bluuebunny/crossref_metadata_2025 huggingface dataset:
Decomposing a San Francisco estuary microbiome using long-read metagenomics reveals species- and strain-level dominance from picoeukaryotes to viruses
Authors: Lui Lauren M. , Nielsen Torben N.
Published: August 2024

Although long-read sequencing has enabled obtaining high-quality and complete genomes from metagenomes, many challenges still remain to completely decompose a metagenome into its constituent prokaryotic and viral genomes. This study focuses on decomposing an estuarine metagenome to obtain a more accurate estimate of microbial diversity. To achieve this, we developed a new bead-based DNA extraction method, a novel bin refinement method, and obtained 150 Gbp of Nanopore sequencing. We estimate that there are ~500 bacterial and archaeal species in our sample and obtained 68 high-quality bins (>90% complete, <5% contamination, ≤5 contigs, contig length of >100 kbp, and all ribosomal and tRNA genes). We also obtained many contigs of picoeukaryotes, environmental DNA of larger eukaryotes such as mammals, and complete mitochondrial and chloroplast genomes and detected ~40,000 viral populations. Our analysis indicates that there are only a few strains that comprise most of the species abundances.

IMPORTANCE

Ocean and estuarine microbiomes play critical roles in global element cycling and ecosystem function. Despite the importance of these microbial communities, many species still have not been cultured in the lab. Environmental sequencing is the primary way the function and population dynamics of these communities can be studied. Long-read sequencing provides an avenue to overcome limitations of short-read technologies to obtain complete microbial genomes but comes with its own technical challenges, such as needed sequencing depth and obtaining high-quality DNA. We present here new sampling and bioinformatics methods to attempt decomposing an estuarine microbiome into its constituent genomes. Our results suggest there are only a few strains that comprise most of the species abundances from viruses to picoeukaryotes, and to fully decompose a metagenome of this diversity requires 1 Tbp of long-read sequencing. We anticipate that as long-read sequencing technologies continue to improve, less sequencing will be needed.
Double subduction controls on long-lived continental tectonics and subcontinental mantle temperatures
Authors: Li Lin-Sen , Capitanio Fabio A. , Cawood Peter A. , Wu Ben-Jun , Zhai Ming-Guo , Wang Xiao-Lei
Published: August 2024

The complexities of convergent margins commonly include the interactions of subduction zones, with many geological records of “double” subduction. Here, we build two-dimensional numerical models to explore the evolution of complex subduction systems by systematically testing single and inward-dipping double subduction beneath a continental upper plate and the impact of continental collision on these systems. When compared to single subduction models, the inward-dipping double subduction shows hindered trench migrations and larger volumes of upwelling mantle enhanced by excess sinking slab mass. Double subduction draws larger volumes of hotter mantle beneath the continent in an area much broader than the marginal basins of single subductions, contributing to subcontinental heating by ~200 °C. As collision jams one margin of a double subduction system, the other margin follows the evolution of migrating single subduction zones, although characterized by persisting higher mantle temperatures and strong upwellings, inherited from the double subduction stage, and large-scale upper plate extension. The modeling outcomes are compared to scaling arguments to test the viability of the mechanism proposed for tectonics of the Cenozoic South China Sea and Neoproterozoic Yangtze Block (southeastern China), where the inward-dipping double subduction provides a context for protracted large-scale continental extension, hotter subcontinental temperatures, and channeled mantle flow not easily reconciled with the dynamics of single subduction zones.
Supplemental Material: Ultrahigh-pressure to high-pressure eclogite in Cuban ophiolitic mélange reveals proto–Caribbean spreading ridge subduction
Authors: Rui Hui-Chao , Yang Jing-Sui , al. et
Published: August 2024

Analytical data (Tables S1–S11).
Limits of Laser Cooling of Light Alkali Metals in a Polychromatic Light Field
Authors: Ilenkov R. Ya. , Prudnikov O. N. , Taichenachev A. V. , Yudin V. I.
Published: August 2024

A model was developed for laser cooling of alkali atoms in a polychromatic field, considering the real structure of atomic levels. The model was tested by the example of the 6Li atom. The minimum achievable temperatures of laser cooling of light alkali atoms were studied for different polarizations of the light field components, and the possibility of cooling below the Doppler limit was shown.
Treating iron deficiency in patients with heart failure: what, why, when, how, where and who
Authors: Graham Fraser J , Guha Kaushik , Cleland John G , Kalra Paul R
Published: August 2024

For patients with heart failure and reduced or mildly reduced left ventricular ejection fraction, iron deficiency is common and associated with more severe symptoms, worse quality of life and an increased risk of hospitalisations and death. Iron deficiency can be swiftly, effectively and safely treated by administering intravenous iron, either as ferric carboxymaltose or ferric derisomaltose, which improves patient well-being and reduces the risk of hospitalisations including those for heart failure. However, the current definition of iron deficiency in heart failure has serious flaws. A serum ferritin <100 µg/L does not identify patients more likely to respond to intravenous iron. In contrast, patients with transferrin saturations <20%, most of whom are also anaemic, are more likely to have a beneficial response to intravenous iron. In this review, we summarise the available evidence for use of intravenous iron in heart failure and provide recommendations for targeted future research and practical considerations for the general cardiologist.
Breast phyllodes tumour with epithelioid feature predisposes to malignant transformation
Authors: Shao Mumin , Zhang Lu , Li Xia , Bi Jiaxin , Jiang Xu , Yu Xuewen , Liang Yingying , Xu Hua , Meng Gang , Gong Xiyu
Published: August 2024

Aims

Phyllodes tumours (PTs) are relatively common fibroepithelial tumours comprising epithelial and stromal component. Usually, PTs show a spindle cell morphology with a fibroblast phenotype, while some tumour cells exhibit epithelioid morphological features and sarcomatoid transformation. However, the molecular characteristics of this morphology subset remain unclear. This study aimed to summarise the clinicopathological, morphological and molecular characteristics of seven cases of PT with epithelioid features.

Methods

Morphological and clinicopathological characteristics were observed and retrieved. Immunohistochemistry, immunofluorescence and electron microscope were performed on seven cases of epithelioid PT to explore immunophenotypic and ultrastructural characteristics. Transcriptomic and proteomic analyses were conducted to compare differentially expressed genes and proteins between epithelioid PT and classical PT.

Results

Patients with epithelioid PT exhibit a high recurrence rate (42.8%). Morphologically, in addition to having epithelioid cytological features, neoplastic stromal cells exhibit moderate to marked atypia and often exhibit sarcomatoid transformation, similar to the characteristics of borderline PT. Transcriptomic and proteomic analyses demonstrated that epithelioid PTs are distinct from classical PTs in gene expression and protein abundance levels. Immunohistochemical analysis showed that among all differentially expressed proteins, epithelioid PT showed abnormal p16/retinoblastoma expression patterns, similar to those of malignant PT.

Conclusions

Epithelioid PT has unique morphological characteristics, biological behaviour and protein expression profile, which meets the diagnostic criteria of borderline PT and is prone to sarcomatoid transformation. It may be a special morphological subgroup of borderline PT and has partial characteristics of malignant PT, which should be taken seriously in pathological diagnosis and clinical management.
Assessing IgG4-related ophthalmic disease and its mimics: a comparison of ACR/EULAR, organ-specific and revised comprehensive diagnostic criteria
Authors: Bakshi Neha , Aggarwal Aditi , Dhawan Shashi , Grover A K , Duggal Lalit , Badwal Sonia , Rao Seema
Published: August 2024

Aims

Diagnosis of IgG4-related ophthalmic disease (IgG4-ROD) rests on the correlation of clinical features, serological testing and histopathology, using internationally accepted diagnostic criteria for objective interpretation; however, several mimickers of IgG4-RD overlap in clinical presentation and histopathology. We assess histopathological features in a series of presumptive IgG4-ROD cases, with emphasis on histopathological mimics and comparison of three IgG4-ROD diagnostic/classification criteria (organ-specific (OS), revised comprehensive diagnostic (RCD) and American College of Rheumatology/European Alliance of Associations for Rheumatology (ACR/EULAR) criteria).

Methods

The histopathology database was screened for cases with clinical/histopathological suspicion of IgG4-ROD. Slides were reviewed, OS, RCD and ACR/EULAR criteria were applied, and the final clinicopathological diagnosis was recorded.

Results

37 patients (24 females, 13 males; 19–73 years) were diagnosed as either IgG4-ROD (n=18) or non-IgG4-related disease (n=19). Non-IgG4-related disease group showed elevated serum IgG4 (55.5%), fibrosis (100%), dense lymphoplasmacytic inflammation (92.8%), with an increase in tissue IgG4+plasma cells (57.1%) and elevated IgG4:IgG+plasma cell ratio (14.3%). ACR/EULAR missed 50% (9/18, sensitivity—52.8%) of true IgG4-ROD cases, while OS and RCD criteria missed 11.1% (2/18, sensitivity—88.9%) of IgG-ROD cases. ACR/EULAR criteria mislabelled 7.14% (1/14, specificity—90.9%) while OS and RCD criteria wrongly categorised 71.4% (10/14, specificity—47.4%) and 50% (7/14, specificity—63.2%) specific non-IgG4-ROD cases as IgG4-ROD. Storiform fibrosis, obliterative phlebitis, increased IgG4:IgG+plasma cell ratio and elevated serum IgG were statistically significant in distinguishing IgG4-ROD from its mimics.

Conclusion

ACR/EULAR criteria showed high specificity but were cumbersome and sensitivity was low, while RCD and OS criteria showed low specificity. Stringent clinicopathological correlation to exclude mimics is critical in avoiding diagnostic errors in IgG4-ROD.
‘Gout was like the boss’. A qualitative study exploring the impact of gout on employment
Authors: Diaz-Torne Cesar , Pou Maria Antonia , Horne Anne , Gasteiger Chiara , Dalbeth Nicola
Published: August 2024

Objective

Previous research has identified that gout impacts various domains of daily life. However, there have been no qualitative studies focusing on employment. This study aimed to understand the impact of gout on employment.

Methods

Semistructured interviews were conducted in Spain and Aotearoa/New Zealand, in people with gout (according to the 2015 American College of Rheumatology/European Alliance of Associations for Rheumatology criteria) who had experienced a gout flare during their employment. The interviews were guided by questions exploring the impact on employment, job changes, disclosure and co-workers’ reactions. Data were analysed thematically.

Results

Eighteen participants were interviewed (89% male, mean age 52.9 years). Six themes were identified. The characteristics of the disease (pain intensity, tophi and joints affected) and the job itself (including physical job requirement and workplace flexibility) determined the experience of working with gout. The experiences were divided into physical (from total incapacity to working despite pain), emotional (feeling responsible, embarrassment, guilt and depression) and social (including disclosure responses and financial impact). Gout management strategies including rapid gout flare management and urate-lowering therapy reduced the number of flares and the intensity of pain, and allowed work attendance and participation.

Conclusion

Both gout and work characteristics influence the employment experience for people with gout. Effective management of gout led to improved work experiences in all its domains.
Study on photoelectric properties of manganese-doped MoS2 thin films
Authors: Sun Zijian , Cai Weiqiang , Xu Jiaying , Ma Xiying , Zhang Xiaoyu
Published: August 2024

This paper investigates the microstructure, morphology and optical properties of manganese (Mn)-doped molybdenum disulfide (MoS2) films with a triangular shape fabricated by the chemical vapor deposition method. X-ray diffraction and X-ray photoelectron spectroscopy show that the Mn element is successfully doped into MoS2 film. Mn doping results in a shift in the absorption spectrum because of the changes in the band structure of the doped films. I–V curves indicate about a 50% reduction in the photocurrent onset voltage for the Mn-MoS2 film under different light intensities. The results demonstrate that Mn doping improves the electronic structure of MoS2 film, which is of significant importance for applications in optoelectronic sensing and photocatalysis.
Broadband controllable defect state of longitudinal waves in one-dimensional pillared phononic crystal beams
Authors: Bian Xiaohui , Zhang Shunzu
Published: August 2024

Defect state of phononic crystals (PCs) has attracted fast-growing attention due to wave energy localization, which can serve as an effective means of controlling elastic waves. In this paper, we investigate the defect state of a one-dimensional (1D) broadband controllable pillared PC beam consisting of pillared permanent magnets on an aluminium beam through numerical simulations and experiments. First, the width and position of the band gap are altered by adjusting the height of the magnetic pillars’. Then, building on this foundation, we successfully observe the controllable defect states of longitudinal waves at the defects of pillared PC beams through a simple adjustment of the height of the defective magnetic pillars’. Finally, we conduct an experimental validation to confirm the feasibility of the localization behavior of elastic waves in the pillared PC system. This research offers a straightforward method to dynamically control the defect state of PCs and enhance the applications for defected PCs, spanning novel filters, defect detectors, and broadband energy harvesting.
Dynamics of a Diffusive Predator–Prey System with Fear Effect in Advective Environments
Authors: Duan Daifeng , Niu Ben , Yuan Yuan
Published: August 2024

We explore a diffusive predator–prey system that incorporates the fear effect in advective environments. First, we analyze the eigenvalue problem and the adjoint operator, considering Constant-Flux and Dirichlet boundary conditions, as well as Free-Flow boundary conditions. Next, we use the principle of comparison to prove the non-negativity of the solution. Our investigation focuses on determining the direction and stability of spatial Hopf bifurcation, with the generation delay serving as the bifurcation parameter. Additionally, we examine the influence of both linear and Holling-II functional responses on the dynamics of the model. Through these analyses, we gain better understanding of the intricate relationship among advection, predation, and prey response in this system.
Node Centrality Based on Edge Dynamics in a Chaotic Network
Authors: Chen Fangyue , Zhou Jin , Lu Jun-an
Published: August 2024

This paper introduces a novel node centrality index based on edge dynamics in a complex network: adjacent edge index. Through the analysis of network dynamics and topology, we provide a neat index to qualify node importance, which is calculated by the eigenvector components corresponding to the Fiedler value of the network. Notably, it identifies nodes whose adjacent edge sets play a significant role in network synchronization. The index indicates that not only a node’s degree but also its location should be considered. To demonstrate the effectiveness of the proposed index, consider a double-star network and a Jazz Musicians network in which chaotic Chua’s circuits as nodes are coupled. By factoring in the dynamic information exchange between nodes and their neighbors, this index offers valuable insights for optimizing strategies in engineering areas such as efficient information dissemination.
EDGE-HYPER-WIENER INDEX ON LEVEL-3 SIERPINSKI NETWORKS
Authors: DU CAIMIN , YAO YIQI , XI LIFENG
Published: August 2024

Using the technique of finite pattern, for level-3 Sierpinski networks, we obtain their exact formulae of edge-hyper-Wiener index, which is the sum of the distances and the square of distances between all pairs of edges.
Benchmarking and Categorizing the Performance of Neural Program Repair Systems for Java
Authors: Zhong Wenkang , Li Chuanyi , Liu Kui , Ge Jidong , Luo Bin , Bissyandé Tegawendé F. , Ng Vincent
Published: August 2024

Recent years have seen a rise in Neural Program Repair (NPR) systems in the software engineering community, which adopt advanced deep learning techniques to automatically fix bugs. Having a comprehensive understanding of existing systems can facilitate new improvements in this area and provide practical instructions for users. However, we observe two potential weaknesses in the current evaluation of NPR systems: ① published systems are trained with varying data, and ② NPR systems are roughly evaluated through the number of totally fixed bugs. Questions such as
what types of bugs are repairable for current systems
cannot be answered yet. Consequently, researchers cannot make target improvements in this area and users have no idea of the real affair of existing systems. In this article, we perform a systematic evaluation of the existing nine state-of-the-art NPR systems. To perform a fair and detailed comparison, we (1) build a new benchmark and framework that supports training and validating the nine systems with unified data and (2) evaluate re-trained systems with detailed performance analysis, especially on the effectiveness and the efficiency. We believe our benchmark tool and evaluation results could offer practitioners the real affairs of current NPR systems and the implications of further facilitating the improvements of NPR.
The Effect of the Rare Earth Element Cerium on the Electrocrystallization and Microstructure of Nickel Electrodeposits in Industrial Electrolytes
Authors: Xu Yang-Tao , Li Yan-Hong , Peng Yin , Zhong Zhi-Qiang
Published: August 2024

To meet the industrial production needs for high-quality and precisely controllable structured high-end nickel foils, rare Earth compounds are added as additives in complex industrial electrolytes to improve the quality of the nickel deposition layer. This study investigates the effects of adding rare Earth compounds to the existing industrial production electrolytes (which already contain various organic and inorganic additives in a mixed acid solution) on the surface microstructure, cerium content, grain size, and crystal orientation of the nickel deposition layer. Using direct current electrodeposition, different concentrations of rare Earth compounds were added to the industrial electrolyte, and the cerium content, grain size, and crystal orientation were characterized. The results show that adding 0.8 g·l−1 CeCl3 accelerates the nucleation rate and shortens the nucleation relaxation time. The addition of rare Earth elements promotes multi-directional preferential growth, resulting in uniform and fine grain size, improved grain structure of the deposition layer, and reduced surface roughness of the nickel plating layer. Therefore, rare Earth elements can be used to regulate the structure, microstructure, and grain refinement of the nickel deposition layer without affecting its composition.
(Invited) Semiconductor Nanostructures for Light Energy Conversion
Authors: Kamat Prashant V
Published: August 2024

This talk will review some of the key developments of semiconductor quantum dots based light energy conversion. Semiconductor nanostructures are finding new ways to design light energy conversion devices (e.g., thin film solar cells and light emitting devices). The decreased consumption of energy during the manufacture and the lessened use of semiconductor materials lowers the overall carbon footprint with energy payback time less than a year for such devices. The early studies which focused on the synthesis of various semiconductor nanostructures and exploration of their size dependent optical and electronic properties have led to their their integration in high efficiency thin film solar cells.. Unlike solar cell devices, photocatalytic processes are yet to deliver conversion efficiencies and stability that can make them compatible for practical applications. Understanding the limitations imposed by interfacial charge transfer processes remains a key to further advance photocatalytic systems for chemical energy storage. Recent developments in utilizing semiconductor nanostructures for light energy conversion and storage will be discussed.
(Invited) Architectural Refinement in Core-Shell Ni/Ni(OH)2 Nanowires Array for Enhanced Supercapacitor Performance - A Comprehensive Electrochemical and Finite Element Study
Authors: Pandey Ravi , Andola Anshu , Kashyap Yashvant , Pandey Himani , Pandey Rakesh Kumar
Published: August 2024

We investigated the electrochemical performance and effect of different aspect ratios of core-shell Ni/Ni(OH)2 nanowires arrayed in an asymmetric supercapacitor with graphene flakes. We created thenanowires with diameters of 35 nm, 100 nm, 150 nm and different height using electrodeposition with help of Anodic Alumina Oxide template, allowing us to regulate their dimensions accurately. We identified an intriguing trend: supercapacitor performance first rises with nanowire height, but then steadily drops when a critical threshold is reached. We used Finite Element Analysis (FEA) to corroborate our experimental results and uncover the underlying electrochemical processes in order to better explain and comprehend this phenomenon. According to the FEA simulations, the nanowire length effects the distribution and accessibility of ionic species surrounding the nanowire array, which influences the charge storage and transfer processes.

Figure 1
(Invited) A CNT Binding Bis(Zinc Porphyrin)Bodipy-C60 Nano Tweezer: Charge Stabilization in Supramolecular C60-Bodipy-(ZnP)2:SWCNT Hybrids
Authors: Kazemi Shahrzad , Alsaleh Ajyal , Karr Paul , D'Souza Francis
Published: August 2024

Single-wall carbon nanotubes (SWCNT) coupled with either electron donor or acceptor are promising functional structures for light energy harvesting and molecular optoelectronics applications. For building such hybrids involving SWCNTs, the p-stacking ability of large aromatic compounds is one of the commonly employed approaches.1-2 Often, the desired donor or acceptor entities are functionalized to carry one or more aromatic entities and allowed to interact with CNTs. However, due to close proximity, the role of SWCNTs in stabilizing the electron transfer product has been a challenge.3 Recently, we overcame this hurdle by employing a multi-modular approach to build donor-acceptor hybrids and successfully demonstrated charge stabilization in the presence of SWCNTs.4 In the present study, we have further improved our design by newly synthesizing a nano tweezer comprised of covalently linked BODIPY-C60 carrying two zinc porphyrin arms as shown in the figure. This compound was further allowed to interact with SWCNT(6,5) and SWCNT(7,6) to form the supramolecular C60-BODIPY-(ZnP)2:SWCNThybrids. Upon spectral, electrochemical, and computational characterization, femtosecond pump-probe spectroscopic studies were performed to establish the occurrence of photoinduced charge separation and charge stabilization. Extending the lifetime of the charge-separated states upon SWCNT binding has been successfully demonstrated in the present molecular design strategy.

D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ Phys. Chem. Letts. 2010, 1. 2586-2593.

B. KC, G. N. Lim, and F. D’Souza, ‘Accelerated Charge Separation in Graphene Decorated Multi-Modular Tripyrene-Subphthalocyanine-Fullerene Donor-Acceptor Hybrids,’ Angew. Chem. Int. Ed.
2015, 54, 5088-5092.

Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992.

Kazemi, Y. Jang, A. Liyanage, P. A. Karr, and F. D’Souza, A Carbon Nanotube Binding Bis(pyrenylstyryl)BODIPY-C60 Nano Tweezer: Charge Stabilization through Sequential Electron Transfer, Angew. Chem. Int. Ed.
2022, 61, e202212474 (1-7).

Figure 1
(Invited) Dynamics of Photoluminescence in Mn-Doped Pb-Halide Perovskite Nanocrystals
Authors: Sarma D. D.
Published: August 2024

Nanocrystals of lead halide perovskites have been shown to have extraordinary photoluminescence properties, spanning the entire visible range achieved by the composition tuning via solid solutions at the halide site. Taking cues from Mn doping of traditional Group II-VI semiconductor quantum dots, Mn doping of the lead halide perovskites has been extensively explored by the community, establishing intense Mn-dopant induced emission that is significantly Stokes shifted from the excitonic emissions of the host. While all reports agree on the essential features of this emission, such as the peak position and the width of the Mn photoluminescence, there appears to be little agreement on the microscopic processes by which the host sensitizes Mn following its photoexcitation and the steps that control the deexcitation leading to the Mn emission. There are even reports of disagreement between different reports on the temperature dependence of the Mn emission and its origin. I shall discuss the present status of this field and establish, with the help of new experimental data as well as the already reported ones, what appears to be the microscopic processes controlling the excited dynamics in the Mn-doped lead halide perovskites.
Regulating the Electrochemical Performance of Simple Halogen-Free Electrolyte Using Ammonium Bromide Additive for Magnesium-Sulfur Battery Applications
Authors: Farrag Mohamed , Zaki Ayman , Yacout Nasser , Moselhy Mostafa , El-Dek Engy , Abdelmonam Abdelmonam , Refai Henan , Xing Wei , Sheha Eslam
Published: August 2024

Magnesium-sulfur (Mg-S) batteries are a promising energy storage system; however, the short cycle life, low coulombic efficiency, and the shuttle effect of polysulfide hinder its practical application. Applying electrolyte additives is a powerful technique to optimize the electrochemical performance of Mg-S electrolytes. Herein, ammonium bromide (NH4Br) is used as an inorganic electrolyte additive in the halogen-free electrolyte (HFE) to guide homogeneous Mg deposition. It can be noticed that the addition of NH4Br decreases the activation energy values from 0.14 eV to 0.10 eV and reduces the value of Mg2+ stripping/plating overpotential. It is found that the introduction of NH4Br to HFE enhances the cycle life and the initial discharge capacity (~1662 mAhg-1) of the Mg-S cells compared with the cells using free NH4Br that deliver initial discharge capacity of ~ 184 mAh g-1, low coulombic efficiency, and short cycle life. Further efforts have been devoted by implementing a BaTiO3 (BTO) as a modified separator to overcome the polysulfide dissolution issue in the cell. The surface of the cell's anode applying a modified separator shows half wt.% S content compared with the bare cell after cycling. This study opens further research for developing novel electrolyte schemes for magnesium-sulfur battery applications.
Tellurium-Boosted Sulfur Cathodes for Lithium/Zinc-Ions Storage
Authors: Zhang Yue , Orhan Okan , Tao Li , Ponga Mauricio , Liu Jian
Published: August 2024

Over the past few decades, lithium-ion batteries (LIBs) have attracted tremendous efforts in research and industry, but their further development is primarily challenged by the limited energy density caused by the intercalation cathodes’ relatively low specific capacities below 200 mAh g-1. Low-cost and abundant sulfur (S) is a promising conversion-type cathode which can theoretically deliver 1675 mAh g-1 through a two-electron reaction, despite that Li-S batteries are suffering from shuttle effect and sluggish redox kinetics caused by the insulating nature of S. In this work, an impressive S cathode structure is studied by leveraging tellurium's properties (electron transfer booster). Comprehensive experimental data suggests that introducing Te can reshape the Li-S electrochemistry and lead to significantly enhanced reversible capacity and superior structural stability. Theoretical calculations reveal the more delocalized charge-density differences around the Te atoms in Li16Te1S7 compared to site-equivalent S atoms in Li2S, and Li16Te1S7 possesses lower energy barriers throughout the Li migration pathway. By tuning the molar ratio of Te/S, it is found that the Te1S7/KB cathode delivers the highest reversible capacity of 1306.7 mAh g-1 at 0.1 A g-1 and maintains a capacity of 959.8 mAh g-1 after 400 cycles at 1 A g-1 in carbonate-based electrolytes. The optimal Te1S7/KB cathode outperforms the S/KB cathode at both coin and pouch cell levels. On the other hand, Te doping can also reduce the polarization of Zn-S batteries, improve the electrochemical reversibility, and eventually contribute to high-areal-capacity cathodes (up to 5.64 mAh cm-2) towards practical applications. Accompanied by the S-ZnS conversion, Te is converted to zinc telluride during the discharge process, as revealed by ex-situ characterizations. Additionally, employing proper amount of co-solvent can suppress Zn dendrites growth and extend the lifetime of Zn-Te1S7 batteries, as investigated by the in-situ techniques of Optical Microscopy and Differential Electrochemical Mass Spectrometry. The use of tellurium as a modifier to enhance the performance of sulfur cathodes is intriguing. This novel materials design has substantial implications for advancing battery technology, especially in improving energy density and stability, which are crucial factors in the development of sustainable energy solutions.
Effect of Cycling on the Physical Properties of the Garnet Solid Electrolyte, LLZO
Authors: Moon Jaron V , Go Wooseok , Dhall Rohan , Tucker Mike C , Doeff Marca M. , Warren Roseanne
Published: August 2024

Solid-state energy storage is the future of high performance, high-energy-dense battery systems. A common solid electrolyte, argued to be viable for such a system is the ceramic garnet solid oxide solid electrolyte, LLZO. LLZO is preferred due to its high ionic conductivity and stability against lithium metal. To date, most mechano-electrochemical studies of this solid electrolyte only focus on the fabrication and cell performance of the solid electrolyte. For the first time, this work explores the effect cycling has on the physical properties of the LLZO solid electrolyte, where, after cycling, surface characterization is completed to understand the degradation effects of cycling, as well as the grain boundary-grain modifications that occur. Initial results indicate lithium nucleation in the grain boundaries occurs, where elemental mapping will allow for quantification of lithium concentration changes in the grain boundaries, indicating whether lithium exists in the grain as a pure metal or as an alloying compound. Indentation techniques are used to show that molecular stoichiometric changes of the solid electrolyte at the grain boundaries create a softer material, which would be more susceptible to dendrite protrusions, allowing for premature cell failure. This work provides valuable insight into the chemo-mechanical response of LLZO to lithium-ion migration across grain-grain boundary interfaces, helping guide materials engineering decisions for a more robust, electrochemically stable solid electrolyte.

Figure 1
Current-Dependent Lithium Metal Microstructure in ‘Anode-Free’ Solid-State Batteries at the Steel|LPSCI Interface
Authors: Becker Juri , Fuchs Till , Richter Felix H. , Janek Jürgen
Published: August 2024

Further improvement of energy densities of state-of-the-art batteries could be achieved with the utilization of lithium metal anodes.1 Due to the reactivity of the alkali metal, the fabrication process needs to be monitored carefully. To circumvent degradation during storage as well as the handling of lithium metal, reservoir-free cells (RFCs) are investigated.2 Using accessible lithium stored within lithiated cathode materials, the lithium anode is formed in a formation step during the first charging cycle. The electrochemical properties of the electrodeposited lithium film are strongly dependent on its microstructure, and can, for example, influence the resoluble amount of lithium during subsequent cycling.3,4 Until now, the microstructure of electrodeposited lithium and how to control it is elusive.

To observe and characterize the microstructure of electrodeposited lithium at the stainless steel|LPSCl interface, a combination of electrochemical impedance spectroscopy, focused ion beam and scanning electron microscopy as well as electron backscatter diffraction was used. With this setup, the correlation between deposition current density and resulting microstructure of the lithium film was investigated. For higher current densities, a twenty times smaller grain size was observed, while the grain density showed a twelvefold increase, which could have a major influence on the subsequent dissolution of lithium. Furthermore, the microstructural evolution during prolonged lithium deposition was investigated.

1 J. Janek and W. G. Zeier, Nat. Energy, 2016, 1, 16141.

2 M. J. Wang, E. Carmona, A. Gupta, P. Albertus and J. Sakamoto, Nat Commun., 2020, 11, 1–9.

3 S. E. Sandoval and M. T. McDowell, Matter, 2023, 6, 2101–2102.

4 D. K. Singh, T. Fuchs, C. Krempaszky, B. Mogwitz, S. Burkhardt, F. H. Richter and J. Janek, Adv. Funct. Mater., 2023, 33, 2211067.
Enhancing Moisture Tolerance of Sulfide Solid Electrolytes through Nano-Level Treatment Utilizing Lewis Acid Additives
Authors: Asgedom Yosef Nikodimos , Su Wei-Nien , Hwang Bing Joe
Published: August 2024

Sulfide solid-state electrolytes (SSSEs), particularly the argyrodite Li6PS5Cl, are considered a promising solid electrolyte for all-solid-state batteries due to their excellent ductility and remarkable ionic conductivity. However, a significant challenge in the large-scale application of SSSEs is their lack of stability when exposed to humid air. To address these challenges, a prominent solution involves treating SSSE particles with Lewis acid additives at the nanoscale level method is employed. Some of the several Lewis acid additives considered in this study are aluminum acetylacetonate, tetrafluoro-1,4-benzoquinone, and tetracyano-ethylene. This treatment process is dispersing the SSSE particles in solution mixtures containing Lewis acid additives. Importantly, this method is designed to have minimal impact on the ionic conductivity of the SSSE. A series of investigations are conducted using various characterization techniques, including X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), in-situ Raman spectroscopy, solid-state nuclear magnetic resonance (NMR), and synchrotron-based X-ray Absorption Near-Edge Structure (XANES). These employed techniques are essential for analyzing the structural and chemical changes in SSSE particles treated with Lewis acid additives, leading to key findings. The key finding of the study is that the SSSE particles demonstrated outstanding atmospheric stability when treated with Lewis acid additives. This stability is attributed to the establishment of a Lewis acid-base interaction between the SSSE and the additives. This interaction effectively shields the SSSE from moisture in humid air, preventing structural deterioration in the bulk region. In other words, the Lewis acid additives create a protective layer that maintains the integrity of the SSSE, even in the presence of atmospheric moisture. Moreover, the Lewis acid additives treated SSSE samples demonstrated enhanced chemical stability in the ASSB system after being exposed to moisture as compared to the pristine SSSE. Highlighting the use of Lewis acid additives to enhance the moisture stability of SSSEs as a promising approach, this improvement in stability is crucial for the practical application of SSSEs in large-scale settings where exposure to humid conditions is inevitable. The study suggests that this method could pave the way for more reliable and durable all-solid-state batteries by addressing a critical limitation of SSSEs.
Solid-State Composite Electrolytes for Lithium-Ion Batteries
Authors: Yang Hui , Wu Nianqiang
Published: August 2024

High-energy density Li-ion batteries are critical to electric vehicles and cell phones. Current commercial liquid-electrolyte batteries raise serious concern on safety and low energy density. Therefore, solid-state electrolyte batteries receive increasing attention due to better safety and higher energy density as compared to liquid-electrolyte counterparts. However, commercialization of solid-state electrolyte batteries is hindered by low ionic conductivity and incompatible interface among different types of materials. Thus, rational material design and interface engineering have been performed to mitigate the problems. In addition, fundamental studies have been conducted to understand the Li -ion transport mechanism and synergetic interfacial chemical interactions in inorganic-organic composite electrolytes. The performance of solid-state electrolytes such as ionic conductivity, electrochemical window, and Li-ion transference numbers have been improved by combination of fundamental studies and rational design of materials.
The Importance of Adhesion in Solid-State Batteries
Authors: Tsai Wan-Yu , Owensby Kyra D'Yana , Sahore Ritu , Browning Katie , Kalnaus Sergiy , Westover Andrew S , Chen Xi Chelsea
Published: August 2024

Solid-state batteries are one of the key technologies to expedite the electrification of the economy. Compared with traditional liquid electrolytes, solid-state electrolytes are intrinsically safer and can enable high-energy designs by pairing with high-capacity cathodes and lithium metal anodes. However, maintaining the solid/solid contact between electrode and electrolyte during electrochemical cycling is non-trivial and the main challenge for all-solid-state batteries. The common strategy for combatting the contact issue is applying stack pressure, which is a sort of scientific shortcut that masks the real challenges of maintaining good contact between the different electrodes and electrolytes. Improving the adhesion between different battery components is a more effective and commercially viable strategy. We hypothesized that increasing the adhesion between electrode and electrolyte will improve electrode integrity, mitigate contact loss, and increase Coulombic efficiency and cycle life.

There are very few studies on the adhesion of battery materials. This is primarily due to limited techniques to measure adhesion at the nanometer and micrometer scales relevant to the battery operation. In this work, we proposed to use atomic force microscopy (AFM) with customized probes to investigate adhesion between a model solid polymer electrolyte (SPE) consisting of crosslinked poly(ethylene oxide) (xPEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and a model cathode active material, LiNi0.6Mn0.2Co0.2O2 (NMC622). We showed that a two-fold increase in polymer stiffness (storage shear modulus, G’) from increasing the crosslinking density, leads to a 40% reduction in the bulk ionic conductivity in the SPE. However, we show evidence that this trade-off relationship between stiffness and ionic conductivity does not significantly impact the battery performance. In drastic contrast, it leads to a decrease in the work of adhesion at the electrolyte|cathode interface, which has a profound impact on the resulting discharge capacity of the battery. How the crosslinking density of the polymer affects the NMC-xPEO adhesion at the microscale and how this affects battery performance remain open questions, which the authors wish to gain insight into from the discussions.
Advancing Electrochemical Energy Storage: The Synergistic Impact of Sulfur Nano-Confinement in Hierarchically Porous Jute-Derived Activated Carbon for Enhanced Supercapacitor Performance
Authors: Shah Syed Shaheen , Aziz Md. Abdul , Oyama Munetaka
Published: August 2024

The availability of energy is a cornerstone for the modernization, automation, and economic growth of nations. With the rapid depletion of fossil fuels and rising environmental concerns, such as CO2 emissions leading to global warming, there has been an intensified search for alternative, renewable energy sources like solar and wind power. However, their intermittent nature necessitates robust electric energy storage systems for effectively harnessing these resources. Electrochemical energy storage devices, particularly batteries and supercapacitors, have emerged as a focal point of recent research due to their potential to bridge this gap. While supercapacitors are known for their high power density and long cycle life, they typically exhibit limited energy density. Recent advancements have shown that composites combining carbonaceous materials with redox-active nanomaterials can significantly enhance supercapacitors' electrochemical performance. In this context, our research explores the development of hierarchically porous activated carbon nanosheets (JAC) derived from jute, an abundantly available biomass. Using a straightforward pyrolysis process, we have investigated its potential in supercapacitor applications. The prepared JAC, when employed as an electrode material in a symmetric supercapacitor with a glycerol-based bio-electrolyte, demonstrated higher specific capacitance compared to its commercial counterparts. Further innovation was achieved through the introduction of sulfur doping in JAC (S-doped JAC). This novel approach leverages the inherent porous nanosheet morphology of JAC and heteroatom modification to yield exceptional electrochemical performance. Our findings reveal that the S-doped JAC composite, particularly the variant with 25% sublimed sulfur (SJAC-25), significantly outperforms the standard JAC in terms of specific capacitance (230 F/g vs. 130 F/g at 1.0 A/g current density) in a glycerol-KOH bio-based electrolyte. Moreover, a symmetric supercapacitor assembled with SJAC-25 showcased an impressive energy density of 32 Wh/kg at a power density of 500 W/kg, maintaining 28 Wh/kg even at a heightened power density of 2500 W/kg. This demonstrates its capability to retain high energy efficiency under varying power conditions. Additionally, the SJAC-25 based supercapacitor exhibited remarkable durability, with about 94% capacitance retention and 86% Coulombic efficiency after 10,000 charge-discharge cycles. Our research not only highlights the potential of processed bio-waste as a viable material for energy storage but also introduces an advanced, scalable, and straightforward synthesis method. This method could pave the way for the preparation of highly porous and sulfur-doped nanoporous carbon, setting a new benchmark for high-performance electrochemical energy storage applications.
Understanding Electrode-Electrolyte Interfaces in Gel Polymer Electrolytes Using in-Operando Raman Spectroscopy
Authors: Pereira Rhyz , Yim Taber , Dopilka Andrew , Kostecki Robert , Kalra Vibha
Published: August 2024

Gel polymer electrolytes hold enormous potential for advancing battery performance and technology, promising high energy densities and safe, rechargeable quasi solid-state batteries. GPEs offer higher ionic conductivities than solid electrolytes and enhanced safety in comparison to liquid electrolytes. A particular advantage of these electrolytes has been their ability to create robust electrode electrolyte interfaces that guide uniform deposition and stripping of lithium via their mechanical strength from the polymer and interface species that form during initial cycling.

Herein we report that 1:1 dimethoxyethane (DME) and dioxolane (DOL) with lithium bistrifluoromethanosulfonyl imide (LiTFSI) and lithium nitrate entrapped in Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) gel polymer electrolytes have shown stability for up to 500 hours in lithium metal symmetric cells at 1 mAh/cm2 and performs at 5mAh/cm2 in dynamic symmetric cell cycling. To understand the fundamental interfacial phenomenon governing lithium deposition and growth in this system in-operando Raman was conducted on an anodeless Cu|PVDF-HFP|Li cell. Copper was sputtered onto the polymer electrolyte before assembly with a thickness of 20nm, providing an optically transparent electrode through which the Raman laser could pass through to detect interfacial species. We observe that PVDF-HFP acted as a chemically stable polymer electrolyte while Raman shifts associated with TFSI anions disappear near the electrode surface. The spectral and electrochemical data allow us to build a model for the growth and evolution of interfaces in an anodeless lithium metal battery cell with a GPE.

Acknowledgement:

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the DOE under contract number DE‐SC0014664.

Figure 1
Microstructure Evolution of Electrodeposited Magnesium on Copper Current Collector during Cycles for Anode-Free Rechargeable Magnesium Battery
Authors: Tsai Wei-Shiang , Wu Ying-Chen , Huang Yu-Shan , Chu Peng-Wei
Published: August 2024

Rechargeable magnesium (Mg) batteries attract lots of interest owing to their high theoretical volumetric energy density and low cost from the natural abundance of Mg. Additionally, Mg is less prone to dendrite growth during charging, which improves the battery safety. However, rechargeable Mg battery systems suffer from sluggish reaction kinetics on the electrodes and poor cycle life, greatly limiting their practical competitiveness. While most studies of rechargeable Mg batteries focus on the development of electrolytes and their feasibilities, the microstructure evolution of the Mg metal anodes during cycles is not fully unveiled. Furthermore, when using Mg metal as the anode, the excessive Mg may limit the overall energy density of the cells. Recently, anode-free battery systems were introduced to further improve the battery capacity. In this report, we investigated anode-free rechargeable magnesium batteries by electrodepositing Mg on a copper (Cu) current collector in an all phenyl complex (APC) electrolyte. Afterward, the microstructure evolution of the electrodeposited Mg after discharge/charge cycles was studied.

The electrodeposited Mg on the Cu current collector with a current density of 2.25 mA/cm2 and a capacity of 1.5 mAh/cm2 shows a uniform distribution of Mg grains with an average grain size of 1.14 ± 0.06 μm. Subsequent Mg stripping with half the deposited capacity (0.75 mAh/cm2) was conducted at various current densities. Stripping with intermediate current density (0.75 mA/cm2) results in non-uniform discharge holes and possible local exposure of the Cu current collector, which could deteriorate the anode integrity. In contrast, the stripped electrodeposited Mg at relatively large (2.25 mA/cm2) and small (0.25 mA/cm2) discharge current densities show dense and uniform discharged holes on the surface. After prolonged discharge/charge cycles at a relatively large current density (2.25 mA/cm2), the electrodeposited Mg still exhibits a uniform surface morphology. In addition to cycling the electrodeposited Mg, a Mg-sulfur (Mg-S) full cell was also assembled with an anode of electrodeposited Mg on Cu and a sulfur/graphite cathode to explore the potential of anode-free rechargeable Mg-S battery.

Figure 1