bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Estimating OCP-Temperature Dynamics for Determining Lithium-Ion Battery Entropy Coefficients
Authors: Widanalage Dhammika , Queisser Oliver , Paarmann Sabine , Wetzel Thomas
Published: February 2024

The open-circuit potential (OCP) of a li-ion cell is a function of both state-of-charge and temperature. Characterising its dependence on temperature is important for thermal simulations as the derivative of the OCP with temperature acts as a reversible heat source term in the model. Known as the entropy coefficient, this derivative is a thermodynamic quantity that varies over the cell’s state-of-charge (SoC). The potentiometric approach [1] is widely used to characterise the entropy coefficient for a given SoC. This involves applying step changes in the temperature and allowing the cell OCP to reach (or approach) a steady-state value, which can take several hours (>8 hours), for a given SoC of interest.

Robust techniques are required that can significantly reduce the experimental time and quantify the entropy coefficient over the full SoC window, leading to higher fidelity battery thermal models. In this work, the dynamics between the OCP and cell temperature are exploited via system identification techniques to derive the entropy coefficient. This is achieved by estimating the underlying kernel function between the cell OCP and temperature dynamics. The kernel function is a non-parametric estimate of the dynamics from which the entropy coefficient can be determined.

In this work temperature signals are designed with multiple frequency components and applied to a cell via Peltier elements. The corresponding OCP response is then analysed, in the frequency domain, to estimate the kernel function. Unlike the potentiometric method, which drives the battery to steady-state and necessitates long experimental durations, the kernel function can be estimated under transients, facilitating faster characterisation. The figure demonstrates comparable results of the entropy coefficient, over the full SoC interval, when estimated via the kernel function and the potentiometric approach. The approach, compared to the potentiometric method, however, brings around a two to three times reduction in experimental time per SoC and gives insight into the OCP and temperature dynamics. The signal design, kernel estimation and entropy coefficient estimation procedures are detailed in this talk.

Schmidt, J. P., Weber, A., et al., Electrochimica Acta
2014, 137, 311-319. DOI 10.1016/j.electacta.2014.05.153

Figure 1
Cell to Pack Modelling of Li-Ion Batteries for Electric Vehicle Applications: Development and Potential Challenges
Authors: Rashid Muhammad , Zhu Tao , Atalay Selcuk , Saniee Nessa Fereshteh , Dinh Truong , McGordon Andrew
Published: February 2024

Electric vehicles (EVs) and hybrid electric vehicles (HEVs) which are powered by Li-ion batteries (LIBs) have the potential to address the challenges of reducing the dependence on fossil fuels and environmental pollution caused by the transportation sector. However, for the reliable and safe operation of the EVs and HEVs, an accurate estimation of the state of charge (SOC) and state-of-health (SOH) of the battery pack is required. The battery capacity degrades with cycling and calendar ageing over time and usage of the vehicles, which reduces the power capability and driving range of the vehicle. An accurate prediction of the battery SOC and SOH can assist the vehicle user in planning to reach the next charging station or the destination with enough range left before the battery gets fully discharged, hence avoiding annoying circumstances.

Battery models have been widely employed in battery health and SOC prediction and can successfully predict the SOC and SOH of individual cells. However, the translation of these models from cell to pack levels adds several unknown critical factors which affect the model prediction capability significantly.

Our proposed ECM model is based on the electrical and thermal behavior of individual cells, and it accounts for critical factors such as cell-to-cell variations, temperature gradients, and aging effects. We also incorporate a series-parallel configuration to simulate the behavior of multiple cells at the module and pack levels. By upscaling the model in this way, we can accurately predict the SOC and SOH of the entire battery pack, and provide reliable estimates of the remaining driving range and charging requirements.

We anticipate that our proposed ECM model will significantly improve the accuracy of SOC and SOH predictions, which will enable EV/HEV users to better plan their trips, avoid unexpected battery failures, and improve the safety of EV/HEV batteries. Furthermore, our study has the potential to inform the design of future battery technologies and contribute to the transition toward sustainable transportation powered by clean energy sources.
(Invited) Understanding the Interplay between Thermal and Electrochemical Phenomena in Li-Ion Cells through in-Situ Diagnosis
Authors: Zhang Guangsheng
Published: February 2024

The interplay between thermal and electrochemical phenomena in Li-ion cells dramatically influence their performance, durability, and safety. Due to the non-homogeneous compositions and anisotropic properties of Li-ion cell components, the electrochemical reactions, heat generation, and temperature distributions in Li-ion cells are generally non-uniform. Such non-uniform distributions are especially problematic for large-format Li-ion cells under extreme conditions such as low-temperature/high-temperature operation, fast charging/discharging, and internal short circuit (ISC). Conventional methods of monitoring cell voltage, surface temperatures and external current are unable to accurately capture internal behaviors of Li-ion cells under such extreme conditions, which hinders understanding of the interplay between thermal and electrochemical phenomena. In comparison, measurement of critical internal parameters, such as local temperatures and local currents through in-situ diagnosis, can provide detailed data for insightful understanding of the coupled phenomena. Our progress on this topic in recent years will be presented and discussed.
(Invited) On the Role of Thermo-Electrochemical Coupling in Li-Ion Batteries
Authors: Kingston Todd A. , Pint Cary L. , Carter Rachel Elizabeth , Love Corey T. , Ishtiaque MD Mahdi UL , Harkaway Andrew , Ramamurthy Jayanth R.
Published: February 2024

Li-ion batteries have revolutionized a wide range of industries, from consumer electronics to vehicles. Their relatively high power and energy density and exceptional Coulombic efficiency are particularly advantageous for portable applications. Significant efforts have gone into studying the impact of thermal conditions on the electrochemical characteristics of Li-ion batteries because, in part, of the wide range of temperatures these devices are operated in. Recently, we have shown that thermo-electrochemical coupling in Li-ion batteries is of critical importance. In this talk, we will highlight some of our recent work that measures the local thermal conditions within the cell using embedded instrumentation and illustrates how significant thermal variations within the cell, specifically thermal gradients, are on electrochemical behavior. Moreover, we will discuss our efforts to pinpoint the underlying mechanisms that give rise to these effects.

Acknowledgments:

The authors thank Dr. Michele Anderson (Office of Naval Research, grant N00014-22-1-2411) for financial support of this work.
(Battery Division Early Career Award Sponsored by Neware Technology Limited) Towards Scalable and Sustainable Battery Recycling for Circular Energy Storage
Authors: Chen Zheng
Published: February 2024

The development of electric vehicles (EVs) and grid storage heavily relies on lithium-ion batteries (LIBs) that exhibit significantly improved performance, low cost, a reduced carbon footprint, and an abundance of resources. However, the growing consumption of LIBs has led to concerns regarding resource scarcity and price hikes for lithium and critical transition metals (such as Co and Ni) that are essential for LIB production. Currently, the recycling industry utilizes pyrometallurgical and hydrometallurgical processes to treat spent batteries. Although these methods are scalable, there is a pressing need for enhanced overall energy efficiency, reduced processing costs, and minimized environmental impact.

Next-generation technologies, such as direct recycling, hold promise as a more cost-effective and energy-efficient alternative. However, the scalability of these approaches must be proven at an industrial scale. This presentation aims to delve into the state-of-the-art LIB battery recycling by comparing various technologies. In particular, we will extensively discuss the technical aspects of direct recycling, focusing on different LIB materials. Furthermore, we will address the key challenges and provide insights for the future development of LIB recycling.
High-Capacity, High-Rate Nanosized Bismuth-Antimony Embedded in N-Doped Carbon Matrix Via Facile Pyrolysis As Anodes for Advanced Li Storage
Authors: SUN CHI Rong , Mohd Sarofil Anith Dzhanxinah , Devina Winda , Kim Jaehoon
Published: February 2024

Antimony (Sb) is an attractive anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity (660 mAh g–1). Nevertheless, it suffers from huge volume expansion and severe particle pulverization during lithiation/delithiation processes, which leads to poor cycling performance. Herein, to address this matter, a composite of bismuth-antimony alloy nanoparticles embedded in N doped-carbon coating (BiSb@NC) is fabricated via a simple pyrolysis method. The design of bimetallic Bi-Sb solid solutions is possible at any molar ratio. The coupled pair, metallic Bi itself, does not only provide high volumetric capacity (3765 mAh cm–3) and low working potential (0.8 V hereafter vs. Li+/Li) but could also synergistically buffer the volume fluctuation due to the different working potentials between the two alloys. Nanosized BiSb alloys can enhance the reaction kinetics through shortened Li+-ion diffusion pathways. Additionally, the N-doped carbon coating also effectively cushions the volume changes of BiSb and maintains effective conductive networks during extended alloying/dealloying reactions with Li+ ions. As a result, the BiSb@NC anode achieves a high reversible capacity of 550 mA h g–1 after 100 cycles at 100 mA g–1 and superior high-rate performance of 350 and 220 mA h g–1 at 2 and 5 A g–1, accordingly despite its high BiSb loading (82 wt%).
(Digital Presentation) Unraveling of the Morphology and Chemistry Dynamics in the FEC-Generated Silicon Anode SEI across Delithiated and Lithiated States
Authors: Yao Koffi , Mou Rownak Jahan , Barua Sattajit , Abraham Daniel P.
Published: February 2024

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ~350% volume expansion of Si which leads to shortened cell life during electrochemical cycling. Understanding the SEI morphology/chemistry and more importantly its dynamic evolution from delithiated and lithiated states is paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the effects of FEC on the dynamics of the resulting SEI may provide hints toward engineering the Si interface. Herein, ATR-FTIR, AFM, tip IR, and XPS probing all show pronounced relative invariance of the FEC-generated SEI compared to the FEC-free SEI between adjacent lithiated and delithiated states beyond the formation cycles. The SEI of Si thin film model surfaces in the baseline 1 M LiPF6 in EC:EMC (1:1) undergoes major morphological and chemical speciation swings between half-cycles while comparatively the SEI upon addition of FEC displays far less dynamic evolution. This morphology and chemistry stability of the FEC-SEI supports the enhanced cycling stability of silicon anodes in FEC-containing electrolytes. The experimental evidence gathered suggests that the FEC-SEI invariance is enabled by an elastomeric polycarbonate matrix that preserves the SEI integrity against the expansion of silicon upon lithiation. In turn, less electrolyte-consuming reconstruction occurs which manifests as and high LiF content from one half-cycle to the next. This work provides critical insights to enhance the silicon anode stability via targeted SEI engineering, namely that LiF protected by an elastomeric protective matrix may be key to buffering the unavoidable mechanical disruption.

Figure 1
Elucidation of Electrochemical Performance of Few-Layered Graphene As Aluminium Battery Cathode Material: Effect of the Common O and S Impurities
Authors: Petnikota Shaikshavali , DOS Reis Glaydson , Kayakool Fathima ALI , Srikanth Vadali Venkata Satya Siva , Välikangas Juho , Lassi Ulla , Thyrel Mikael
Published: February 2024

Of late, few-layered graphene (FLG) is being tested as an efficient aluminum battery (AB) cathode material. FLG is typically prepared by reducing and exfoliating graphene oxide (GO), commonly prepared by wet-chemical methods. Therefore, FLG is bound to have impurities (commonly O and S). Consequently, it is crucial to study the influence of the S and O impurities in FLG on its performance as an AB cathode material. To conduct such a study, we considered FLG prepared by exfoliating GO using microwave irradiation. The considered FLG has O and S impurities (bonded to C atoms in FLG), collectively weighing 2.9 – 4.7 at.% (4.1 – 6.9 wt.%). The considered FLG as a cathode material in AB pouches delivered stable discharge capacities of around 100 mAh/g at 0.1 A/g current rate over 500 cycles and high irreversible capacities for the first few cycles. The effect of the O and S impurities was negligible when the FLG was cycled at 1.0 A/g, but initial energy storage capacities and cyclic behavior varied with the voltage window. However, the storage capacities at the end of 10000 cycles are similar, irrespective of the voltage window. Overall, the O and S impurities in FLG lead to initial high irreversible capacities, ruling out the commercial use of FLG. We therefore recommend careful characterization of O and S impurities (and any such impurities) before reporting FLG-related materials as AB cathode materials. Removing these impurities will help FLG outperform its class of materials because it shows excellent rate capability with excellent discharge capacities at a high current density of 5 A/g, even with O and S impurities.
Development of High Electrochemical Performance-Reliability TiO2 Nanoparticle-Mulberry Paper Based Supercapacitor
Authors: Lee Seonghun , Yoon Hyungsub , Yun Tae Gwang
Published: February 2024

The paper-based energy storage systems with lightweight, thin and large scalability have been attracted much attention in the field of next generation research. Along with the advantages of these papers, they have excellent flexibility and wettability, so they have high power density even under mechanical bending and twisting deformation, making them suitable for wearable devices. However, conventional paper has limited electrochemical stability due to its low chemical resistance and decomposition in organic or acidic electrolytes.

Mulberry paper can be an outstanding alternative for overcoming the limitations of conventional paper-based energy storage systems. Mulberry fibers form a stronger mechanical network and are longer than conventional paper fibers, so they have excellent chemical strength. Therefore, in this study, a supercapacitor with high electrochemical performance and reliability was produced based on mulberry paper.

As high electrochemical performance active materials, TiO2 nanoparticle and graphene oxide nanocomposites were used. A TiO2 nanoparticle was coated on a mulberry paper substate, graphene oxide was coated, and heat treatment was performed at 700℃ under nitrogen atmosphere for 3 hours. Mulberry paper was carbonized to increase areal energy density. It was strongly fixed by the reduced graphene oxide to maintain the flexibility of carbonized mulberry paper and prevent the delamination of the TiO2 nanotube without protection layer.

Therefore, it is suitable for wearable energy storage systems because it can maintain excellent charge-discharge cycle reliability and flexibility carbonized mulberry paper by improving areal energy density from carbonized mulberry paper and metal oxides and preventing the delamination of the metal oxide.
NMC811 Electrodes with High Mass Loadings Enabled By Non-Solvent Induced Phase Inversion
Authors: Weijers Mark , Karanth Pranav , Ombrini Pierfrancesco , Ripepi Davide , Ooms Frans , Mulder Fokko M.
Published: February 2024

Higher energy density Li-ion batteries that can enable longer driving ranges are currently subject to intensive research interest. Increasing the thickness of electrodes and reducing the proportion of inactive components per cell is one way to achieve this. In thick electrodes, a higher electronic and ionic overpotential and mechanical failure (cracking, delamination etc.) induced by binder migration during the drying process leads to sluggish (dis)charge performance or even cell failure respectively. Here we report non-solvent induced phase inversion as a scalable, effective method to arrive at thick NMC811 electrodes.

By tuning the non-solvent properties and other processing conditions to be compatible with Ni-rich electrodes, it was possible to obtain NMC811 electrodes with mass loadings up to 11 mAh/cm2 (single sided) which outperform their conventional processed counterparts in Li/NMC half cells. This improvement could be attributed to the altered carbon-binder structure, which improves the pore connectivity and lowers the electrode tortuosity factor. The rapid solvent removal also reduces the long-range binder migration during drying. With imaging and porosimetry techniques we show the structural change which leads to the observed improved electrochemical performance. The method also shows good compatibility with double sided slot-die electrode coating procedure, making this a technique with potentially high industrial feasibility towards making thicker NMC811 and other electrodes.
Highly Conformal Solid Electrolyte for Li-Ion Batteries By Atomic Layer Deposition
Authors: Madadi Milad , Heikkinen Mari , Philip Anish , Karppinen Maarit
Published: February 2024

Lithium phosphorus oxynitride (LiP
x
O
y
N
z
, commonly known as LiPON) is a state-of-the-art solid electrolyte material with suitably low resistivity and high ionic conductivity for all-solid-state thin-film microbatteries [1,2]. Thin and pinhole-free layers of LiPON can be fabricated using atomic layer deposition (ALD) [3]. Uniquely among thin-film fabrication methods, ALD is a technique that works for coating even challenging 3D interfaces [4,5]. In this work, LiPON ALD processes were optimized for two different lithium precursors at reasonable temperatures (~300 °C) and precursor pulse/purge lengths (< 5 s), and LiPON films were deposited onto PillarHall® lateral high-aspect-ratio (LHAR) test structures to investigate the conformality of the material. Comparative testing was performed between the two lithium precursors.

The results indicated that more conformal LiPON films can be deposited using the appropriate precursors – in this case, lithium tert-butoxide (LiO
t
Bu) yielded greater penetration depths than lithium hexamethyldisilazide (Li-HMDS). The improved conformality observed when using LiO
t
Bu indicates that this precursor is a better choice for LiPON coatings on high-aspect-ratio structures. The ALD technique allowed for the deposition of highly conformal LiPON films, ~50–115 µm deep into 100–500 nm gaps. This opens possibilities for the use of LiPON as a solid electrolyte in batteries with high-surface-area electrodes. High surface areas are important not only for unlocking higher power densities (faster charging and discharging) in batteries, but also for enabling the use of thin-film technology in fabricating microbatteries with meaningful energy storage capacities.

References

[1] LaCoste, J. D.; Zakutayev, A.; Fei, L. A Review on Lithium Phosphorus Oxynitride. J. Phys. Chem. C
2021, 125, 3651–3667.

[2] Oudenhoven, J. F. M.; Baggetto, L.; Notten, P. H. L. All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts. Adv. Energy Mater.
2011, 1, 10–33. https://doi.org/10.1002/aenm.201000002.

[3] Nisula, M.; Shindo, Y.; Koga, H.; Karppinen, M. Atomic Layer Deposition of Lithium Phosphorus Oxynitride. Chem. Mater.
2015, 27, 6987–6993.

[4] Oudenhoven, J. F. M.; Baggetto, L.; Notten, P. H. L. All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts. Adv. Energy Mater.
2011, 1, 10–33.

[5] Xia, Q.; Zan, F.; Zhang, Q.; Liu, W.; Li, Q.; He, Y.; Hua, J.; Liu, J.; Xu, J.; Wang, J.; Wu, C.; Xia, H. All-Solid-State Thin Film Lithium/Lithium-Ion Microbatteries for Powering the Internet of Things. Adv. Mater.
2023, 35, 1–48.

Figure 1
Enhancing Carbon Fiber Properties through Lignin-Cellulose Composites: A Comparative Study of Hardwood Vs. Softwood Lignin Sources
Authors: Rajaras Azega , Bengtsson Jenny , Theliander Hans , Lundgren Per
Published: February 2024

Carbon fibers are integral to a wide range of applications, including automotive, construction, packaging, textiles, and emerging fields such as energy storage electrodes like flexible supercapacitors. However, concerns related to limited availability and environmental impact associated with fossil-based carbon fiber production have sparked growing interest in sustainable alternatives, particularly those derived from lignin and cellulose composites. This conference work presents a comparative analysis of the mechanical properties of lignin-cellulose composite carbon fibers derived from hardwood and softwood lignin sources, elucidating the significant influence of lignin origin on fiber performance.

Our study focuses on the advantages and disadvantages of utilizing a composite of hardwood lignin vs. softwood lignin with cellulose in carbon fiber production, comparing these materials to commercially available carbon fibers. We emphasize the mechanical performance of these composite fibers, specifically highlighting the tensile strength and tensile modulus as a key metric. Notably, our results demonstrate that carbon fibers derived from hardwood lignin/cellulose composites exhibit superior mechanical strength compared to those from softwood lignin/cellulose composites. To gain fundamental insights into the reasons behind this mechanical disparity, we employed Raman spectroscopy to analyze the carbon structures within the fibers. Our findings revealed that carbon fibers produced from hardwood lignin exhibited a higher degree of graphitization, helping in achieving of typically desirable pre-graphite turbostractic carbon structures. These structural enhancements significantly contributed to the improved mechanical characteristics observed. In summary, our research underscores the critical importance of lignin source selection in the production of lignin-cellulose composite carbon fibers. The mechanical performance of these fibers is closely linked to the carbon morphology influenced by the lignin source. Therefore, understanding and controlling the lignin source from hardwood or softwood is pivotal for tailoring carbon fiber properties to meet specific application requirements. This study not only advances the knowledge in sustainable carbon fiber production but also offers valuable insights into achieving desirable properties for a wide range of applications, including advanced energy storage systems and structural materials.
Borate-Coated Co-Free LiNi0.5Mn1.5O4: Enhanced Performance and Stability for High-Power-Density Libs
Authors: Nisar Umair , Bansmann Joachim , Wohlfahrt-Mehrens Margret , Axmann Peter
Published: February 2024

Cobalt free LiNi0.5Mn1.5O4 (LNMO), also known as high-voltage spinel, has emerged as a promising cathode material for high energy-density and high power-density lithium-ion batteries (LIBs), making it a viable candidate for applications in large-scale energy storage systems (ESS) and transportation (1-5). Despite its potential, LNMO faces challenges, such as rapid capacity degradation and the formation of an unstable cathode electrolyte interphase (CEI), which have impeded its commercialization(4-5). To address these issues, we present a cost-effective and scalable approach involving the application of a borate-based surface coating to LNMO (borate-LNMO). In this study, we systematically applied varying amounts of borate coating to LNMO and assessed their electrochemical performance in both half- and full-cell configurations. Initial optimization of the coating amount revealed that borate-LNMO materials exhibited superior rate capability, and enhanced stability when compared to bare LNMO. Float testing demonstrated a stable LNMO/electrolyte interface for borate-LNMO materials, in contrast to the continuous increase in leakage (parasitic current) observed with bare LNMO over time. Furthermore, borate-LNMO materials exhibited superior cycling performance in full-cell setups, both at ambient (25℃) and elevated (45℃) temperatures. This enhanced performance can be attributed to the formation of relatively stable CEI and SEI interphases, resulting in reduced electrolyte decomposition, lower transition metal dissolution at the LNMO/electrolyte interface, and minimized cross-talk between the cathode and anode. Post-mortem SEM analysis of the cycled graphite anodes revealed a thicker and denser SEI in bare LNMO cells, whereas borate-LNMO cells exhibited a thinner and porous SEI. These findings suggest that borate-coated LNMO could be a promising solution for cost-effective and high-power LIBs.
Polarization Reduction of a Novel Cell Configuration Based on Thin-Film Electrolyte on Porous Oxide Framework for Solid State Batteries Application
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Jimenez Ricardo , Calzada Lourdes , Sobrados Isabel
Published: February 2024

In early 1990s, rechargeable Li batteries using inorganic ionic conductors as solid electrolytes have been proposed. Because of their improved safety features, solid state batteries have received great attention recently. Although using Li metal as an ideal high-capacity anode has been a long-term goal, the critical issues remaining to be solved are the polarization contributed from the solid electrolyte and the electrode/electrolyte interface. Thus, to form a Li-conducting thin film with good adhesion with an adequate conducting and porous oxide framework in between Li anode and thin electrolyte may be a solution for the reduction of above-mentioned polarization observed in the solid state batteries. Thus, the main objective of this study is to (i) calculate/estimate the polarization reduction in a solid state cell using thin-film inorganic electrolyte and metallic Li as anode, (ii) to complete the experimental design for in-situ formation of thin electrolyte based on sol-gel deposition of an oxides precursor on a porous and conducting oxide framework followed by heat-treatment at temperatures > 700°C. The verification of polarization reduction contributed from the proposed thin-film electrolyte as well as the porous/conducting framework will be carried out in the near future.
Investigating Charge Transfer Mechanisms at Graphene-Electrolyte Interfaces for Enabling Rechargeable Li-CFx Batteries Via Electrochemical Fluorination
Authors: Pu Jiankun , Viswanathan Venkatasubramanian
Published: February 2024

Li-CFx batteries are a promising high energy density option for wider electrification of the transportation sector, but limited rechargeability remains a major challenge. In this study, we explore electrochemical fluorination of graphene as a potential solution and build a mechanistic understanding of this process. Specifically, we investigate the charge transfer mechanisms at the graphene-electrolyte interfaces during fluorination, which is a key component for enabling rechargeability. We employ density functional theory and molecular dynamics simulations to examine the effect of electrode surface morphology, electrolyte composition, and temperature on the thermodynamics and charge transfer kinetics. We explore the role of electron and ion hopping mechanisms in charge transfer and evaluate the influence of surface defects and adsorbates on the charge transfer rate. Our findings provide important insights into the fundamental mechanisms governing charge transfer at graphene-electrolyte interfaces and can guide the design of the electrochemical fluorination process of graphene for enabling rechargeable Li-CFx batteries. This work represents a critical step towards achieving the next milestone in the wider electrification of the transportation sector.
Microelectrode Set Made of Carbon Nanotubes for the Detection of Biomolecules and Neurotransmitters
Authors: Alvarez Noe T , Gupta Pankaj
Published: February 2024

Electrode miniaturization is an alternative path for the development of sensitive electrochemical sensors. The low charging current, enhanced mass transport and their suitability to be employed in resistive mediums has made microelectrodes attractive for detection of biomolecules. Carbon nanotubes (CNTs) are unique nanomaterials with high electrical conductivity and mechanical strength. They are known for their chemical stability and the ability to assemble them into nano and microelectrodes makes them an appealing alternative electrode material compared to metals. This talk will report the fabrication of an electrochemical-set that has CNT microelectrode assemblies as working, reference, and counter electrode components and have been tested for the detection of heavy metals (Pb2+), neurotransmitters (dopamine), and other biomolecules (nicotinamide adenine dinucleotide (NADH), furosemide). Limits of detection of 0.5 nM for dopamine, 18 nM for NADH, 2 nM for Furosemide, and 0.4 ppt for Pb2+ have been achieved. Different voltammetric techniques were employed during the study: cyclic voltammetry (CV), square wave voltammetry (SWV), amperometry, and square wave anodic stripping voltammetry (SWASV). The robustness of the electrodes and the simplicity of its fabrication have been demonstrated. Furthermore, a simple method for the fabrication nanoelectrode arrays that can be employed as working electrodes will be presented. The background and key components that are considered important to achieve this performance will be reported.
(Invited) Directed Evolution and Machine Learning for Improved ssDNA-SWCNTs Sensor for Nitric Oxide Detection
Authors: Sajjadi Sayyed Hashem , Rabbani Yahya , Behjati Sara , Zubkovs Vitalijs , Cattaneo Stefano , Basoli Valentina , Grad Sibylle , Boghossian Ardemis Anoush
Published: February 2024

Single-walled carbon nanotubes (SWCNTs) show great potential for biosensing applications due to their unique optical properties. SWCNTs emit fluorescence in the near-infrared (NIR) region that is stable, biotransparent, and highly sensitive to changes in their environment. The biocompatibility and the selectivity of their interactions can be engineered through SWCNT surface functionalization. One of the most common functionalization approaches is the non-covalent wrapping of SWCNTs with single-stranded DNA (ssDNA). Though the ssDNA sequences can be varied to control the optical response of these SWCNT sensors, the dependence of the optical response on the sequence is unknown and unpredictable. This lack of information on the relationship between the ssDNA sequence and sensor performance is a major bottleneck in engineering SWCNT-based optical sensors.

In this work, we develop a guided approach to engineer optical ssDNA-SWCNT sensors. Using a combination of machine learning and directed evolution[1], we designed an optical sensor for nitric oxide (NO), a pro-inflammatory mediator that induces inflammation[2]. We demonstrate a 7-fold enhancement in sensor response compared to the state-of-the-art sensor based on the (AT)15 sequence[3]. This approach thus provides a powerful means of overcoming existing bottlenecks in SWCNT sensor design, ushering a new generation of near-infrared technologies for biomedical research and clinical diagnostics.

References

[1] B. Lambert, A. J. Gillen, N. Schuergers, S. J. Wu, A. A. Boghossian, Chem. Commun.
2019, 55, 3239.

[2] J. N. Sharma, A. Al-Omran, S. S. Parvathy, Inflammopharmacology
2007, 15, 252.

[3] J. Zhang, A. A. Boghossian, P. W. Barone, A. Rwei, J. H. Kim, D. Lin, D. A. Heller, A. J. Hilmer, N. Nair, N. F. Reuel, M. S. Strano, J. Am.
Chem. Soc.
2011, 133, 567.
Polyhydroxy Fullerene for Synthesizing Noble Metal Nanoparticles
Authors: Krishna Vijay , Xu Yue , Williams Roberts
Published: February 2024

The redox properties of fullerene and its derivatives enable them to function as electron relays through either oxidation or reduction. Polyhydroxy fullerene (PHF), also known as fullerol or fullerenol, is highly water-soluble derivative and a well-known antioxidant. We have found that PHF is also very effective in reducing noble metal precursors and stabilizing metal nanoparticles by forming covalent M-O bonds.

Traditionally, noble metal nanoparticles, such as gold are synthesized using a reducing agent like sodium borohydride (NaBH4) or sodium citrate at elevated temperatures and alkaline pH, with stabilizers added during nucleation to control the size and dispersion of the nanoparticles. While sodium citrate is sometimes used as a single reducing and stabilizing agent, it is not an effective stabilizer and is often replaced with polymers to improve colloidal dispersion. In contrast, PHF can be used as a single reducing and stabilizing agent for metal nanoparticles. The nanoparticles were synthesized by simply mixing the metal precursors with PHF in an aqueous phase and stirring at room temperature. The size and morphology of synthesized nanoparticles were characterized with high-resolution transmission electron microscopy, aberration corrected TEM, and dynamic light scattering. These nanoparticles were monodisperse with size ranging from 2 nm to 100 nm in diameter, which could be controlled by changing the concentration of the two reactants. We utilized multiple tools to investigate the mechanism of reduction and nanoparticle formation. We propose a kinetic agglomerate-dissociation mechanism to describe the formation of gold nanoparticles using PHF. Kinetic agglomerates form instantaneously upon mixing the two reactants due to electrostatic interactions. During the reduction process reactive carbonyl peaks were observed with electron energy loss spectroscopy. The carbonyl moieties were observed only after agglomerate formation and subsequently changed to Au-O bonds between PHF and synthesized gold nanoparticles, which was confirmed with Fourier-transform infrared spectroscopy and density-functional theory calculations, and X-ray photoelectron spectroscopy. Further, we demonstrated that the synthesis of gold nanoparticles using PHF can be affected by pH due to changes in hemiketal structure of PHF. Compared to citrate ions, PHF-coated gold nanoparticles are more stable, remaining so for over two years.

The novel PHF-mediated synthesis method can also be applied to other noble metals like platinum, palladium, and silver and create bimetallic nanoparticles. The surface PHF coating on noble metal nanoparticles integrates the properties of both metal and carbon nanoparticles, resulting in superior functional applications. Our findings open up new opportunities for metallic nanoparticle preparation methods, properties, and applications.
Doping Graphene By Physisorption to Influence Electrochemical Activity and Probing Local Electrochemistry on 10 Micron Spots
Authors: Saraf Ravi , Lim Jay Min , Saraf Akshat , Korlacki Rafal
Published: February 2024

Graphene as an electrochemical electrode for energy devices and catalytic activity is a catch 22 situation. Pristine graphene is highly conducting with exquisite chemical inertness to avoid poisoning of the electrode surface. However, this inertness leads to poor chemisorption which is generally considered a prerequisite for electron transfer during redox. Thus, pristine graphene is a poor electrochemical electrode. The challenge is being addressed by distorting the perfect sp2 structure by interfacing with other 2D materials to form (complex) heterostructures, and/or doping other atoms or punching holes (i.e., vacancies). However, chemical stability, i.e., inertness, becomes vulnerable at the defects. Here we propose a concept of “doping” where the graphene becomes electrochemically active, and the pristineness is maintained. The dopant is physiosorbed to the graphene. The outcome will be a redox active graphene electrode. DFT simulations are conducted to explain the structure.

The electrochemical behavior will be studied by a special opto-electrochemical method called the Scanning electrometer for Electrical double-layer (SEED). SEED quantitively measures local electrochemistry on a 10-micron spot to avoid edge effect and (potential) cracks in graphene.

Figure 1
Exploring Fullerene-Perovskite Interactions by Means of Density Functional Simulations
Authors: Posada Perez Sergio , George Gibu , Poater Albert , Solà Miquel
Published: February 2024

Boosting renewable energies is the 7th goal in the 2030 Agenda for Sustainable development whose premise is to accelerate the transition towards a low-carbon competitive economy. Sunlight is the largest exploitable resource of energy and it has promoted an extraordinary growth of photovoltaic (PV) cell technology to supply the demand. Several PV manufacturers are now working on bringing solar cell devices based on organic-inorganic hybrid perovskite (PSCs) to market due to their easy fabrication procedures, low cost, and the fast improvement of their efficiency (PCE).

In order to enhance the possibility for PSCs to be competitive throughout the market, a very recent technology introduces Fullerene (C60) and its derivatives -specially [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)- in PSC devices to work as electron transport layer (ETL), additives, or to control the crystal growth, either in conventional or inverted devices. The use of fullerenes have eliminated/reduced the hysteresis,[1] improved the device stability in comparison to fullerene-free standard PSCs,[2] and favors the high-scale preparation because the high-temperature step.

Nevertheless, important features in the state-of-the-art fullerene-perovskite devices remain unexplored. It is known that fullerenes passivate the perovskite defects, improving the optoelectronic properties, but it has not been systematically explored to date. It is not extensively investigated the effect of binding groups of fullerenes, how fullerenes passivate the perovskite surfaces and how passivation influence surface energetics and the corresponding carrier dynamics. In this work we use periodic density functional simulations to explore the interaction of fullerenes with different perovskite surfaces, considering as well possible defects (Iodide anti-sites) and vacancies (cation vacancies). Computing the binding energy, the adsorption energy site, bandgaps, and density of states we are able to compare these relevant descriptors with the experimental efficiency, in order to find the key descriptors that govern the fullerene-perovskite interactions. In this presentation, we will show our results for APbI3 (A= methylammonium, Cs) perovskite surfaces with the most common fullerenes like C60 and PC61BM. Our simulations show different binding energies depending on the perovskite and surface vacancy and the effect on the electronic structure will be discussed.

1. J. Xu, et. al., Nat. Commun.
2015,6, 7081; Y. Zhong, et. al., Adv. Funct. Mater.
2020, 1908920.

2. V. Ferguson, et. al., Energy Environ. Mater.
2019, 2, 107–118; T. Gatti et. al., Nano Energy, 2017, 41, 84−100.

Figure 1
Pillared Graphene for Supercapacitor Applications
Authors: Hassan Omar , Franklin Giovanna Formiga , Simon Patrice , Dubois Lionel , Taberna Pierre-Louis , Duclairoir Florence
Published: February 2024

Since the discovery of graphene in 2004 [1], it has been considered a “Wonder” material with lots of potential due to its attractive properties. Owing to such properties, graphene is theoretically expected to have an electrochemical double layer capacitance of 550 F/g [2]. However, due to the high cost and difficulty of producing and handling single sheets of graphene, the presence of graphene in the market was hindered. Luckily, many methods were devised to synthesize graphene-like materials that would be easier and cheaper to produce. Unfortunately such methods end up producing reduced Graphene Oxide (rGO) with stacked graphene layers due to pi-pi interactions, which impedes the full utilisation of the graphene’s surface area. Pillaring the graphene using organic linkers was proven to be one of the useful techniques in partially preventing the restacking of the graphene sheets in rGO [3].

Herein, three molecular pillars with different chemical nature and lengths will be presented as pillaring agents for graphene and the performance of their corresponding pillared graphene assemblies as electrode materials for supercapacitors will be assessed against that of rGO as a reference sample. To assess the success of the pillaring technique and to decipher the chemical composition of the samples, various characterization techniques were employed such as XRD, TGA, XPS, EA, SEM, FT-IR, Raman spectroscopy and conductivity measurements. Different electrolytes were used to test the electrochemical performance in different environments (acidic and neutral with different cation sizes). The pillared graphene assemblies demonstrated an enhanced capacitive performance compared to reference samples and a correlation between such performance and the different physico-chemical characteristics is to be highlighted.

References:

[1] S. Novoselov et al., Science, 306, (2004) 666.

[2] Zhu et al., Small, 10 (2014) 3480

[3] Banda et al., ACS Nano, 13 (2019) 1143.

Figure 1
Graded onset of parasternal intercostal inspiratory activity detected with surface electromyography in healthy young females and males
Authors: Hudson Anna L. , Luu Billy L. , Gandevia Simon C. , Butler Jane E.
Published: February 2024

We demonstrated that surface EMG is a valid method to measure graded inspiratory EMG in the parasternal intercostal muscles in healthy young male and female participants during quiet breathing and loaded breathing. Across the 1st-to-5th interspaces, there was more homogenous activation in women and more graded activity in men across parasternal intercostal muscles during breathing. By recording surface EMG from both male and female participants, we have revealed sex differences in inspiratory activity across intercostal muscles.
The hormonal control of parturition
Authors: Hamburg-Shields Emily , Mesiano Sam
Published: February 2024

Parturition is a complex physiological process that must occur in a reliable manner and at an appropriate gestation stage to ensure a healthy newborn and mother. To this end, hormones that affect the function of the gravid uterus, especially progesterone (P4), 17β-estradiol (E2), oxytocin (OT), and prostaglandins (PGs), play pivotal roles. P4 via the nuclear P4 receptor (PR) promotes uterine quiescence and for most of pregnancy exerts a dominant block to labor. Loss of the P4 block to parturition in association with a gain in prolabor actions of E2 are key transitions in the hormonal cascade leading to parturition. P4 withdrawal can occur through various mechanisms depending on species and physiological context. Parturition in most species involves inflammation within the uterine tissues and especially at the maternal-fetal interface. Local PGs and other inflammatory mediators may initiate parturition by inducing P4 withdrawal. Withdrawal of the P4 block is coordinated with increased E2 actions to enhance uterotonic signals mediated by OT and PGs to promote uterine contractions, cervix softening, and membrane rupture, i.e., labor. This review examines recent advances in research to understand the hormonal control of parturition, with focus on the roles of P4, E2, PGs, OT, inflammatory cytokines, and placental peptide hormones together with evolutionary biology of and implications for clinical management of human parturition.
Saving Energy and High‐Efficient Inspection to Offshore Wind Farm by the Comprehensive‐Assisted Drone
Authors: Huang Xianfei , Wang Gaocai
Published: February 2024

Facing the method’s limitations of the existing drone inspection on offshore wind farms, we adopt a new comprehensive‐assisted drone automated inspection scheme under the comprehensive assistance. Our objectives are saving energy and high‐efficient inspection. The such inspection is used to formulating the two mixed‐integer nonlinear programming problems based on two new drone basic models: the mobile edge computing driven drone computation system model and the drone flight model. To solve the problems, we split them into four subproblems, and a new improved heuristic algorithm is created to address. In turns, the waypoints, total inspection time, inspection energy consumption, and traveling distance of unmanned aircraft vehicle (UAV) and the traveling distance of boat are obtained by K‐means algorithm and the smallest enclosing circle (SEC) algorithm, the Lin‐Kernighan Heuristic 3 (LKH‐3) algorithm, and the LKH. Finally, conducting the comprehensive optimization and simulation, the simulation numeric results are gotten. The simulation results demonstrate that as for the two aspects of the total energy consumption and inspection efficiency under different data amount and average wind speed, the scheme improves at most 44% and 23.5% than the current other three; the scheme achieves the objective of saving energy and high‐efficient inspection.
Role of Probiotics against Human Cancers, Inflammatory Diseases, and Other Complex Malignancies
Authors: Naeem Hammad , Hassan Hammad Ul , Shahbaz Muhammad , Imran Muhammad , Memon Anjuman Gul , Hasnain Ammarah , Murtaza Shamas , Alsagaby Suliman A. , Al Abdulmonem Waleed , Hussain Muzzamal , Abdelgawad Mohamed A. , Ghoneim Mohammed M. , Al Jbawi Entessar
Published: February 2024

Probiotics have growing medical importance as a result of their potential in the prevention and therapeutic support of several complex diseases, including different types of cancers. The anticarcinogenic properties of probiotics are attributed to various mechanisms, including alterations in the composition of the intestinal microbiota, suppression of cell proliferation, stimulation of apoptosis, inhibition of NF-kB, reduction in levels of H2AX, 8-hydroxy-deoxyguanosine, RIG-I, downregulation of IL-17, and TNF signaling pathway. Furthermore, probiotics have demonstrated significant advantages in the prevention and management of other complex diseases, including diabetes, obesity, and cardiovascular diseases. Probiotics had a considerable effect in reducing inflammatory infiltration and the occurrence of precancerous lesions. Additionally, the administration of probiotics led to a decrease in the appearance level of genes related to proinflammatory pathways, including NF-κB, IL-17, and TNF signaling pathways. However, further research studies are required to comprehend the processes via which probiotics exert their effects and to authenticate their potential as alternative therapeutic interventions.