bluuebunny/crossref_metadata_2025 huggingface dataset:
Cellulose Based Antimicrobial Nanocomposite Surface Coatings for Sensing of Biological Contaminants
Authors: Keleher Jason J. , Sheets Katey M , Kamuda Heather M
Published: February 2024

Biomimetic nanocomposite systems have emerged as polymeric scaffolds that utilize cooperative relationships to enhance physiochemical properties for the next generation of biosensors. These composite systems can be synthesized from biopolymers such as cellulose to manipulate the highly ordered, three-dimensional network and natural properties to create a tunable pore structure for “micro-reactor” functionality. Thus, it is vital to understand the fundamental mechanistic interactions between the biopolymer system and the functional additives incorporated within the matrix. This work focuses on designing and characterizing a conductive biopolymeric coating for the detection or electrochemical sensing of biological contaminants present on high-touch surfaces. Specifically, cellulose base polymers infused with photochemically prepared antimicrobial metal nanoparticles (MNP’s) and functional additives will be employed as the scaffold coupled with secondary functionalization via metal-coordination assisted photopolymerization of conductive polymers (i.e., aniline, pyrrole). Initial results of the antimicrobial effectiveness of the polymeric base network using an epi-fluorescent optical tweezer show an increased rate of bacterial cell death with the inclusion of MNP’s exhibited through a decrease in the green signal (live cells). Upon secondary functionalization of these composites, studies have shown uniform polymeric chain growth evident by enhanced charge transfer, 30-50 milliamps, through the matrix upon an applied voltage of 5 volts. Unraveling the adsorption/desorption phenomena between the “high touch” surfaces and the carrier media is essential. Initial results show that this correlation between adsorption/desorption rates and surface texturing (surface energy and roughness) can provide insight into the adhesion force threshold. Furthermore, the kinetic results served as a foundation for advancing an electrically active antimicrobial nanocomposite biopolymer coating with a tunable surface topography to exhibit site-specific responsivity in the presence of a biological contaminant. Results show that upon adhesion of a biological contaminant (specifically mucin), there is an impedance change caused by the increased resistance from the adherent which disrupted the resting potential and decreased the current output at the adsorption site. However, the contaminant was removed upon an applied voltage, and the potential returned to an equilibrated state.
Improved Structural Stability of CuO Via Bi Doping for Glucose Sensing
Authors: Zhong Jiajing , Zheng Weiran
Published: February 2024

Glucose sensing is of great importance in fields such as medical diagnostics, food industry, and environmental monitoring. Copper oxide (CuO) has shown promising results as an electrochemical sensor for glucose detection due to its high sensitivity and selectivity towards glucose molecules[1]. However, one of the key challenges is to maintain the morphology and crystal structure of CuO during long-term glucose electrooxidation. CuO is prone to phase transformation, which can lead to changes in its crystal structure and affect its electrochemical performance. Moreover, the stability of CuO can be affected by external factors such as applied potential and pH, which can induce corrosion and degradation of the CuO layer over time.

In this contribution, we propose a novel approach to improve the structural stability of CuO via surface bismuth doping. The Bi-doped CuO was prepared via an ultrasonic method, generating homogenously distributed Bi atoms on the surface of CuO thin flakes. At Bi doping level between 5% to 10%, the structure of CuO retains, indicating the replacement of Cu by Bi atoms other than phase separation. The long-term electrochemical test showed <1% current loss with the 10% Bi-doped CuO while >30% current loss with the CuO (Figure 1), suggesting that Bi atoms can act as the structural stabilizer for CuO electrocatalyst. Moreover, no significant sensitivity loss (~650 mA mM−1 cm−2) was observed after Bi doping.

Our results demonstrate significant improvements in the CuO sensor's stability and accuracy, which can pave the way for its practical applications in various fields.

Figure 1 Amperometric response of CuO and Bi-doped CuO (percentage shows the Bi/Cu ratio) during long-term glucose electrolysis.

Reference:

W. Zheng, Y. Li, L. Hu, L.Y.S. Lee, Sensors & Actuators: B. Chemical
2019, 282, 187-196

Figure 1
(Digital Presentation) Evaluation of a WSN Integrated to an IoT Services in a Food Chain's Blockchain System
Authors: Siueia Cátia , OKunsebor William , Sitoe Mario
Published: February 2024

Although Wireless Sensor Networks (WSN) have been greatly operating in a vast area of the industry. The food industry is one area that deserves its entire attention due its operarional framework complexity that largely involves a challenge environment of the food supply chain such as accurate control temperature of fluids. In this paper, we have considered an IoT platform which embebbeded a WSNs in a food supply chain's Blockchain scenario. In this paper, we seek for estimating the energy consumption of an IoT platform that integrates a WSN um a Smart food chain's Blockchain system. An Extreme learning machine (ELM) is introduced to estimate the energy consumption of the entire platform. Additionally, a framework of energy storage scheme is presented. The energy consumption forecasting reveals to attain sustainable results at a full cycle of the process.

Keywords: Extreme learning machine, blockchain, wireless sensor network, IoT, energy storage
(Invited) Cavitas Biosensors for Non-Invasive Monitoring of Blood Chemicals
Authors: Mitsubayashi Kohji
Published: February 2024

More than ten years have passed since various wearable sensors such as wristband sensors have been developed and commercialized, but most of them are for the purpose of measuring physical information such as heart rate. In medical and healthcare science, wearable sensors that measure biological and chemical information from the body are required. Of course, biosensing of interstitial fluid chemicals is possible like Abbott's Libre, but there is a need for non-invasive and unrestrained sensing techniques, and the development of such wearable sensors will expand future market size.

We have developed several cavitas biosensors targeting the chemical analytes in the human body cavities. So far, we have developed a soft contact lens-type glucose sensor, enabled continuous measurement of tear glucose, and reported its correlation with blood glucose levels. In addition, we fabricated a mouth guard type sensor with excellent aesthetics incorporating a small potentiostat and a Bluetooth transmitter (total weight: 1 g) and reported that it is possible to monitor oral information with some smart-watches with Bluetooth communication.

In addition, we constructed an imaging system that converts blood-derived gas components into bio-moving images and succeeded in producing moving images of percutaneous gases from various skin surfaces. As a result, we found that transcutaneous gas can be stably and highly sensitively measured from the external auditory canal. As a new cavitas biosensor, we also fabricated headset-type gas sensors to monitor not only percutaneous ethanol gas after drinking alcohol, but also acetone gas (a lipid metabolite) from the ear canal, thus indicating the possibility of a new wearable biosensor.

In this presentation, I will discuss the above research results and the possibility of future non-invasive wearable biosensors such as cavitas devices.

Figure 1
(Invited) Smartphone Diagnostics Meets CRISPR
Authors: Wei Qingshan
Published: February 2024

Smartphone-based optical imaging and sensing devices are among the next-generation biosensors that have shown great potential to transform the field of point-of-care (POC) diagnostics. With the rapid improvement of hardware (e.g., lens, image sensor, and CPU), smartphone has become a transformative microscopy and sensing platform that can support various detection or biomedical measurement applications, especially for resource-limited settings. On the other side, smartphone diagnostics can maximize its potential for early disease detection by coupling with specific molecular assays, such as nucleic acid amplification tests and immunoassays. This talk will highlight our recent effort in creating advanced field-portable biosensor platforms based on smartphones and the integration of smartphone device with CRISPR assay to generate a new functional POC diagnostic platform. An unexpected trans-cleavage behavior of Cas12a against double-stranded DNA substrates is discovered, which greatly eases the design of CRISPR-Dx reporter molecules. Promising applications ranging from POC diagnostics of human diseases to rapid assessment of biomanufacturing products will also be illustrated.

Figure 1
(Invited) Stretchable and Biodegradable Sensors Based on Liquid Metal-Polymer Composites Encapsulated in Microfluidics
Authors: Jiang Xingyu , Yang Shuaijian , Zhong Leni
Published: February 2024

Photolithography and related advances have made microfluidics, microelectromechanical systems and related systems accessible to many biomecial labs. These systems have found uses in biochemical assays, pharmaceutical screening and many fields of applications. Conductive inks made from lipid metal-polymer composites (MPC) can be encapsulated within elastomer-based microfluidic channels that serve as conducting wires that are flexible, stretchable and completely biodegradable. Such flexible devices have allow the introduction of electrical and photonic signals seamlessly into living tissues. These properties can dramatically expand the capability of stretch electronic devices as biomedical sensors, as well as sensors for electrophysiology, tissue engineering, regenerative medicine and gene therapy. MPC-based epidermal liquid metal-based electronics, such as blood oxygen sensors and sweat detection devices, allow real-time health monitoring. I will also discuss the idea of an “electronic blood vessel” that integrates sensing with regeneration. Eventually, these sensors can also harness the chemical energy within bodies to comprise self-power devices.
(Invited) Soft Electrochemical Biosensors and Supercapacitors
Authors: Cheng Wenlong
Published: February 2024

In the telehealth and Internet of Things (IoT) context, the development of wearable biosensors has become increasingly necessary to remotely monitor chemical and biological markers anytime, anywhere via a smartphone. To achieve a "burdenless" wearing experience, these devices should ideally be soft and thin, seamlessly integrating with human skin. Electrochemical signal transduction is a promising approach due to its ability to facilitate miniaturization and integration with state-of-the-art technology. However, traditional electrochemical devices, including biosensors and supercapacitors, are often constructed using rigid, planar bulk electrodes with limited electroactive surface areas.

In this presentation, I will introduce our innovative skin-like electronic skins and tattoos that utilize standing enokitake mushroom-like vertically aligned gold nanowires as electrochemical electrodes. These soft and three-dimensional electrodes possess high surface areas for efficient electrochemical reactions. Gold is an ideal material due to its biocompatibility, chemical inertness, ease of synthesis/surface functionalization, and band-gap-matching with many semiconductor materials. We will discuss our gold nanowire-based soft biosensing platform in the form of patches, fibers, and tattoos for wireless detection of glucose, lactate, pH, and cationic ions.
Nanostructured Electrochemical Devices and Self-Powered Systems for Biosensing
Authors: Lin Yuanjing
Published: February 2024

Flexible and integrated systems for smart biosensing have attracted tremendous research interest in recent years, mainly due to the rapidly expanding market of wearable and portable devices for applications in clinical diagnosis and physiological monitoring. In our work, novel and unique hierarchical nanostructures were designed and synthesized to realize electrochemical devices with high performance, especially the sensor stability and energy storage capability. Meanwhile, scalable and printable approach was developed to integrate these electrochemical devices into monolithically integrated self-powered systems. The as-developed nanostructured electrochemical devices in conjunction with printable approach show great potency in fabrication of various wearable integrated self-powered devices for personalized healthcare monitoring applications.
(Invited) Therapeutic Drug Monitoring Using Quantitative Surface Enhanced Raman Scattering
Authors: Boisen Anja
Published: February 2024

We have for the past ten years developed nanopillar-based substrates for Surface Enhanced Raman Scattering (SERS) and have applied them in e.g. food quality monitoring and detection of toxins. In an ongoing project financed by the Danish Bio Innovation Institute, we are pursuing quantitative detection of small drug molecules in patient blood samples. The aim is to be able to detect e.g. concentration of anti-cancer medication within half an hour, hereby allowing rapid and personalized dose adjustment. I will show examples of recent findings and results within sensor development, instrumentation and blood analysis.
Parallel Amperometric and Potentiometric Multianalyte Detection in a Microfluidic System
Authors: Tuladhar Pragun R , Lowery William , Cliffel David E
Published: February 2024

The adoption of microfluidic technologies in electrochemical biosensor development has enabled quantitative biomarker monitoring that use significantly lower volumes of reagents and samples, miniaturized electrodes, and inexpensive fabrication techniques, while presenting opportunities for multianalyte detection. We describe the fabrication of amperometric and potentiometric biosensors on a multichannel, platinum screen-printed electrode (SPE) and demonstrate their operation in parallel on a microfluidic multianalyte electrochemical sensor array (µMESA) platform.

Working electrodes (WEs) of an SPE were were modified with either enzymes or ion selective membranes (ISMs) for amperometric or potentiometric measurements respectively. Oxidase enzymes were dissolved in an osmium (II) bis(2,2'-bipyridine)chloride-poly(vinylimidazole-allylamine) redox polymer and immobilized on four WEs. The use of this osmium-based electron transfer mediator has been previously reported to lower the oxidation potential of analytes and to improve overall sensor performance. The remaining four WEs were modified by electrodeposition of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), an intrinsically conductive polymer. Solid contact ISMs were prepared by combining ionophores, lipophilic ion exchangers, and a fluorosilicone polymer, and drop casting the mixtures on PEDOT:PSS-coated WEs. Plasticizer-free ISMs improve sensor lifetime by lowering the glass transition temperature and eliminating leaching of plasticizers from the ISM. By utilizing these strategies, we fabricated amperometric sensors for glucose and lactate, and potentiometric sensors for K+ and Ca2+ ions. Glucose is a primary substrate for energy metabolism while lactate is a major metabolite and signaling molecule. K+ ions maintain cell membrane physiology and homeostasis whereas Ca2+ ions serve as messengers during muscle activity and neurotransmission.

Sensor characteristics like sensitivity, selectivity, linear range, and operational longevity for each biosensor were assessed using chronoamperometry or chronopotentiometry techniques on a potentiostat/potentiometer instrument. The results indicate that the sensor fabrication strategies described, in combination with our µMESA platform, can be used to measure changes in metabolite concentrations under laminar flow. Ultimately, this versatile technology may provide novel insights into complex physiological and pathological processes in biological systems.
(Invited) Functional Nucleic Acids as Bacterial and Viral Sensors
Authors: Li Yingfu
Published: February 2024

Rapid detection of infectious pathogens is vital for preventing costless outbreaks and improving human health. Current detection methods oftentimes lack the means to detect infectious pathogens in a simple, rapid, and reliable manner at the time and point of need. Functional nucleic acids (FNAs) – specifically DNA aptamers and DNAzymes – have the potential to overcome these limitations by acting as key components for point-of-care (POC) biosensors due to their distinctive advantages that include high binding affinities and specificities, excellent chemical stability, ease of synthesis and modification, and compatibility with a variety of signal-amplification and signal-transduction mechanisms. In this presentation, I will discuss the work completed in my laboratory, in collaboration with several other groups at McMaster, towards developing simple-to-use analytical devices with integrated FNAs to detect bacterial and viral pathogens, such as E. coli, Salmonella, SARS-CoV-2, porcine epidemic diarrhea virus (PEDV), directly in water, food or clinical samples.
Engineering Photoelectrochemical Detection by Combining Nanozyme and Oxygen Reduction
Authors: Ganganboina Akhilesh BABU
Published: February 2024

Efficient photoelectrochemical (PEC) detection requires a deep understanding of the processes involved in generating, separating, and reacting photoinduced carriers at interfaces. However, slow interfacial reactions and the need for appropriate photoactive layers pose significant challenges to constructing advanced PEC platforms. In this study, platinum single-atom catalysts (Pt SACs) were integrated onto semiconductor surfaces as a proof of concept, amplifying PEC signals by boosting oxygen reduction reactions. Pt SACs were also shown to exhibit efficient peroxidase-like activity, depressing PEC signals through Pt SACs-mediated enzymatic precipitation reactions. By utilizing the oxygen reduction and peroxidase-like activity of Pt SACs, a robust PEC sensing platform was successfully constructed for the sensitive detection of SARS-CoV-2. This research provides valuable insights into the use of SACs for sensitive PEC analysis.

Figure 1
Gold Nanoparticles Decoration of Zinc Oxide Nanostructures for Bio-Sensing Applications
Authors: Almog Rakefet , Shashar Eden , Sverdlov Yelena , Kadan-Jamal Kian , Shacham-Diamand Yosi
Published: February 2024

ZnO nanowalls (NWLs) is a non-toxic, high surface-to-volume ratio semiconducting nanostructure which has already showed potential applications in biosensing applications

Recently, it was discovered that decorating the metal oxide nanostructures with noble metal nanoparticles (NP) opens the doors to fabricating biosensors to detect volatile organic compounds. The aim our work is to improve the knowledge and understanding of fabricating ZnO nanowalls decorated with metal nanoparticles.

ZnO nanowalls wereas deposited both on rigid on flexible substrates at low temperature using rather simple and low-cost processes.

We examined the formation process of ZnO nanowalls on Polyimide substrate and studied the new obtained structure at the nanoscale, at different conditions such as growth temperature, concentration and time. The morphology of the ZnO nanowalls obtained under each of these conditions was studied. The crystal structure of the ZnO nanowalls at different growth temperatures was studied by X-ray diffraction.

Next, NP decoration of gold and platinum was conducted. A study of the nucleation and growth of the ZnO nanowalls, and of the NP decoration at different schemes of surface functionalization, was conducted.

The first attempts for NP deposition achieved NP clusters with irregular morphology, however at well-kept conditions we succeeded in achieving a good dispersion of NP (figure 1(b).)

The metal nanoparticle surface functionalization poses some material-related questions regarding the behavior of that nano-structured material, when exposed to volatile organic compounds (e.g. Ethylene). This will allow us to develop a novel family of biosensors that enable sensitivity, rapidity, and selectivity for the detection of a wide range of target analytes.

The final goal is a flexible all-in-one, highly sensitive and selective biosensors using relatively simple and low cost materials and processing. The sensors will use recent advances in functionalized Gold NP decorated ZnO electrodes based sensors.

Figure 1
Optimization of Osmium Metal Loading in Redox Polymer for Biosensing Applications
Authors: Lowery William , Tuladhar Pragun R , Cliffel David E
Published: February 2024

Historically, polymers have been utilized to provide a three-dimensional interface for proteins and enzymes in devices such as biosensors and biohybrid solar cells. While these polymers can provide a scaffold onto which biomolecules can be immobilized, their true utility comes from the ability of some polymers to enhance electrochemical processes. Osmium-containing redox polymers are crucial in biosensor applications because they can exclude signals from interferent molecules by shifting the operating voltage of the working electrode. While osmium redox polymers have been used for many years, there is little literature available discussing the incorporation of the osmium onto the polymer backbone. Specifically, how the polymer properties are affected by varying metal loadings is particularly lacking. In this work, the metal loading, or the percentage of polymer side chains containing an osmium unit, is varied from 2 – 32% (as determined by 1H NMR). The electrochemical properties of the osmium-containing polymers are then determined by cyclic voltammetry. It is hypothesized that higher osmium loading will correlate with easier electron transfer and overall improved sensor performance when interfaced with biosensors. Preliminary data has supported this hypothesis and further reinforces the need for such a comprehensive, yet fundamental study of osmium redox polymers to inform the biosensor community.
(Digital Presentation) Obtaining Copper-Deficient Cobalt Ferrite Nanoparticles from Facile Glycerol-Assisted Synthesis and Electrochemical Sensing of Acetaminophen
Authors: Alfonso Guillermo , Granja Claudia Patricia , Morales Jimmy , Dector Andrés , Gómez Cuaspud Jairo Alberto
Published: February 2024

Copper-deficient cobalt ferrite nanoparticles were synthesized by a simple combustion method. In the synthesis, tests of different polyalcohols were carried out, demonstrating the effectiveness of glycerin as a cosolvent, facilitating the preparation of electrode modifier nanomaterials. A standing time (eight hours) before calcination causes a decrease in the secondary phase of hematite. In acidic conditions (pH 2.5), the limit of detection (LOD) was calculated as (99.4 nM), the limit of quantification (LQO) turned out to be (331 nM). and RSD 3.31%. The superior electrocatalytic activity of the copper-deficient cobalt ferrite modified electrode Co0.87Cu0.13Fe2O4/GCE correlates very well with its resistance Rct found by the EIS technique and which defined its electron transfer capacity. The detection limit obtained for Co0.87Cu0.13Fe2O4/GCE in the present study (99.4 nM) is lower than the other electrodes studied here. The results show the possibility of determining acetaminophen in complex biological matrices
Attempts to Electrochemically Synthesize Palladium Superhydrides By High Pressure Method – Combination of Electrolytic Hydrogen Charging and Electroplating of Protective Coatings –
Authors: Hashimoto Tomoya , Fukumuro Naoki , Yae Shinji
Published: February 2024

Introduction

Incited by the possibility of room-temperature superconductors in superhydrides, numerous them have been synthesized using a diamond anvil cell under high pressures up to several hundred GPa. Although palladium has widely researched for a long time as a prototype hydrogen-absorbing metal, the palladium superhydrides has not yet been obtained under such high pressures. A recent theorical calculation has predicted that the palladium superhydrides (e.g., PdH10) may be synthesized by combing electrolysis and high pressure1), but it is not certain whether it can be achieved. In this study, we attempted to synthesize the palladium superhydrides by using electrolytic hydrogen charging under high pressures, and subsequently applied protective coatings to suppress the hydrogen desorption from the palladium hydrides at ambient pressure.

Experimental

Figure shows a schematic illustration of the high-pressure apparatus. The high-pressure apparatus can apply the pressure of up to 400 MPa to the electrolyte in the electrolytic cell by pumping water into a sealed high-pressure vessel using a plunger pump and pressure multipliers. A cold-rolled palladium foil of 30 ~ 40 μm in thickness was used as a cathode, and a zinc plate was utilized as a soluble anode. Hydrogen was electrochemically loaded into the palladium foil at 0 V vs. Zn in an electrolyte consisting of 0.1 mol dm-3 sulfuric acid and 4.6 mmol dm-3 zinc sulfate under various pressures for 6 hours. Subsequently, the palladium foil was coated with the zinc film at constant current density 25 mA cm-2 for 120 seconds under the high pressure. The specimen was removed from the electrolytic cell in the high-pressure vessel at ambient pressure, and the hydrogen concentration of the palladium hydride PdH
x
was determined by thermal desorption spectroscopy. Structural analysis was conducted using X-ray diffraction and scanning electron microscopy.

Results and discussion

A number of bubbles were observed on the palladium foil surface during the electrolytic charging at ambient pressure. On the other hand, no bubbles were observed at 300 MPa. The zinc film with approximately 1.4 μm thick was coated on the PdH
x

surface after the electrolytic hydrogen charging. The hydrogen concentration of the PdH
x

was approximately x = 0.7 immediately after synthesis, which decreased to x = 0.2 without the zinc coating. On the other hand, the hydrogen concentration of the PdH
x
was maintained at least 1 week with the zinc coating. This result indicates that the zinc film acts as a barrier to hydrogen desorption from PdH
x
, and suggests that if the palladium superhydrides could be synthesized by electrolytic hydrogen charging under high pressure, it could be taken out to ambient pressure while maintaining its concentration.

Reference

1) W. Guan, R. J. Hemley, and V. Viswanathan, PNAS,
118, e2110470118 (2021)

Figure 1
Anodic Oxidation and Corrosion Resistance of Ta-Containing High Entropy Alloys
Authors: Ishizawa Toshimasa , Nishimoto Masashi , Muto Izumi , Sugawara Yu
Published: February 2024

Stainless steels are corrosion resistant, but pitting corrosion sometimes occurs in chloride solutions. Anodic oxidation is one of the effective methods to increase the pitting corrosion resistance. However, unlike valve metals, stainless steels are difficult to improve pitting corrosion resistance by anodic oxidation. In this study, Fe-based alloys containing valve metals were fabricated to investigate anodic oxidation and corrosion resistance.

Equimolar CrFeNbNiTa and (CrFeTa)30(NbNi)5 alloys were fabricated by arc melting, and pure metals of Cr, Fe, Nb, Ni, and Ta were used as raw materials. After casting, the ingots were heat-treated at 1200 ℃ for 2 h (furnace-cooling) and cut into 2 mm thick sheets. After that, the specimen surfaces were polished up to 1 μm with a diamond paste. The microstructures were observed using an optical microscope and a scanning electron microscope. The chemical compositions and elemental distributions of the specimens were analyzed by energy dispersive X-ray spectroscopy. Potentiodynamic polarization was performed in 1 M H2SO4. As a reference, Type 304 stainless steel was used.

The equimolar CrFeNbNiTa alloy was composed of two phases. One was Cr- and Fe-rich and the other was Nb- and Ni-rich. The (CrFeTa)30(NbNi)5 alloy was a single phase. In the potentiodynamic polarization measurements, the current densities of oxygen evolution reaction of equimolar CrFeTaNbNi and (CrFeTa)30(NbNi)5 alloys were lower than that of Type 304 stainless steel. Moreover, the passive current densities of equimolar CrFeTaNbNi and (CrFeTa)30(NbNi)5 alloys were higher than that of Type 304 stainless steel.
Anionic Additive-Integrated Electrolyte Therapy: Enhancing High-Voltage Stability and Performance in Lithium-Ion Batteries
Authors: Ahuja Aakash , Kumar Ajit , Sengupta Abhinanda , Lohani Harshita , Kumari Pratima , Mitra Sagar
Published: February 2024

Significant endeavours have been undertaken to advance the development of eco-friendly, abundant, cost-effective, and high-performance cathode materials for lithium-ion batteries. Among the various contenders for next-generation energy storage systems, spinel LiNi0.5Mn1.5O4 has emerged as a leading high-voltage cathode candidate, owing to its aforementioned benefits. Nonetheless, the widespread adoption of LNMO-based lithium-ion batteries is substantially impeded by the electrochemical instability of conventional carbonate electrolytes above 4.5 V. High-voltage cycling of such batteries results in rapid capacity degradation and metal-ion dissolution from the LNMO electrode into the electrolyte, particularly at elevated temperatures, further causing deposition of metal-ions on anode electrode. Therefore, stabilizing the electrode/electrolyte interface is crucial to achieve improved electrochemical performance of the Li-ion cell at high voltages. The utilization of sacrificial electrolyte additives is regarded as a straightforward and efficacious method to accomplish this objective. These additives form a protective layer on the cathode surface, mitigating electrolyte decomposition and transition metal-ion dissolution and deposition on anode’s surface. Various additives facilitating high-voltage cathode materials have been documented, encompassing fluorides and sulfonates. However, borate salt-containing additives are particularly promising within this context.

In the present study, we endeavour to elucidate the surface modifications transpiring on the electrode’s surface when minute quantities of borate-based salt are employed as an additive in the conventional EC:EMC electrolyte for high-voltage operation. We explored the impact of the additive salt in a standard LiPF6-EC/EMC base electrolyte on the discharge capacity and rate performance of the LiNi0.5Mn1.5O4/Graphite based Li-ion cell. The electrochemical behaviour, morphological behaviour, and electrode-electrolyte interphase layer stability on the electrode were meticulously examined using high-resolution transmission electron microscopy (HR-TEM), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). These characterisations conformed the presence of an electrode-electrolyte interface forming a thin-layer via the sacrificial decomposition of the utilised additive. The introduction of this salt exhibits favourable effects on enhancing the electrochemical performance of the LiNi0.5Mn1.5O4/Graphite in high-voltage lithium-ion batteries. Notably, the utilised additive excels in mitigating irreversible capacity loss and reducing cycling fade, as it preferentially decomposes and forms a conductive, protective film that impedes subsequent electrolyte decomposition, thereby substantially enhancing cell performance.
Unraveling Plasmonic Effects in Plasmon-Enhanced Lithium–Oxygen Batteries
Authors: Chae Kyunghee , Kim Minju , Marques Mota Filipe , Kim Dong Ha
Published: February 2024

Rechargeable lithium–oxygen batteries have high theoretical energy density compared to the conventional Li–ion batteries. However, the recharging process is primarily disturbed by the large overpotential caused by sluggish OER kinetics. Plasmonic materials have unique properties with light, known as surface plasmon resonance (SPR). In this study, we demonstrate plasmonic effect in the Li–O2 battery system by incorporating gold nanoparticles on the Ketjen Black (KB) cathode. During discharge, plasmonic Au NPs induce a Li2O2 morphology change to small particles, which are easily decomposed during recharge. Most importantly, the SPR-induced hot carriers help to form and decompose Li2O2 and suppress carboxylate side-products, decreasing recharge voltages and increasing the round-trip efficiency up to 80.2%. Meticulous analyses of the catalytic properties of the Au NPs and the SPR-induced near-field enhancement and local heat effects are here additionally shared.

Keywords: Li–O2 battery, Plasmonics, Light-enhanced batteries, Hot carriers, Near-field enhancement
Electrochemical Model-Based State-Space Approach for Real-Time Parameter Estimation of Lithium-Ion Batteries
Authors: Cho Kyeongeun , Kim Sanghyun , Kim Seongyoon , Choi Jung-Il
Published: February 2024

Lithium-ion batteries are widely used in various applications, including electric vehicles and renewable energy storage systems, due to their high energy density, long cycle life, and low self-discharge rate. Accurate estimation of battery state of charge (SOC) and state of health (SOH) is crucial for their safe and efficient operation.

In this study, we propose a model-based state-space solver for real-time monitoring of lithium-ion batteries under various operating conditions. The state-space model simplifies a single-particle model and enables simulations considering the current state of the battery using a Kalman filter. The model includes a one-dimensional Single Particle Model with Electrolyte (SPMe) and uses eigenfunction expansion to solve the mass conservation equation for the electrolyte phase. The final form of the state-space model for the solid and electrolyte phase includes a voltage equation using lithium-ion concentration. The proposed solver was validated by comparing it with the SPMe solver, and the results agree well.

To achieve on-line updating of the battery model parameters, we propose a multi-scale parameter adaptive method based on dual Kalman filters for estimating the SPMe model parameters. The fast time-varying parameters are separated from the slowly time-varying parameters, and then each group is estimated by a different Kalman filter with a different time constant. This method enables the estimation of both the SOC and all parameters, including the SPMe model parameters. Additionally, we provide a parameter adjustment method for dual extended Kalman filters when estimating multiple parameters.

The proposed method reduces the influence of the initial state error on the algorithm and improves its robustness. Experimental results demonstrate that the accuracy of the algorithm is improved by separating the fast and slow parameters and estimating them with different Kalman filters. The proposed solver can be used with Kalman filters and the like in an onboard environment due to its fast calculation speed.

Figure 1
In-Situ Observation of the Formation and Relaxation Processes of Concentration Gradients in a Lithium Bis(fluorosulfonyl) Amide–Tetraglyme Solvate Ionic Liquid Using Digital Holographic Interference Microscopy
Authors: Kamesui Go , Nishikawa Kei , Ueda Mikito , Matsushima Hisayoshi
Published: February 2024

Introduction

Next-generation Lithium-ion batteries (LIBs) require fast charge–discharge operations, during which a steep concentration gradient (CG) is formed between the two electrodes. The formation of a concentration profile between the electrodes in an LIB with a solvate ionic liquid (SIL) is observed at a distance of less than 1 mm using holographic interferometry. This in situ technique enables the visualization of concentration profile formation near both electrodes during electrolysis, which relaxes after the electrolysis is stopped. The diffusion coefficients near both the electrodes are calculated from the concentrations of transient species near the electrode surfaces. The diffusion coefficient is smaller on the anode side of the cell than that on the cathode side owing to the viscosity of the electrolyte in the diffusion layer. This viscosity effect may have caused the concentration profile to become asymmetrical during the relaxation of the CG.

Experimental

Li metal was used for the anode and cathode. The distance between the electrodes was 600 μm. The electrolyte was a SIL mixture of LiFSA (lithium bisfluorosulfonylamide) and G4 (tetraglyme) at a molar ratio of 1:1. After 100 seconds of Li electrodeposition and dissolution at a constant current density (3 mA cm-2), the current was stopped, and the relaxation process of the concentration gradient generated by electrolysis was observed with a laser interference microscope (Lyncee Tec) for 1700 seconds. The Li+ concentration near the electrode was calculated from the optical phase difference based on the bulk electrolyte outside the diffusion layer. The electrode surface concentration and transference number of Li+ were used to obtain the diffusion coefficients of Li+ near both electrodes. The time variation of the diffusion layer thickness during and after electrolysis was measured to study the mass transfer phenomenon during the formation-relaxation process of the concentration gradient.
Investigation of a 2D Metallic Selenide for Supercapacitative Applications
Authors: Li Weihao , Ganin Alexey
Published: February 2024

The study investigates the suitability of a 2D metallic selenide material for use in supercapacitors, which are rapidly gaining recognition as a viable energy storage solution. While supercapacitors are highly efficient at charging and discharging, their lower energy density is a limiting factor. This research focuses on identifying new materials that can enhance the energy density of supercapacitors while maintaining their rapid charging capabilities. The study examines CrSe2, a promising chalcogenide material that has recently been suggested for use in hybrid composite systems. The research shows that CrSe2 can be made in bulk quantities and exhibits high stability in certain electrolytes. The electrochemical properties of CrSe2 are measured for the first time and found to be consistent with an electric double-layer capacitance. Additionally, the material demonstrates a high specific capacitance, indicating potential for use in supercapacitive applications. The study concludes that the metallic-type conductivity of CrSe2 could be responsible for its superior performance over high surface area carbon black samples.
Highly Fluorinated and Boron Containing Anion Derived Stable Anode and Cathode Interfaces for Long Cycle and High Voltage Sodium Metal Batteries
Authors: Lohani Harshita , Duncan Dale , Kar Mega , Kumari Pratima , Mitra Sagar
Published: February 2024

Sodium metal is a propitious anode for the development of next generation metal batteries owing to its low reduction potential (-2.71 V) and high theoretical capacity (1165 mAh g-1)1. Among various electrolytes, carbonate solvents can be useful to develop high voltage metal batteries with wide temperature range2. However, the aggressive reactivity of sodium metal in carbonate electrolytes lead to the formation of unstable solid electrolyte interface on the metal anode which renders poor long cycling performance to the battery3. In this work, we have fabricated thin and inorganic components (F and B rich) rich solid electrolyte interface (SEI) on Na metal anode and cathode electrolyte interface (CEI) on oxide-based cathode to improve long cycling stability of sodium metal battery. Here, fluorine (F) and boron (B) containing anion is compared with conventional hexafluorophosphate anion (PF6-) in binary carbonate solvent system (EC:EMC). The stable stripping/plating behaviour of both symmetric (Na/Na) and asymmetric cell (Al/Na) in case of F and B containing anion is found compared to the PF6
- anion.

The excellent long-term cycling stability of full cell (Na/Na0.67Fe0.5Mn0.5O2) is further attributed to the improved electrochemical stability window and better aluminium passivation on employing F and B containing anion in the electrolyte system as compared to PF6
- anion. The dual role of F and B containing anion to form stable interfaces on both the anode and cathode side provides a pathway in the development of fluorinated electrolytes for high voltage sodium metal batteries.

References:

(1) Yang, T.; Luo, D.; Liu, Y.; Yu, A.; Chen, Z. Anode-Free Sodium Metal Batteries as Rising Stars for Lithium-Ion Alternatives. https://doi.org/10.1016/j.isci.

(2) Xu, G.; Huang, S.; Cui, Z.; Du, X.; Wang, X.; Lu, D.; Shangguan, X.; Ma, J.; Han, P.; Zhou, X.; Cui, G. Functional Additives Assisted Ester-Carbonate Electrolyte Enables Wide Temperature Operation of a High-Voltage (5 V-Class) Li-Ion Battery. J Power Sources
2019, 416, 29–36. https://doi.org/10.1016/j.jpowsour.2019.01.085.

(3) Akkisetty, B.; Dimogiannis, K.; Searle, J.; Rogers, D.; Newton, G. N.; Johnson, L. R. Enflurane Additive for Sodium Negative Electrodes. ACS Appl Mater Interfaces
2022, 14 (32), 36551–36556. https://doi.org/10.1021/acsami.2c06502.
Synthesis and Electrochemical Characterization of Novel Electrolyte Additives for High Performance in Lithium-Ion Batteries with Si-Based Anodes
Authors: Schmidt-Meinzer Noah , Krossing Ingo
Published: February 2024

Silicon is a promising active material for the anode in lithium-ion batteries (LIB), since it enables much higher energy densities than graphite - the state-of the art material for LIB-anodes. However, the utilization of silicon brings many challenges, which originate mainly from the enormous volume change between the lithiated and delithiated state (300%). One of the consequences is a constant re-formation of the solid electrolyte interphase (SEI), which is accompanied by a loss of active Li+. This leads to a strong capacity fading, which results in a very short cycle life. [1]

An efficient and economical approach to tackle these problems is the utilization of additives in the electrolyte. Additives are small molecules or salts that decompose during the first cycles of the battery life resulting in an interphase with modified composition and thereby an improved SEI. Depending on the additive the SEI can reduce the impedance of the cell and help to maintain the structural stability of the anode. [2]

In this work four new additives were synthesized and electrochemically tested with a silicon-based anode. Improvements regarding capacity retention were found for all additives in half-cell measurements. Hence, after 500 cycles additive 1 showed a 26 % increased capacity retention, while additive 4 induced an improvement of 43 % compared to the base electrolyte. Electrochemical impedance measurements were conducted and simulated directly after the formation as well as after 100 cycles. The resistance of the first semi-circle showed a reduction of 40 % and 26 % after formation and 100 cycles respectively, when the additive 1 is used. The second semi-circle showed no significant change after formation, but a 27 % reduction of resistance after 100 cycles, when the additive 1 is used. The semi-circles can be attributed to the Li ion migration in the SEI. Therefore, the SEI build from the decomposition of additive 1 favours charge-transfer compared to the SEI build from the base electrolyte. Scanning electron microscopy (SEM) images of lithiated and delithiated electrodes show smaller cracks on the surface when using additive 1 compared to the electrode treated with the base electrolyte. This phenomenon shows an increased cohesive force of the new formed SEI mitigating the effects of the enormous volume expansion in the electrode.

[1] Zuo X., Zhu J., Müller-Buschbaum P. & Cheng Y.-J. Silicon based lithium-ion battery anodes: A chronicle perspective review. Nano Energy. 31, 213-143; 10.1016/j.nanoen.2016.11.013 (2017)

[2] Eshetu, G.G., Zhang, H., Judez, X. et al. Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes. Nat Commun
12, 5459; 10.1038/s41467-021-25334-8 (2021)

Figure 1
Two Dimensional Pb-F-Cl and Ba-F-Cl As Supercapacitor Electrode Materials
Authors: Servottam Swaraj , Rao Chintamani Nagesa Ramachandra
Published: February 2024

Two-dimensional (2D) materials have gained great importance since the discovery of graphene. Of these several 2D materials, PbFCl and BaFCl, have not been exploited for electrochemical applications. Herein, we have prepared single and few-layered nanosheets of PbFCl and BaFCl by exfoliation through ultrasonication in different solvents such as water, dimethylformamide and N-methyl-2-pyrrolidone. The Hansen-Solubility-Parameters of the solvents played an important role in exfoliation of bulk phase of PbFCl and BaFCl. These materials were studied for supercapacitor properties by means of cyclic voltammetry (CV) curves, galvanostatic charge–discharge (GCD) curves and electrochemical impedance spectroscopy (EIS). Exfoliated 1–2 layered PbFCl exhibits a high-specific capacitance of 158 F g−1 at a scan rate of 10 mV s−1.

References: -

Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater.
6, 183 (2007).

Manjunath, K., Servottam, S., Soni, A. & Rao, C. N. R. A study of two-dimensional PbFCl and BaFCl. Bulletin of Materials Science
43, 1–7 (2020).
High-Capacity Nickel-Based Layered Oxides Containing Niobium Ions for Lithium-Ion Batteries
Authors: Yamaki Saeka , Ugata Yosuke , Yabuuchi Naoaki
Published: February 2024

Lithium-ion batteries have been widely used in recent years, from portable electronic devices to electric vehicles. Although LiNiO2, is expected to be ideal electrode materials for electric vehicle applications due to its high reversible capacity, Ni ions migrate from octahedral sites of transition metal layers to tetrahedral sites of adjacent Li layers during charging. This process is partly reversible process but Ni ions are left the tetrahedral sites of the Li layer after the continuous cycle test, which prevents the re-insertion of Li ions, resulting in capacity degradation. [1]

To suppress the capacity degradation LiNiO2, the effect on the phase transition behavior by Nb substitution for Ni ions in LiNiO2 is examined.

The samples with different Nb contents LixNi1–xNbxO2, are synthesized and tested as electrode materials. The Nb-substituted sample shows highly improved cycle characteristics compared with non-substituted LiNiO2. SEM observation of the samples reveals that the primary particles become smaller, suggesting that the Nb-substituted influences the crystallization process for LiNiO2. By comparing the results of electrochemical and structural characterizations for the samples with or without Nb substitution, the origin of the improvement of electrode reversibility is discussed in details.

Reference [1] N. Ikeda et al., and N. Yabuuchi, Journal of Materials Chemistry A, 9, 15963 (2021).