable interfaces might be particularly advantageous to increase the efficacy of the therapies, the energy consumption of the medical devices and the patient’s quality of life.

We have developed several solutions to obtain metal patterns on elastomers that are stretchable, strongly adhered and with high charge-storage capacity. The methods are based on SCBI (Supersonic Cluster Beam Implantation) that allows to form a nanocomposite made of metal nanoparticles embedded in the elastomer, which acts as seed where thin film electrodes are created either through physical vapor techniques or by electro or electroless deposition.

Here we compare electrodes made of Pt, Pt-Ir, Ir and IrOx obtained via electrochemical and physical vapor techniques. We present how, by tuning the process parameters, is possible to control the electrodes properties such as the charge-storage capacity, the corrosion under electrical stimulation and stability to tensile and compressive stresses. We show how the electrochemical and mechanical properties are correlated to the micro-structure, the grain morphology, and the stoichiometry. It is also shown how obtaining the electrodes with the right specific surface area is essential to guarantee stability against corrosion under high currents input.
Development of an Electrochemical Sensor for Histamine Detection, Based in the Formation of Complexes with Chelating Agents
Authors: Felix Navarro Cinthya Paola , Gallegos Tabanico Amed , Jimenez Canale Jorge , Santacruz Ortega Hisila , Sarabia Sainz Jose
Published: February 2024

Histamine(β-imidazolylethylamine) (His) is a biogenic amine. It is an important mediator involved in

various physiological and pathological processes, including neurotransmission and numerous brain

functions, secretion of some hormones,regulation of gastrointestinal, circulatory functions, and

inflammatory reactions. However, a high level of histamine in the human body causes an allergy-like

syndrome called histamine intolerance or histamine poisoning (toxic level 50 mg per 100 g of

product). The source of elevated histamine level is due to fermented foods, processed meat, and

spoilage of the foodstuff, in particular seafood,due to uncontrolled microbial growth. Therefore,

monitoring of histamine is a critical task for the food industry and food safety. Also, electrochemical

sensors have received extensive attention researchers in the development of rapid His detection

methods due to their low cost, portability, higher sensitivity, and suitability for on-site screening. The

general objective of this work is to develop an electrochemical sensor for the detection of Histamine

based on the modification of gold screen printed electrodes using L-cysteine (L-Cys) as a quelant agent

for the capture of our analite of interest. To study each step of the modification on the electrode

surface, electrochemical techniques were used: Electrochemical Impedance Spectroscopy (EIS) with

a frequency of 50kHz and Cyclic Voltammetry(CV) with a window potential of -0.6 to 0.6 V and scan

rate of 0.5V/s . As partial conclusions, the modification of the electrode with L-cys/Cu(II) was

demonstrated by electrochemical methods. Thus, the developed sensor has the potential application

for Histamine detection
Development of an Integrated Multi-Method Electrochemical Biosensor for Rapid-on-Site Detection and Quantification of Cyanotoxins
Authors: Ogungbile Abraham , Icin Izthak , Vernick Sefi
Published: February 2024

The accumulation of Cyanotoxins (CTXs) in water reservoirs is an emerging global concern. Exposure to microcystin-LR (MC-LR), among the most common CTXs, is associated with hepatotoxicity and carcinogenesis and leads to both acute and chronic damages. Stringent regulation has recently been imposed by the World Health Organization, limiting the allowed MC-LR concentration in drinking water to <1 μg/L. Current methods for MC-LR detection require expensive equipment, trained personnel, and labor-intensive preparation. Therefore, there is an urgent need for an affordable, on-site diagnostic tool providing a rapid quantitative determination of MC-LR in various water types. In this study, we have developed an electrochemical (EC) biosensor that comprised of a miniaturized and multiplexed microchips, functionalized with anti-MC-LR antibodies, and MC-LR detection is based on the transduction of bimolecular binding into an electrochemical signal. The transduction method applied is based on the comparison of two (2) electrochemical techniques: a label-free Electrochemical Impedance Spectroscopy (EIS) a labeled Electrochemical Immunoassay (ECI) detection of MC-LR in <10 min. The former, the EIS-based detection method, demonstrated the feasibility of detecting ultra-low (3 ppt or ng/L) MC-LR concentrations, and preliminary results also showed that the biochip demonstrated its use in rapid quantitative detection of microcystins in raw cyanobacterial cultures. However, the latter, ECI-based detection method showed a detection limit of 3µg/L (3ppb) of purified MC-LR concentrations, which is an order of magnitude less sensitive than the EIS-based detection method. These LODs obtained from the two methods are superior to currently employed solid-phase immunoassays and other analytical methods. Based on our findings, we anticipate that in the near future electrochemical biosensors would be an essential tool in water monitoring and environmental diagnostics.

Figure 1
A Single Trapped Vesicle Enhances the Sensing of Dynamic in-Teractions between Tau Protein and Lipid Membrane
Authors: Chen Ke-Le , Yu Ru-Jia , Long Yi-Tao
Published: February 2024

The interaction between tau protein and lipid membrane is of considerable interest in neuroscience, as it promotes inter-neuronal tau spreading in neurodegenerative diseases. Here, we report a vesicle-enhanced nanopore electrochemistry for sensing the dynamic lipid-tau interaction at a sub-millisecond time scale. This method is developed by confining a model vesicle of ~ 30 nm within a lipid-modified nanopipette orifice with a comparable diameter, which increases the sensing ability in lipid-tau interaction to a signal-to-noise ratio of 10.8. Both tau and phosphorylated tau present a periodic dynamic behavior in this biomimetic system, showing typical ionic current oscillation. By comparing the oscillation frequency, p-tau shows a higher affinity to the lipid vesicles, considering its lowered binding frequency towards vesicle. This result is also supported by the Biolayer interferometry. For this well-distributed current oscillation, we proposed volume shrinking as a possible mechanism, which is further supported by finite element simulations. To elucidate the possibility of lipid-tau interactions inducing vesicle shrinkage, TEM was employed for vesicle characterization in bulk solution. With a 14 h incubation of SUV with tau proteins, the diameter shrunk from ~30 nm to ~22 nm. The difference of affinity between tau and p-tau toward synaptic-mimic vesicles helps to provide fundamental insight into the regulation of tau proteins in synaptic vesicle motility and consequently contributes to the understanding of neural dysfunction in neuro-degenerative diseases.

Figure 1
Freshness Indicating Substance Sensor in Meat Using Molecularly Imprinted Carbon Paste Electrode
Authors: Yoshimi Yasuo , Sato Yui , Iwasaki Takumi , Aaryashree Aaryashree
Published: February 2024

Fresh fish and meat are rich in adenosine-triphosphate (ATP), which over time is converted via adenosine-diphosphate (ADP) and adenosine-monophosphate (AMP) into the flavor component inosinate, which, with more time, is converted into the unpleasant-tasting components inosine and hypoxanthine . These six substances are indicators to measure the freshness and maturity of meat and fish. If these substances can be easily measured at the distribution site, fair trade based on objective judgments of freshness and ripeness will become possible.

We are attempting a simple disposable sensor using molecularly imprinted polymer-immobilized carbon paste (MIP-CP). Graphite particles immobilized with a radical polymerization initiator were immersed in a solution of the target materials, inosine, methacrylamidophenylboronic acid, methacrylic acid, and methylenebisacrylamide, and graft polymerized by photoirradiation. The particles were washed with hydrochloric acid to remove the inosine to obtain graphite covered with an MIP layer. This was mixed with ferrocene-containing silicone oil to form a paste and applied to a commercial carbon screen-printed electrode (Zensor, Taipei) to obtain disposable electrodes.

Differential pulse voltammetry was performed in buffer solutions containing inosine or sodium inosinate; the current at 0.9 V vs. Ag/AgCl increased with increasing inosine concentration, but there was little sensitivity to sodium inosinate concentration as shown in the Figure. These results indicate that a sensor has been created that shows a highly selective response to inosine, which is the template for MIP. The measurement takes about 30 seconds. We will continue to improve the reproducibility and develop a sensor that can detect the other five indicator substances in the same way.

This work is partially supported by Small-Business Innovation Research (SBIR) Program of Bio-oriented Technology Research Advancement Institution (BRAIN), in Japan (SU23A03).

Figure 1
Development of Glutamate Sensor Based on Mxene/NiO Modified Screen Printed Carbon Electrode
Authors: Aziz Adnan Bin , Alom Nur , Han Tan Kim , Saidur R , Jamal Mamun
Published: February 2024

Glutamate plays a vital role as a neurotransmitter, contributing significantly to both physiological and pathological processes. Although enzymatic electrochemical sensors exhibit the ability to selectively detect glutamate, the presence of enzymes introduce sensor instability. Consequently, there is a pressing need for the advancement of enzyme-free glutamate sensors [1-3]. In this study, we have developed an incredibly sensitive non-enzymatic electrochemical sensor for detecting glutamate.

This was achieved by synthesizing nanoparticles of nickel oxide (NiO) and physically combining them with MXene on a Screen-printed carbon electrode (SPCE)[2]. Fig. 1 shows the MXene-NiO nanoparticles (NPs) modification process on SPCE. In this work, cyclic voltammetry and amperometric techniques were carried out in a three-electrode system with an oxygen-saturated environment, where MXene-NiO/SPCE, pt wire, and Ag/AgCl electrode were used as working, counter, and reference electrode respectively. MXene-NiO/SPCE showed significant electro-catalytic activity in catalyzing the oxidation of glutamate in 0.1 M NaOH solution. A linear relationship was established between the current response and Glutamate concentration after the electrochemical experiments were conducted while working parameters were optimized. We conducted an extensive investigation of glutamate-sensing mechanism. The optimized sensor exhibited an irreversible oxidation process for glutamate, involving the transfer of one electron and one proton. It displayed a fast response time of < 5 s and a linear response within the concentration range of 20 to 300 µM at a pH of 7, with a LOD of 17.5 µM, sensitivity of 4500 µA.mM−1.cm−2. The morphology of the MXene-NiO composites was characterized using SEM, EDX, XRD, FT-IR, and UV spectroscopy techniques. The investigation into interference on the MXene-NiO/SPCE revealed a noteworthy current response to glutamate even in the presence of uric acid and ascorbic acid. As a result, the development of a reliable, enzyme-free glutamate sensor could be enabled by this simple sensor based on MXene-NiO composites.

Fig. 1. The process of MXene/NiO/SPCE electrode.

Reference

[1] M. Jamal et al., Microsyst. Technol., 24, 4217–4223, 2018. doi: 10.1007/s00542-018-3724-6.

[2] M. Jamal et al.,
Biosens. Bioelectron., 40, 213–218, 2013. doi: 10.1016/j.bios.2012.07.024.

[3] K. M. Razeeb et al., Vertically Aligned Nanowire Array-Based Sensors and Their Catalytic Applications. In: Vestergaard, M., Kerman, K., Hsing, IM., Tamiya, E. (eds) Nanobiosensors and Nanobioanalyses, Springer, Tokyo, 2015.

Figure 1
Study on Factors Affecting Water Resistance of Titanium Negative Electrode Materials for Na Batteries
Authors: Ishikawa Tetsuya , Yabuuchi Naoaki
Published: February 2024

【Background】

In recent years, sodium-ion batteries, which use abundant Na ions as charge carries, have been attracting attention as an alternative to lithium-ion batteries. Sodium-ion batteries are expected to be used as large-scale energy storage devices due to moderate energy density, but air storage stability of the layered oxides is an important issue to be considered. In this study, air storage stability of titanium layered oxides with different chemical compositions and structures, P2 Na2/3Cr1/3Mg1/6Ti1/2O2, P2 Na0.67Li0.22Ti0.78O2, P2 Na2/3Cr2/3Ti1/3O2, and P3 Na0.58Cr0.58Ti0.42O2, is systematically examined, from which the factors affecting air storage stability is discussed.

【Results and Discussion】

Figure 1 shows the X-ray diffraction patterns of P2 Na2/3Cr1/3Mg1/6Ti1/2O2 (P2 NaCrMgTi) before and after soaking in water for 30 minutes (and then dried after vacuum filtration). After the soaking test, although the profile of diffraction lines is broadened, its original crystal structure is retained. On the other hand, for P2 Na2/3Cr2/3Ti1/3O2 (P2-NaCrTi), and P3-Na0.58Cr0.58Ti0.42O2 (P3-NaCrTi), hydrated phases are formed.

Figure 2 compares charge/discharge curves of these layered oxides after the soaking test. Electrodes with P2-NaCrMgTi, which have a minor change in crystal structure, shows the deterioration in initial Coulomb efficiency, but no reduction in discharge capacity is evidenced. In contrast, both P2-NaCrTi and P3-NaCrTi, where the hydrated phases were formed, shows the degradation in electrode reversibility. From these results, air storage stability of these different layered oxides is discussed in detail.

Figure 1
Solid Electrolyte Coated NCM523 for Composite Cathode in All-Solid-State Batteries
Authors: Kim Jun tae , Shin Hyeon-ji , Jung Hun-Gi
Published: February 2024

All-solid-state battery using sulfide solid electrolyte has advantages such as high lithium ionic conductivity and wide electrochemical stability window. Although it is attracting great attention in that it is capable of high power and high energy density, there are problems to be improved.

Organic liquid electrolytes in conventional lithium ion batteries have excellent wettability and can form uniform lithium ion transfer channels in electrodes. However, in the case of all-solid-state battery, the formation of a solid-solid interface is limited due to the solid characteristics. In addition, the degradation of the interfacial contact between the active material and solid electrolyte in the composite electrode due to the volume change of the active material with (de)-intercalation of lithium ion during cycling causes loss of the lithium ionic pathway and deterioration of cell performance. This study focuses on improving battery performance by coating the surface of active material with solid electrolyte to maintain an even lithium ion transfer path in the composite electrode. The solid electrolyte coating of the active material has a decisive effect on the electrochemical behavior of the cell because it affects the formation of smooth lithium ionic pathway and suppression of voids in the composite electrode. Therefore, the focus of this study is to confirm the formation of uniform solid electrolyte coating layer according to the size of the solid electrolyte.

Therefore, the particle size of the solid electrolyte was diversified using a liquid-phase process and a dispersant, and the solid electrolyte coating was performed using a dispersion process. It was confirmed that an even solid electrolyte coating layer was formed as the particles size of the solid electrolyte decreased, and the electrochemical performance was improved due to the solid electrolyte coating layer. In addition, it was confirmed that the lithium ionic pathway was maintained even after long cycling with the solid electrolyte coating layer, and also the side reactions occurred less according to the homogeneous electrochemical reaction.
Accelerated 3D Simulation for Analyzing Electrochemical and Thermal Distribution in Lithium-Ion Batteries
Authors: Kim Sanghyun , Kim Seongyoon , Ha Jinho , Choi Jung-Il
Published: February 2024

Understanding the spatial and temporal internal behavior of lithium-ion batteries (LIBs) is crucial for ensuring safe operation and preventing unexpected faults during manufacturing and diagnosis processes. Traditional approaches, such as the pseudo-two-dimensional (P2D) model, provide a simplified representation of LIBs but limit the analysis of continuum-scale electrochemical distribution inside the cell.

This study proposes an accelerated three-dimensional (3D) simulation methodology, expanding the conventional P2D model into a pseudo-four-dimensional (P4D) model, including three dimensions of cell structure and a pseudo-dimension inside electrode particles based on the porous electrode theory. In this study, the electrochemical model in the pseudo-four-dimension is combined with a thermal model, considering energy balance with ohmic heat, reaction heat, entropic heat, and internal short circuit (ISC) heat generation.

To analyze the P4D model, we apply the following numerical strategies: 1) Elimination of nonlinearity inside model equations using Taylor series expansion, 2) Separation of electrochemical and thermal model variables using a staggered time-stepping method, and 3) Determination of time step size based on the gradient of model output. The proposed method is validated by comparing simulation results for an LFP cell with experimental results and a commercial software under constant current discharge operations (1C, 2C, 3C, and 5C).

The accelerated 3D simulation methodology offers significant advantages for exploring internal inhomogeneous properties under different materials operating conditions, ensuring battery safety and reliability under various scenarios. We demonstrate that the proposed method enables the investigation of internal distributions of concentration, potential, and temperature inside battery cells, paving the way for designing and managing batteries with various materials.

Figure 1
Ion Transport in Plasticized Li1.5Al0.5Ge1.5(PO4)3 Based Electrolytes
Authors: Lifshitz Moran , Greenbaum Anna , Sasaki Kaito , Gladkich Alex , Feldman Yuri , Golodnitsky Diana
Published: February 2024

The development of an efficient devices for energy storage, conversion, and transmission is one of the key priority areas today. At the center of these activities is the development of all-solid-state high-energy and high-power lithium-ion batteries.

Our research is focused on the study of ion transport in a plasticized-by-ionic-liquid composite membrane formed by electrophoretic deposition (EPD). The EPD membrane comprises above 85% of high-ion-conductivity ceramic matrix Li1.5Al0.5Ge1.5(PO4)3 (LAGP) and less than 15% polyethyleneimine (PEI). The EPD rate and morphology of the membrane were characterized by SEM, TOFSIMS and DSC methods. 0.3M LiTFSI–PYR14TFSI was infused in the membrane to form a quasi-solid electrolyte. The complex, non-Debye dielectric response of the quasi-solid electrolyte, tested over the temperature and frequency ranges of (-140oC) to (+100oC) and 10-2 – 106 Hz, has been described in terms of several distributed relaxation processes separated by different frequency and temperature ranges. While at low temperatures, the main contribution is from LAGP, in the middle- and high-temperature regions, the superposition of a few non-Arrhenius processes is observed. Relaxation is perturbed by clear phase transition related to melting of the ionic liquid. Different scales of the ionic transport and corresponding relaxation of the apparent dipole moment in the materials are discussed.
Ab Initio Molecular Dynamics Study on Self-Healing Solid Polymer Electrolyte for Lithium Metal Batteries
Authors: Zhan Yu-Ting , Nachimuthu Santhanamoorthi , Jiang Jyh-Chiang
Published: February 2024

Lithium metal batteries (LMBs) have generally become potential candidates for energy storage devices because of their high energy density. However, the practical applications of LMBs have been limited due to the low safety of liquid electrolytes. Compared to liquid electrolytes, solid-state polymer electrolytes (SPEs) have excellent mechanical strength. However, there is room for improvement because traditional PEO-based SPEs need more mechanical properties and electrode contacts for flexible energy device applications. Self-healing solid polymer electrolytes (SHSPEs) have excellent flexibility and healing ability and can also suppress dendrite formation to increase the safety of LMBs. In this study, a novel SHSPE is designed by a combination of the zwitterionic copolymer, SBMA ([2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide)-co-BA (Butyl Acrylate), and a lithium salt, LiTFSI. We explored their solvation structures and reactivity on the Li metal anode using Density functional theory (DFT) and ab initio molecular dynamics (AIMD) methods. Besides, we also studied the reactivity of the considered SHSPE on the Cu (100) surface to explore the SEI formation mechanisms. The cationic NR4
+ and anionic SO3
- groups of SBMA interact electrostatically and form cross-linked network structures within the electrolyte framework, providing the designed SHSPE with prominent self-healing capacity. The decomposition reactions of SHSPE on the Li metal anode are explored, and the resultant decomposition products that contribute to the formation of the solid electrolyte interphase (SEI) are identified. Furthermore, AIMD results indicate that highly concentrated SO3
- groups in the SHSPE promote Li ion diffusion, which increases Li ionic conductivity. The present findings provide design criteria for developing highly conductive self-healing SPEs.
Electrochemical Preparation and Characterization of Gold Coatings on Stainless Steel Bipolar Plates for Corrosion Protection in PEM Electrolyzers
Authors: Hoess Christian Elieser , Leimbach Martin , Kurniawan Mario , Fritz Mathias , Bund Andreas
Published: February 2024

With the increasing demand for CO2 reduction in all industrial sectors, the utilization of renewable energy and a sustainable storage structure plays an essential role to reach a clean energy system. Hydrogen is one of the important elements which can be used as an energy carrier due to its high specific energy density (ca. 40 kWh/kg) and also as a reducing agent in steel production to greatly lower CO2 emissions. Currently, hydrogen is mainly produced via steam reforming of natural gas which produces large amounts of CO2 gas. This can be replaced by a much cleaner process of water electrolysis using a PEM (Proton Exchange Membrane) electrolyzer. The projected high demand for PEM electrolyzer stacks urges an industrial scaled-up manufacturing process of the electrolyzer’s components such as the bipolar plates (BPP) and porous transport layers (PTL). To reduce the production costs, an inexpensive base material like stainless steel can be utilized but needs a stable, conductive, and protective thin coating to withstand the highly acidic conditions during electrolysis at the anode.

This contribution will discuss recent results on applying a noble metal coating (e. g. Au) to increase surface conductivity and to protect the stainless steel BPP from corrosion. Several electrochemical deposition methods including the pretreatments were investigated to ensure a stable and homogenous coating. Different layer combinations with Ni as an adhesive layer were also tested and compared for their corrosion stability. So far, a single-layer Au coating showed good performance as a protective coating.
Crevice Corrosion Initiation and Growth of Die-Cast ADC12 Aluminum Alloy
Authors: Takeuchi Kaito , Muto Izumi , Nishimoto Masashi , Sugawara Yu
Published: February 2024

Die-cast ADC12 (Al-3Cu-10Si) aluminum alloy is widely used because of mechanical properties and castability. In atmospheric environments, crevice corrosion sometimes occurs on ADC12; therefore, improvement of corrosion resistance and elucidation of corrosion mechanisms are needed.

As-cast specimens of ADC12 were used in this study. Pure Al sheets were used for comparison. The microstructure of ADC12 was composed of α-Al and Al-Si eutectic phases. Intermetallic particles (IMPs) containing Cu existed. IMPs containing Fe also existed. The size of IMPs was around 1 μm.

Crevice was made between a polycarbonate nut and bolt, and immersion test was performed in 0.1 M NaCl. After immersion, the dissolution of α-Al was observed inside the crevice. To ascertain the effect of pH on α-Al phase dissolution, immersion test was carried out in 0.1 M HCl and 0.1 M NaCl (pH 10.0) In 0.1 M HCl, α-Al dissolved, and the corrosion morphology was similar to that inside the crevice.
An Easy-to-Use 3D-Printed Electrochemical Cell for I
n Situ Raman Spectroscopy
Authors: Kawashima Kenta , Son Yoon Jun , Wang Ziqing , Rose Roger F. , Marquez-Montes Raul A. , Smith Lettie A. , Chukwuneke Chikaodili E. , Mullins Charles Buddie
Published: February 2024

In energy conversion devices such as electrolyzers and batteries, the monitoring of electrode surfaces during electrochemical processes is essential to understand their operation mechanisms. One of the promising techniques is in situ Raman spectroscopy, which can analyze (i) electrode surface structure, (ii) surface species (reaction intermediate species), and (iii) localized electrolyte species.1 The bottleneck for using this technique is the high cost and complexity of commercially available electrochemical cells designed for in situ Raman spectroscopy. To solve these issues, a few research groups provided 3D-printed spectroelectrochemical cells with low cost and less complexity.2,3 However, the spectroelectrochemical cells so far reported require a specific sample type (i.e., particles). We need a low-cost and less-complex spectroelectrochemical cell that can be used for more varieties of samples.

In this study, we will provide a new design of a spectroelectrochemical cell that has compatibility with various sample types [i.e., substrates (e.g., metal foil strips, fluorine-doped tin oxide-coated glass, indium tin oxide-coated glass, etc.) and particle]. Specifically, a versatile, low-cost, and less-complex electrochemical cell for in situ Raman spectroscopy will be fabricated using a stereolithography (SLA) 3D printer with resin as a printing material. Herein, using the SLA 3D-printed spectroelectrochemical cell, we will also demonstrate a few example studies for electrolyzer and battery applications.

References

W. Zheng, Chemistry–Methods, 3, e202200042 (2023).

M. F. dos Santos et al., Anal. Chem., 91, 10386–10389 (2019).

G. D. da Silveira et al., Anal. Chim. Acta, 1141, 57–62 (2021).
Understanding the Role of Cracks in Active Oxygen Species Formation during Oxygen Evolution Reaction
Authors: Wang Sihong , Song Fang
Published: February 2024

Understanding the formation and location of catalytic intermediates is crucial for unraveling the mechanism of oxygen evolution reaction (OER), a key process in electrochemical water splitting. Despite the availability of various in-situ and ex-situ characterization methods, the formation and location of intermediates remain elusive, hindering the development of more efficient electrocatalysts. In this work, we discovered a stable static active oxygen species formed during the chemical oxidation of cobalt hydroxide flakes, providing a unique opportunity to probe the intermediates involved in OER. We are able to monitor the equilibrium conversion between stable peroxo structure and superoxo radical via EPR and Raman test, shedding light on the nature of the active oxygen species. In addition, CoOOH flakes with cracks were synthesized via controlled chemical oxidation, enabling the investigation of the role of crack/edge structures in the electrocatalytic activity. Statistical regression analysis combining morphological features, electrochemical performance, and Raman spectroscopy confirmed a strong correlation between morphology evolution, OER activity, and active oxygen species, highlighting the importance of controlling the morphology of electrocatalysts for enhancing their performance. Therefore, we propose that the source of active oxygen intermediates can be attributed to the presence of crack/edge structures. The crack-rich CoOOH exhibit significantly higher current density at a lower overpotential, providing a new direction for the design of efficient water oxidation electrocatalysts. Overall, this work offers important insights into the mechanism of OER and provides a basis for the development of more efficient and sustainable electrocatalysts for energy conversion and storage.
Altering the Interfacial Microenvironment of the Photocatalytic System for Boosted H2O2 Generation from Biomass Waste
Authors: Xia Ruiqin , Guo Zhengxiao
Published: February 2024

The catalytic and environmentally friendly synthesis of H2O2 is crucial in green chemistry. Many researchers are dedicated to its study, and various methods have been proposed, but these methods usually require organic solvents or dissipative reagents. It has been reported recently that different biomass could be converted to hydrothermal carbonaceous carbon (HTCC) photocatalysts capable of producing H2O2 with high efficiency. Herein, we report a method to further increase the catalytic efficiency of HTCC, from 0.53 mmol gcat
-1 h-1 to 1.35 mmol gcat
-1 h-1 under air, by simply changing the neutral solution to basic (pH = 11) where the contact environment between HTCC and the solvent is changed. The radical trap experiment and electron paramagnetic resonance (EPR) spectroscopy confirmed a two-step oxygen reduction reaction as the primary catalytic pathway. The mechanism study indicates that OH- in the solution could react with the acidic terminal functional groups of HTCC originating from the synthesis and hole-induced oxidation within HTCC during photocatalysis, thus enhancing the generation of active species and electron transfer. This study paves a new way to improve the photocatalytic efficiency of HTCC by altering the microenvironment of solvent and photocatalysts.
(General Student Poster Award Winner, 2nd Place) Enhanced Oxygen Evolution Reaction Performance through Alkaline-Earth Metal Doped Fe-Rich Nano Dry-Petals: A Cost-Effective and Eco-Friendly Electrocatalyst Approach
Authors: Lahrichi Amina , El Issmaeli Youness , Kalanur Shankara S. , Natarajan Sadesh Kumar , Pollet Bruno Georges
Published: February 2024

The progress towards hydrogen production via electrolysis technologies rely on the advancement of economical, abundant, non-toxic, stable, and efficient non-precious metal catalysts for oxygen evolution reactions (OER). As the second most abundant metal on Earth, iron (Fe) offers a cost-effective alternative to more expensive OER catalysts derived from ruthenium (Ru), iridium (Ir), cobalt (Co) and nickel (Ni). However, Fe-based catalysts typically display limited OER activity. Here we present a unique strategy of introducing an alkaline-earth metal into Fe-rich crystal for the enhanced OER activity in alkaline condition. To achieve this, a facile method was developed to obtain a nano dry-petals structured M-FeOOH electrocatalyst. The optimized M-FeOOH electrocatalyst exhibits an impressively low overpotential of +259 mV at a current density of 10 mA cm-2 in 1.0 M KOH which was found to be superior to the pristine FeOOH electrode. Through a series of experiments and density functional theory (DFT) calculations, we reveal that the addition of an alkaline-earth metal to FeOOH as a dopant optimizes the electronic structure and free energy for adsorbed intermediates synergistically. As a result, the OER activity of the M-FeOOH electrocatalyst is significantly improved. Our results highlight the possibility of doping FeOOH OER catalysts using an affordable and eco-friendly approach, setting the stage for the development of advanced OER electrocatalysts.
Electrochemical Monitoring of Super-Engineering Polymer Depolymerization: A Rapid and Simple Approach
Authors: Kim Jee Woo , Kim Byung-Kwon
Published: February 2024

The mechanical properties and processability of polymers are strongly influenced by their molecular weight, underscoring the critical importance of controlling depolymerization during storage in polymer synthesis and application. However, conventional methods of determining molecular weight, including viscosity measurements, gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy, typically necessitate substantial quantities of polymer samples and protracted measurement times. Moreover, certain polymers may undergo continuous degradation post-polymerization, rendering depolymerization analysis via traditional means highly challenging. Hence, there is an imperative need to develop novel analysis techniques that overcome these limitations and facilitate comprehensive depolymerization characterization.

To surmount these challenges, we have developed a novel electrochemical method utilizing cyclic voltammetry to facilitate polymer depolymerization measurement. For measuring degree of depolymerization, we used thermal depolymerization process. As the polymer's molecular weight diminishes because of thermal depolymerization, the solution viscosity decreases correspondingly, thereby enabling unimpeded redox species diffusion and a proportional increase in steady-state current. By constructing a calibration curve of current versus thermal depolymerization time for a polymer, we can swiftly and accurately determine its molecular weight tendency in solution. Our investigations indicate that this electrochemical technique is more efficient and cost-effective as it necessitates smaller sample volumes and shorter measurement times than conventional methods, and it exhibits excellent potential for analyzing and maintaining polymer properties across various industries.

[1] Kim, J. W., Kim, S. J., Song, I. Y., Lee, W. E., Heo, K., Kim, S. Y., ... & Kim, B. K. (2022). Simple and rapid electrochemical monitoring for depolymerization of polyamic acid. Analytica Chimica Acta, 1233, 340489.
(Invited) TiO2 Single Nanotubes Decorated with Fe3O4 Nanoparticles for Photocatalytical Environmental Applications
Authors: Sepúlveda Sepúlveda Lina Marcela , Saldan Ivan , Sopha Hanna , Macak Jan M.
Published: February 2024

Self-organized TiO2 nanotubes arrays, formed by electrochemical anodization of Ti, have attracted tremendous scientific and technological attention, due to their remarkable properties such as the tunability of dimensions, their directionality, high surface area, high stability, and ability to absorb a significant amount of incident light [1,2].

The most widely used electrolyte for the synthesis of TiO2 nanotube layers is based on ethylene glycol containing small amounts of water and fluoride ions. However, nanotubes prepared in these electrolytes present a double-walled structure. The outer wall consists of almost pure TiO2, and the inner wall consists of TiO2 contaminated with carbon and fluoride species [3,4]. In recent years, the selective etching of the inner nanotube wall on Ti layer enabled the synthesis of single-wall nanotubes that showed superior photo-electrochemical performance compared to their double-walled counterparts [5]. An extensive etching also enabled the synthesis of single-tube powders, which can be in turn effectively decorated with Fe3O4 nanoparticles to act as magnetically guidable photocatalysts [6,7].

The presentation will discuss the synthesis of these nanotube morphologies and their performance in the photocatalytic degradation of model dye in the liquid phase as well as model drugs that are problematic in wastewaters. We will demonstrate how the photocatalytic performance is influenced by the single nanotubes and single nanotubes decorated with Fe3O4 magnetic particles. Experimental details and photocatalytic results will be presented and discussed.

References:

[1] J. M. Macak et al., Curr.
Opin. Solid State Mater.
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2007,1-2, 3.

[2] K. Lee et al., Chem. Rev.,
2014, 114, 9385.

[3] S.P Albu et al., Adv. Mater.
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[4] A. Dronov et al., Appl. Surf. Sci.,
2018, 434, 148.

[5] M. Motola et al., Electrochem. Commun
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2018, 97, 1.

[6] D. Beketova et al., ACS Appl. Nano Mater
.,
2020
, 3, 155.

[7] M. Sepúlveda et al.,
Ceram Int., 2023
, 49, 6764.
(Invited) Design of Specific Polymer Binders for Stabilization of Si Based Anode in Lib
Authors: Matsumi Noriyoshi
Published: February 2024

In recent years, intense efforts have been focused on stabilization of silicon-based anode in Li ion secondary batteries due to their remarkably high theoretical capacity. At the same time, strategy has not yet been established on how to stabilize the silicon based anode sufficiently during long cycles so that it will be feasible for practical use.

In this talk, several different approaches on stabilization of silicon-based anode will be introduced both in terms of polymer binders design and active materials design.

Our group synthesized several self-healing polymer binder and polymer coating material which are efficient for the use in silicon-based anode. Poly(borosiloxane) (PBS)1 was prepared by dehydrocoupling polymerization between mesitylborane and diphenylsilanediol in the presence of transition metal catalyst. PBS was found to show self-healing property at 45oC when coated onto Si electrode. When PBS coated Si electrode was employed for anodic half cell (Si/EC:DEC (1/1=v/v)/Li), it showed much improved durability when compared with PVDF coated Si based cell or bare Si based cell. We also reported a design of BIAN (bis-imino-acenaphthene) based conjugated polymer (P-BIAN) /Poly(acrylic acid) (PAA) composite binder for Si based anode2,3. Due to combination of n-type imine-based conjugated polymer (H-bonding acceptor) and PAA (H-bonding donor), synergistic effect in stabilization of Si/C composite anode was observed due to both of desirable electronic structure of P-BIAN and H-bonding based self-healing properties. In this system, anodic half cell delivered specific discharging capacity of above 2000 mAhg-1 for 600 cycles. As alternative approaches, we are also working on preparation of specific Si based anodic active materials which showed extremely high durability. b-SiC/N-doped carbon4 was found to show excellent durability even in the presence of conventional binder materials due to restricted volumetric changes of b-SiC during lithiation/delithiation. We also report coating of mechanically highly robust silicon oxycarbide on micro silicon5, which was also found to be quite effective.

References

1) Patnaik, S. G.; Jayakumar, T. P.; Sawamura, Y. Matsumi, N. ACS Appl. Ener. Mater.
2021, 4, 2241.

2) Gupta, A.; Badam, R.; Matsumi, N. ACS Appl. Ener. Mater.
2022, 5, 7977.

3) Gupta, A.; Badam, R.; Nag, A.; Kaneko, T.; Matsumi, N. ACS Appl. Ener. Mater.
2021, 4, 2231

4) Nandan, R.; Takamori, N.; Higashimine, K.; Badam, R.; Matsumi, N. J. Mater. Chem. A.
2022, 10, 5230.

5) Nandan, R.; Takamori, N.; Higashimine, K.; Badam, R.; Matsumi, N. J. Mater. Chem. A.
2022, 10, 15960.
(Invited) Coordinatively Cross-Linked Binders for Silicon-Based Electrodes for Lithium Ion Batteries
Authors: Huet Lucas , Moreau Philippe , Devic Thomas , Dupre Nicolas , Roue Lionel , Lestriez Bernard
Published: February 2024

We have proposed a simple and versatile preparation of Cu(II)- or Zn(II)-poly(carboxylates) reticulated binders by the addition of Cu(II) or Zn(II) precursors into a pre-optimized carboxymethyl cellulose / citric acid binder solution. These binders lead systematically to a significantly improved electrochemical performance when used for the formulation of silicon-based negative electrodes [1,2]. Mechanical characterizations reveal that the coordinated binders offer a better electrode coating cohesion and adhesion to the current collector, as well as higher hardness and elastic modulus, which are even preserved in presence of a carbonate solvent (i.e. in battery operation conditions). Ultimately, as shown from operando dilatometry experiments, the electrode expansion during lithiation is reduced, mitigating electrode mechanical failure [2]. In complement, we used scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy to probe the nanoscale morphology of such electrodes. This technique reveals the homogeneous coordination of carboxylated binder with Zn cations and its layering on the silicon surface. The SEI formed after the first cycle is denser with Zn-coordinated binder and preferentially observed on binder-depleted zones [3]. In summary, the superiority of coordinated binders can be attributed to their capacity to better stabilize the electrode and the SEI layer due to improved mechanical properties. This resulted in a lower SEI impedance, a higher first cycle coulombic efficiency, and a 40% improvement of capacity retention after 60 cycles for highly loaded electrodes of over 6 mAh.cm-2. Noteworthy, this formulation principle allows for better reproducibility and manufacturing quality of the electrodes [4].

[1] D. Mazouzi, R. Grissa, M. Paris, Z. Karkar, L. Huet, D. Guyomard, L. Roué, T. Devic, B. Lestriez, Electrochimica Acta, 304 (2019) 495-504

[2] L. Huet, D. Mazouzi, P. Moreau, N. Dupré, M. Paris, S. Mittelette, D. Laurencin, T. Devic, L. Roué, B. Lestriez, ACS Applied Materials & Interfaces, 15 (2023) 15509-15524

[3] L. Huet, P. Moreau, N. Dupré, T. Devic, L. Roué, B. Lestriez, Small Methods, 2022, 2200827

[4] L. Huet, H. Houisse, N. Herkendaal, T. Devic, L. Roué, B. Lestriez, Energy Technology, 2023, 2201483

Figure 1
Next-Generation Battery Components Derived from Soft Dendritic Colloids
Authors: Petrecca Michael J. , Shenoy Akhil , Leatherman Jaden R. , Velev Orlin D. , Fedkiw Peter S.
Published: February 2024

Growing demands for energy storage are causing rapid development of next-generation batteries. Researchers typically use commercially available Li-ion components and processing techniques to investigate new chemistries and cell architectures. Herein, we propose an emerging materials-development platform: shear- driven precipitation of polymeric materials to develop application-specific battery components. In this process, polymer particles with high aspect ratios, called soft dendritic colloids (SDCs), are formed via turbulent solvent-nonsolvent induced phase separation. Two specific component applications are presented.

The first application is nano-composite redox active polymer electrodes for Li-ion batteries. Redox polymer electrodes are currently limited by low intrinsic electronic conductivity. As a result, large amounts of conductive additives are added to the composite electrodes, lowering the gravimetric performance. The network forming capabilities of the SDC morphology provides intimate contact between active material and conductive material to enable free-standing electrodes that are produced via simple vacuum filtration. We present cyclic voltammetry and charge/discharge data using poly(2,2,6,6-tetramethyl-1-piperidinyloxy methacrylate) as the SDC material.

The second application is composite separator assemblies to mitigate lithium polysulfide shuttling in Li-S batteries. Polysulfide shuttling is considered a technological hurdle plaguing Li-S battery development. Separators can be functionalized to reduce polysulfide shuttling by incorporating additives onto or within the separator matrix, which either bind or repel the soluble species to prevent crossover to the anode. We demonstrate that SDC materials are a promising platform for fabricating nanocomposite separators using a variety of nanomaterials. The nano composite separators show increased thermal stability, cycling stability, and polysulfide rejection as compared to commercial materials.
(Best Presentation Award - 3rd Place) Evaluating the Safety Limits of Soft Shorting in Li-Ion Batteries
Authors: Schumacher Bret , Marbella Lauren , Steingart Daniel A.
Published: February 2024

This study aims to redefine the safety limitations of lithium dendrite soft shorting in lithium-ion batteries using isothermal microcalorimetry and thermal reduction tests. Lithium dendrites are generally assumed to pose a safety risk by causing fatal short circuits, which can lead to thermal runaway and catastrophic battery failure. This assumption has led to massive amounts of time and capital on dendrite suppression and elimination research.

Thermal reduction tests on delithiated lithium cobalt oxide were conducted to determine the absolute temperature at which thermal runaway occurs in one of the most volatile conventional systems. Isothermal microcalorimetry was conducted on the same system to measure the heat generated by the soft short circuit. Our results showed that the absolute temperature generated by the lithium dendrite soft short circuit was significantly less than the onset of thermal runaway via a thermal reduction route. These findings challenge the general assumption that lithium dendrites will directly lead to thermal runaway events in lithium-ion batteries.

Our study suggests that while lithium dendritic shorting may pose a safety risk in lithium-ion batteries, it will not directly lead to a catastrophic thermal event. Further research is needed to explore the potential implications of deactivating the metallic lithium in the system via this soft shorting pathway.