bluuebunny/crossref_metadata_2025_split huggingface dataset:
Investigating Intercalation of Chloroaluminate Anions in Graphene-Based Materials for Rechargeable Aluminum-Ion Batteries
Authors: Yoon Hana , Rezaee Mehdi , Lee Yeong A , Yim Kanghoon , Tamarany Rizcky , Lee Chan-Woo , McGraw Valerie S. , Taniguchi Takashi , Watanabe Kenji , Kim Philip , Yoo Chung-Yul , Bediako Daniel Kwabena 
Published: September 2023

Development of energy storage systems with high energy and power density, high safety, long cycle life, and low cost is crucial for various applications, including portable electronics and grid storage of renewable energies. Among various battery technologies, rechargeable aluminum ion batteries are particularly attractive due to the abundance, low cost, and safety of aluminum. However, unlike lithium ion batteries, many aspects of the fundamental intercalation processes and dynamics in these aluminum-based battery systems remain unresolved.
In this study, we investigate the intercalation of chloroaluminate ions in atomically thin carbon cathodes using mesoscopic devices for charge transport and operando optical microscopy. These measurements provide insights into the energetics and dynamics of intercalation processes in atomically thin samples. We compare the atomically thin single crystal measurements to the cycling response of a high-performance rechargeable aluminum ion battery consisting of a few-layer graphene–multiwall carbon nanotube composite cathode. Our findings show that these nano-composites exhibit a high specific capacity and cyclic stability at high current densities, with a ~3-fold improvement in overall ion diffusivity in the aluminum ion battery. However, the battery cells still exhibit chloroaluminate diffusivities less than ~1% of those in mesoscopic single crystals. Our results highlight the distinction between intrinsic and ensemble electrochemical behavior in aluminum-based batteries and demonstrate that engineering ion transport to enhance diffusivity in these devices can lead to significant improvements in battery performance.
How Cyclic Aging at Different Temperatures Affects Safety of Li-Ion Pouch Cells
Authors: Feinauer Max , Abdellatif Abdelaziz , Sichler Peter , Wohlfahrt-Mehrens Margret , Waldmann Thomas 
Published: September 2023

Li-ion battery safety behavior is critical and should be examined carefully. However, safety testing is typically performed only on pristine cells. This neglects the significant effect of aging conditions, such as ambient temperature, on safety behavior. For example, aging at low temperatures results in Li plating and thus drastically reduces safety [1–3]. Cells aged at higher temperatures with a pronounced solid-electrolyte-interface (SEI) layer on the anode show an increased onset of self-heating leading to improved safety [3,4].
The temperature dependent cyclic aging behavior of commercial Li-ion pouch cells is evaluated using an Arrhenius plot. Further Post-Mortem analyses of aged cells from both branches of the V-shaped Arrhenius plot confirm two dominant aging mechanisms: Li plating and SEI growth for the low and high temperature ranges, respectively.
Heat-wait-seek (HWS) tests under quasi-adiabatic conditions in an accelerated rate calorimeter (ARC) are used to evaluate safety behavior and identify critical temperatures such as the onset of self-heating. Multiple sensors (voltage, resistance, temperature, strain, and ultrasonic transmission) are placed on the pouch cell to provide a better understanding of the processes taking place during HWS tests. These sensors show that some critical events, such as the onset of swelling, venting, or separator melting, are only slightly affected by aging. In contrast, the onset of self-heating depends on the aging mechanism and state of health (SOH) of the cell, as a more pronounced aging has a greater impact on the change in safety. This knowledge can be used, for example, by cell manufacturers to estimate the minimum safety of aged cells based on tests of new cells.

References

[1] T. Waldmann, M. Wohlfahrt-Mehrens, Electrochimica Acta 230 (2017) 454–460. https://doi.org/10.1016/j.electacta.2017.02.036.
[2] A.A. Abd‐El‐Latif, P. Sichler, M. Kasper, T. Waldmann, M. Wohlfahrt‐Mehrens, Batteries & Supercaps 4 (2021) 1135–1144. https://doi.org/10.1002/batt.202100023.
[3] M. Feinauer, A.A. Abd-El-Latif, P. Sichler, A. Aracil Regalado, M. Wohlfahrt-Mehrens, T. Waldmann, Journal of Power Sources 570 (2023) 233046. https://doi.org/10.1016/j.jpowsour.2023.233046.
[4] M. Börner, A. Friesen, M. Grützke, Y.P. Stenzel, G. Brunklaus, J. Haetge, S. Nowak, F.M. Schappacher, M. Winter, Journal of Power Sources 342 (2017) 382–392. https://doi.org/10.1016/j.jpowsour.2016.12.041.

Figure 1
Highly Conductive Solid Electrolytes for Fluoride Battery Application
Authors: Mineshige Atsushi , Sugiura Maiko 
Published: September 2023

Recently, fluoride batteries are attracting attention as electrochemical high-energy-density storage devices. There are various types of fluoride ion conductors such as fluorite-type, tysonite-type, and fluorite-related-type and so on. Among them, MSnF4-type fluorides (M: Pb, Ba) have high ion conductivity, and are good candidates for electrolyte materials to be used in fluoride batteries. Up to now, the highest conductivity among fluoride ion conductors was obtained for PbSnF4 with the fluorite-related-type structure, exhibiting pure and high ion conductivity of 2x10-2 S cm-1 at room temperature. In the present study, BaSnF4 (BSF) was prepared by using mechanical milling (MM) process, and its ion conducting behavior was reinvestigated.
A BSF pellet was prepared via MM process, followed by a thermal annealing at 573 K, and it was found that the pellet was a tetragonal BSF phase. Crystal structure and ion conducting pathway of tetragonal BSF prepared by the MM method could be clarified by the neutron diffraction experiment on the basis of a [−SnBaBaSn−]-layered structure along c axis with three nonequivalent fluorine sites: F1, F2, and F3 [1]. According to an impedance analysis, the fluoride ion conductivity of the obtained BSF pellet was 2.6x10-3 S cm-1 at 298 K. Conductivity decreased after pulverization compared to the original one due to an increase in the grain boundary resistance. However, it was largely improved by compaction higher than 434 MPa. Furthermore, conductivity retrieved by the heating up to 423 K under dry Ar atmosphere, and the conductivity was 2.1x10-3 S cm-1 at 298 K after 607 MPa compaction and heat treatment to 423 K. Therefore, BSF green compact exhibiting high conductivity to be applied to the high performance fluoride batteries could be obtained by suppressing the grain boundary resistance.
This work was supported by the RISING2 (JPNP16001) and RISING3 (JPNP21006) project, NEDO, Japan.
Reference
[1] K. Mori et al., J. Phys. Chem. C 2021, 125, 23, 12568.
Optimized Graphene Hydrogels for Electrochemical Applications from High-Concentration GO/Gnp Dispersions
Authors: Chamberland Joshua P , Sellathurai Andrew J , Parent J Scott , Barz Dominik PJ 
Published: September 2023

As the world combats climate change, energy storage solutions will be required to bridge the gap between the supply and demand of renewable energy sources. Supercapacitors have a higher power density and cyclic stability than batteries, making them more useful for selected applications. These devices utilize high surface area electrode materials, such as graphene, with enough active sites for sufficient ion adsorption to occur. Graphene hydrogels self-assemble via the hydrothermal reduction of graphene oxide (GO) dispersions. These three-dimensional structures have high specific surface areas while avoiding the use of binders. Binders usually negatively impact the conductivity of the material and require the use of conductive additives which lower specific performance data. As such, graphene hydrogels are attractive as a supercapacitor electrode material.
Recently, graphene nanoplatelet (GNP) dispersions stabilized by small amounts of GO were used to form more cost-effective and better-performing hydrogels. Though GO/GNP hydrogels are a suitable alternative to those formed from dispersions of GO, the formulation of this material has yet to be optimized. In this work, we investigate the formation of GO/GNP hydrogels by assessing the influence of several input parameters on the specific surface area and mechanical stability of the hydrogel structure. A set of experiments based on a design of experiments is used. Based on the results, an optimized hydrogel is formed and characterized. Compared to typical hydrogels formed from dispersions of GO, the optimized GO/GNP hydrogel leads to significant improvements in both the specific surface area and conductivity of the material. When used in a supercapacitor, low internal resistance and high stability are observed while volumetric capacitance is increased by up to over 400%.
(Invited) Rapid, Large Area Preparation of Few-Layer Graphene Films Using Xenon Flash Lamp Pyrolysis for High-Performance Structural Micro-Supercapacitors
Authors: Bhardwaj Ayush , Okoroanyanwu Uzodinma , Watkins James 
Published: September 2023

Graphene offers excellent electrical conductivity and very high surface area, which holds great promise for energy storage applications including supercapacitors. Current preparation methods for graphene require relatively long processing times, extremely high temperatures within controlled atmospheres, and/or involve multi-step reactions that present challenges for high throughput fabrication of graphene-based energy storage devices. We report a novel photothermal route to large-scale production of graphene within milliseconds using a commercially available polymers (polybenzoxazine, polyacrylonitrile and polyaniline) and a high intensity xenon flash lamp on various substrates, including carbon fibers, at ambient conditions. The xenon flash lamp provides large-area illumination and a wide emission band (300 nm –1100 nm) that was used to convert the polymeric material directly into few layer graphene upon millisecond exposures. The precursor material is heated to extremely high temperatures in a fraction of a second – a duration that is much shorter than the timescale for thermal equilibrium. This enabled the conversion of the polymeric material into few layer graphene in air and at room temperature, and without thermally damaging the substrate. Conversion to few-layer graphene was strongly dependent on pulse energy and the local temperature which was controlled via pulse power modulation. The obtained graphene composites at optimized conditions exhibited excellent conductivity (0.1 ohm-cm) with ID/IG ratio of 0.3 (Figure 1a). Particularly, graphene derived from polyaniline resulted in the formation of macroporous network (Figure 1b) with good adhesion to the carbon fiber, all of which facilitate the transport of ions through the material. The fabricated supercapacitor devices exhibited a very high areal capacitance of 200 mF/cm2 at 10 mV/s with retention of more than 70% of their capacitance, even at scan rates up to 100 mV/s. Moreover, mechanically, and structurally stable graphene derived from polyaniline on carbon fiber was utilized for the preparation of structural energy storage devices. We assembled symmetric structural supercapacitor comprised of carbonaceous material (carbon fiber and few-layer graphene) and polymer gel electrolyte. This resulted in the preparation of large area device (40 cm2) as shown in the Figure 1c with the capacitance exceeding 2000 mF and almost complete retention of capacitance after 5000 cycles.
The preparation of high-quality graphene via photothermal pyrolysis of polymer is amenable to high throughput processing, enabling large-scale production of high performance structural electrochemical energy storage devices.

Figure 1
Solar Cell Application of 1D Heterostructure Based on Single-Walled CNT
Authors: Qiu Xiyang , Zhang Bowen , Wang Shuhui , Zheng Yongjia , Otsuka Keigo , Xiang Rong , Maruyama Shigeo 
Published: September 2023

The experimental synthesis of one-dimensional (1D) van der Waals heterostructures, first introduced in 2020 [1], has attracted much research attention. Discussions upon this coaxial stack of different atomic layers are not only limited to synthesis and characteristics, but also extended to applications. Many unique properties of the 1D van der Waals heterostructures, such as the adjustable band gap, strong quenching of photoluminescence of MoS2 by inner single-walled CNT, enable this structure to be a potential active layer material for solar cells [2].
For the synthesis of 1D van der Waals heterostructures, we first use dispersed high-purity semiconducting single-walled carbon nanotubes (s-SWCNT) solution obtained from Kataura group [3] as inner tube material. With an anodic aluminum oxide (AAO) membrane filter and HCl, we managed to fabricate a free-standing s-SWCNT film [4]. Then following our established CVD process [5], we are wrapping this inner s-SWCNT tube with an insulating boron nitride layer, and a semiconducting MoS2 layer. After that, the as-prepared 1D van der Waals heterostructures film will be utilized for solar cell fabrication.
The solar cell is adopting an n-i-p structure, in the order of glass-ITO-SnO2-Active layer-Spiro-Au. After spin-coating and annealing SnO2 (electron transporting layer) onto ITO-patterned glass, the 1D van der Waals heterostructure film is laminated on the SnO2 layer. Spiro (hole transporting layer) will be then spin-coated onto the film. Finally, gold is vapor-deposited onto the device in a vacuum chamber, as the top electrode [6].
Through photocurrent measurement of 1D van der Waals structure film using Esko film, a mixture of metallic-SWCNT and s-SWCNT, we found it is photosensitive with exposure to light and laser. The 1D van der Waals structure film using high-purity s-SWCNT is then expected to generate higher photocurrent, the experimental result will be updated in the future. By the IV measurement of the solar cell, we observed the photovoltaic effect of the device. Moreover, this new conceptual solar cell is believed to possess many advantages at the same time, such as flexibility, durability, non-toxicity, and sustainability [2]. However, further research on the choices of materials and optimizations of device parameters is still required in order to reach sufficient power conversion efficiency as a photovoltaic device.
[1] R. Xiang et al., Science
367, 537–542 (2020)
[2] R. Xiang et al., Natl Sci Open
1, 3 (2022)
[3] J. Cui et al., ACS Appl. Nano Mater
2, 1, 343–350 (2019)
[4] C. Zhang et al., ACS Nano
16, 11, 18630–18636 (2022)
[5] M. Liu et al., ACS Nano
15, 5, 8418–8426 (2021)
[6] J.-M. Choi et al, Adv. Funct. Mater.
32, 2204594 (2022)
Real-Time Macrophage Phenotype Identification Using Single Walled Carbon Nanotubes and Machine Learning
Authors: Nadeem Aceer , Roxbury Daniel 
Published: September 2023

Macrophages play a critical role in the immune system, as both pro and anti-inflammatory immune cells these are the first line of defense from foreign bodies. Although methods for identifying Macrophage Phenotype (M1, M2) currently exist, these methods are limiting to factors like time, cost, operational training, and sample size. Cost and time effective identification of macrophage phenotypes can not only lead to better therapeutic research but also help in creating a platform for real time monitoring of the wound healing process as well as other (macrophage related) disease progression.
Single Walled Carbon Nanotubes are ideal optical biosensors due to their intrinsic near-Infrared (nIR) emission, which is highly sensitive, easily tunable and indefinitely photostable. Due to such desirable properties, non-covalent functionalization of these fluorescent nanotubes has resulted in them being used as in vitro and in vivo sensors for numerous applications. Even so, the full extent of nanotube applicability is yet to be explored due to their underdeveloped potential as next generation bioimaging and bio-sensing probes. Here we demonstrate a platform using DNA functionalized Single Walled Carbon Nanotubes and machine learning to identify macrophage phenotype with 99% accuracy and effectively estimate the number of each polarization state in a sample.
Optical Nanosensors for the Detection of Quaternary Ammonium Compounds
Authors: Dewey Hannah , Sultana Nigar , Budhathoki-Uprety Januka 
Published: September 2023

Quaternary ammonium compounds (QACs) are common active ingredients in chemical disinfectants, household cleaners, cosmetics, pesticides, etc. Recently QACs have been detected in human blood and breast milk during the COVID-19 pandemic. Humans can be exposed to QACs through dermal adsorption during application, hand-to-mouth ingestion of disinfectant residues, and inhalation of indoor air upon treatment with disinfectant spray. Exposure to these chemicals can cause respiratory illness such as asthma and chronic obstructive pulmonary disease, increase inflammatory cytokines, decrease mitochondrial function, and disrupt cholesterol biosynthesis. However, the complete biological fate of QACs is currently unknown. Therefore, a real-time continuous monitoring system in complex biological environments is crucial to learn the long-term effects of QACs on human health.
Photoluminescent single-walled carbon nanotubes (SWCNTs) are great candidates for developing optical probes to monitor biological systems due to their outstanding photophysical properties in the tissue-transparent near-infrared spectral region, high sensitivity, and high stability. Furthermore, nanotube-based sensors exhibit a great potential for an implantable, real-time, wireless optical detection technology. Herein, we developed a carbon nanotube-based optical sensor for the detection of QACs in complex solution. Our findings from this research could provide a basis for engineering an optical detection technology to gain insight on the long-term effects of QACs to human health.
(Invited) Bio-Applications of Carbon Nanotubes for NIR Imaging Probes and Guided Bone Regeneration Membranes
Authors: Okazaki Toshiya 
Published: September 2023

Single-walled carbon nanotubes (CNTs) have been expected for biological and medical applications because of their unique optical and chemical properties. One of the promising applications is imaging probes because CNTs show fluorescence in the near-infrared (NIR) region, which is highly transparent for biomaterials. We have reported the synthesis method of the epoxide-type oxygen-doped CNTs (Ep-CNTs) and their application as a near-infrared fluorescent probe [1-3]. Treated (6, 5) nanotubes show photoluminescence at ~1280 nm, which corresponds to the most transparent regions for biomaterials [1]. Immunoassay and fluorescence vascular angiography of mice were demonstrated by using the produced Ep-CNTs as infrared fluorescent labels [1,3] and imaging agents [1,2], respectively. From a practical point of view, the biodistributions of the Ep-CNTs imaging probe after administration to mice were investigated in detail [2]. In addition, the biological responses of mice following administration, which are relevant to safety, were also introduced [2].
More recently, we found that CNTs exhibit high compatibility with bone tissue [4]. The guided bone regeneration (GBR) technique is commonly applied to reconstruct alveolar bone and treat peri-implant bone defects. It was found that CNT-based membrane for GBR exhibits high strength to provide a space for bone formation and provide cellular shielding to induce osteogenesis.
In this meeting, we will report above biological and medical applications of CNTs in detail.
1. Y. Iizumi, M. Yudasaka, J. Kim, H. Sakakita, T. Takeuchi, T. Okazaki, Oxygen-doped carbon nanotubes for near-infrared fluorescent labels and imaging probes, Sci. Rep., 8, 6272 (2018).
2. T. Takeuchi, Y. Iizumi, M. Yudasaka, S. K. Kondoh, T. Okazaki, Characterization and biodistribution analysis of oxygen-doped single-walled carbon nanotubes used as in vivo fluorescence imaging probes, Bioconjugate Chem., 30, 1323−1330 (2019). (Cover Article)
3. K. Kojima, Y. Iizumi, M. Zhang, T. Okazaki, Streptavidin-conjugated oxygen-doped single-walled carbon nanotubes as near-infrared labels for immunoassays, Langmuir, 38, 1509-1513 (2022).
4. Y. Xu, E. Hirata, Y. Iizumi, N. Ushijima, K. Kubota, S. Kimura, Y. Maeda, T. Okazaki, A. Yokoyama, Single-walled Carbon Nanotube Membranes Accelerate Active Osteogenesis in Bone Defects: Potential of Guided Bone Regeneration Membranes, ACS Biomater. Sci. Eng., 8, 1667-1675 (2022).
Red and Blue Emissive Graphene Quantum Dots for Biomedical Applications
Authors: Kost Veronika , Mauro Diandra , Da Ros Tatiana 
Published: September 2023

Graphene quantum dots (GQDs) are a promising class of carbon nanomaterials characterized by unique photophysical and photochemical properties, which can be adjusted by using adapt preparation methods.1 Despite the wide range of synthesis routes suitable for GQDs production, achieving reproducible and properly controllable synthesis remains a challenging task.2,3

GQDs are characterized by high solubility in water, high biocompatibility, and low toxicity, which determine their wide application in bioimaging, biosensing, drug delivery, diagnosis, and therapy of cancer, and other more.4-7

Their synthesis was carried out by ultrasonic top-down technique starting from graphene oxide or using a bottom up approach starting from different precursors, including melamine and its polymer, or a mixture of citric acid, boric acid, and urea. The synthesis conditions, as well as ratios of the reagents, were varied to get control over the structure, size, and composition and, as a consequence, their photophysical properties.
The nanomaterials from GO presented excitation wavelength-independent photoluminescent behavior in the red region when excited in the range from UV till yellow light (300-550 nm). The emission maximum was observed at 647 nm when irradiated at 400 nm, while the one diriving from the bottom up strategies showed different fluorescence properties, with very interesting quantum yield. These properties let us consider these nanomaterials promising for investigating biological systems both in vitro and in vivo.

References
1) Tian et al. Mater. Today Chem. 2018, 10, 221–258.
2) Miao Nano Today. 2020, 33, 100879.
3) Moon et al. Nat. Commun. 2021,12, 5879.
4) Hadad et al. Nano Research, 2021, 14, 674-683.
5) Bayda et al. Nanoscale Adv., 2021, 3, 5183-5221.
6) Ding et al. Carbon, 2020, 167, 322-344.
7) She et al. Carbon, 2022, 191, 636-645.