bluuebunny/crossref_metadata_2025_split huggingface dataset:
LaAl3 Intermetallic Alloy Anode for Fluoride-Ion Battery
Authors: Sasano Shun , Ishikawa Ryo , Kawahara Kazuaki , Shibata Naoya , Ikuhara Yuichi 
Published: December 2024

An all-solid-state fluoride-ion battery is one of the promising candidates for next-generation secondary batteries owing to its high energy density compared to a commercial lithium-ion battery [1]. While the practical capacities of cathodes have recently shown improvements in discharge capacities (up to 200 – 500 mAh g–1) [2], the capacities of anodes are still one order of magnitude smaller than that of cathodes, and moreover, their cycle stability are also very low [3]. It is therefore important to improve the electrochemical performance of the anodes in fluoride-ion batteries. Aluminum (Al) is one of the promising metals owing to the high theoretical capacity (2980 mAh g–1) and the low redox potential (–1.7 V vs. Pb/PbF2). However, there is no report on the practical use of Al because of the significantly low F– ion conductivity of AlF3 (10–11 S cm–1 at room temperature). To secure the low F– ion conductivity of AlF3, we explore the intermetallic alloy between Al and La because LaF3 shows a higher F– ion conductivity (10–8 S cm–1) than that of AlF3. Here, we show that LaAl3 reversibly delivers the high capacity with relatively small capacity fade [4].
LaAl3 intermetallic alloy was prepared from La with a purity of 99.9% and Al with a purity of 99.999% by arc melting, and then annealed at 950℃ for 336 h. The LaAl3 phase was confirmed by powder X-ray diffraction. To prepare the anode composites, the LaAl3 powders were mixed with La0.9Ba0.1F2.4 (solid electrolytes) and acetylene black (conductive aids) powders in the weight ratio of 3:6:1, using planetary ball mills with ZrO2 balls under a rotation speed of 100 rpm for 20 h. Using galvanostatic cycling, we performed charge/discharge tests of the all-solid-state fluoride-ion battery, where LaAl3 and PbF2 were used as anode and cathode active materials, respectively. The initial discharge and charge capacities are 445 mAh g–1 and 202 mAh g–1, respectively. While the 1st discharge curve shows a monotonous potential increment, the subsequent charge and discharge curves show stable potential plateaus at –2.0 V and –1.5 V. To elucidate the charge/discharge mechanism of LaAl3, we performed structural and chemical analysis of the 1st discharged and charged LaAl3, using scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy (EELS). We found that LaAl3 is decomposed into LaF3 and AlF3 nanocrystals in the initial discharge process. Detailed discussion will be given in this presentation.

Acknowledgements

This presentation is based on results obtained from a project, JPNP21006, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

References

[1] M.A. Reddy et al., J. Mater. Chem. 21 17059 (2011).
[2] K. Nakayama et al., J. Mater. Chem. A, 10, 3743 (2022).
[3] M.A. Nowroozi and O. Clemens, ACS Appl. Energy Mater., 1, 6626 (2018).
[4] S. Sasano et al., J Electrochem. Soc. 170 120523 (2023).
First-Principles Study of Layered Electrode Materials for Multivalent Batteries
Authors: Park Haesun , Kim Deahyun 
Published: December 2024

Energy storage systems that efficiently shuttle multivalent cations such as calcium (Ca) or magnesium (Mg) have been increasingly spotlighted due to their potential for achieving high energy density at a lower cost. The advancement of these multivalent energy storage systems necessitates the exploration and development of electrode materials that not only offer high capacity but also ensure the reversible accommodation of multivalent cations. Recent studies on monovalent alkaline ions such as potassium and sodium, which exhibit a similar ionic radius to calcium, have demonstrated their capability for reversible intercalation into inorganic compounds with layered structures. This notable finding suggests a strong potential for the successful intercalation of divalent ions in analogous structures, thereby enhancing the versatility and efficiency of these energy storage systems.
In this context, we have employed first-principles calculations to systematically investigate and reveal that layered structures are conducive to topotactic intercalation of Ca or Mg, attributes characterized by favorable phase stability, electrochemical performance, cation mobility, and transition metal redox behavior. These layered materials, through our detailed computational analysis, show promise for the next generation of high-performance, cost-effective multivalent energy storage systems.
Study of the Local and Average Structure of Vanadium Oxides As Potential Cathodes for Mg-Ion Batteries
Authors: Samanta Anwesa , Cabana Jordi 
Published: December 2024

Being a divalent cation with the lowest mass, Mg2+ has garnered quite attention in recent times due to the high volumetric capacity of it’s batteries. Theoretical studies reveal that the combination of a Mg anode and a spinel oxide cathode would be able to surpass the current limits found in widely used Li-ion batteries Therefore, to design materials with high diffusion and reversible insertion capacity, a conclusive demonstration of the intercalation mechanism of Mg2+ into metal oxides, is required.
Among the numerous options for cathodes, vanadium oxides show evidence of the largest capability toward reversible intercalation of Mg ions. In particular, spinel-type MgV2O4 shows a capacity of 200 mAh/g, corresponding to the cycling of ~0.7 mol Mg2+ per mol of oxide, and layered α-V2O5 reaches 300 mAhg-1, intercalating 1 mol Mg2+ per mol of oxide. The extent and reversibility of these reactions were confirmed by elemental, redox and structural characterization in recent work [1,2]. This high capacity is only observed at 110°C and it is accompanied by a large hysteresis in potential during the electrochemical cycling. The push to overcome these bottlenecks demands a more comprehensive definition of the underlying mechanisms of reaction than is currently available.
Previous X-ray Diffraction (XRD) measurements conducted on the oxide indicated a loss of reflection intensity due to a loss in their crystallinity which makes structural characterization using typical diffraction techniques difficult. Through this work, we mainly make use of pair distribution function techniques to study the changes in the local structures of these oxides in both their pristine and charged state, to find out the local symmetry is being preserved even at the cycled state, thus giving new insights in further pushing the efficiency of multivalent battery materials.
Reference:
1. Hu, L., Jokisaari, J.R., Kwon, B.J., Yin, L., Kim, S., Park, H., Lapidus, S.H., Klie, R.F., Key, B., Zapol, P. and Ingram, B.J., 2020. High capacity for Mg2+ deintercalation in spinel vanadium oxide nanocrystals. ACS Energy Letters, 5(8), pp.2721-2727.
2. Yoo, H.D., Jokisaari, J.R., Yu, Y.S., Kwon, B.J., Hu, L., Kim, S., Han, S.D., Lopez, M., Lapidus, S.H., Nolis, G.M. and Ingram, B.J., 2019. Intercalation of magnesium into a layered vanadium oxide with high capacity. ACS Energy Letters, 4(7), pp.1528-1534.
First Principles Calculation of Sodium Intercalation in Transition-Metal Dichalcogenides
Authors: Cao Jiangming , Mercer Michael P. , Silva Andrea , Kramer Denis 
Published: December 2024

Sodium ion batteries (SIBs) are an attractive substitute to lithium ion batteries, particularly for grid-scale energy storage, due to low cost and abundance of sodium [1]. Two-dimensional (2D) transition-metal dichalcogenides (TMDs) have evoked widespread attention as promising electrode materials [2], particularly as potential anode materials. Based on a database of 2D-TMDs, there is a need to determine the stability of 3D-TMDs before/after sodiation to optimise SIB anode materials.
In this work, using density functional theory (DFT) calculations, we conduct a systematic study of the series of TMDs for their electrochemical performance and structural properties based on 2D ground state structure of TMDs [3,4]. A voltage map is presented where the sodiated voltage of 3D-TMDs can be consulted, including p-MoS2, p-CdI2, p-NbTe2, p-WTe2, p-PdS2 and p-PdCl2 prototypes. With this voltage map, we can explore which TMDs can be as a suitable electrode materials for SIBs. Group VI elements (Mo, W) emerge as promising candidate from the voltage map. Further exploration of these candidates reveals that a prismatic → octahedral phase transition occurred during sodiation for CrS2, MoS2, CrSe2 and WS2, while MoSe2 and WSe2 show low voltage in prismatic coordination without phase transition. Some of Mo and W systems appearing to be promising anode materials because of relatively low voltage. However, phase transition during sodiation of CrS2, MoS2, CrSe2 and WS2 leads to an increase in voltage, making these less effective as anode materials.Additionally, the phase changes could be associated with other detrimental volume changes, hysteresis and possible degradation issues.

Keywords: transition-metal dichalcogenides, sodium-ion batteries, phase transition during sodiation, first principles calculation.

Reference

[1] Kundu, D., Talaie, E., Duffort, V. & Nazar, L. F. The emerging chemistry of sodium ion batteries for electrochemical energy storage. Angewandte Chemie - International Edition 54, 3432–3448 (2015).
[2] J Morales, J Santos, and J L Tirado. Electrochemical studies of lithium and sodium intercalation in MoSe2. Solid State Ionics, 83:57–64, 1996.
[3] Andrea Silva, Jiangming Cao, Tomas Polcar, and Denis Kramer. Design guidelines for two-dimensional transition metal dichalcogenide alloys. Chemistry of Materials, 34:10279–10290, 2022.
[4] Andrea Silva, Jiangming Cao, Tomas Polcar, and Denis Kramer. Pettifor maps of complex ternary two-dimensional transition metal sulfides. npj Computational Materials, 8(1):178, 2022.
Fluoride Ion Conductivity of Rb-Doped KSbF4
Authors: Kawahara Kazuaki , Ishikawa Ryo , Shibata Naoya , Ikuhara Yuichi 
Published: December 2024

All solid-state fluoride ion batteries (FIBs) are considered to be higher energy density and safer energy storages than the current lithium ion batteries [1]. There is a serious issue for practical use of FIBs i.e., the fluoride ion conductivities of solid-state electrolytes at room temperature are quite low (< 10-6 S cm-1), and operating temperature of FIB should be 420 K or higher [2]. Therefore, the faster fluoride ion conductors are strongly desired to operate FIB at room temperature. Potassium tetrafluoroantimonate (KSbF4) is a promising candidates that have a faster ionic conductivity [3].
In this study, we doped Rb into KSbF4 to expand conduction pathways in volume, and we investigated the composition dependence of ionic conductivity of K1-x
Rb
x
SbF4 by using electrochemical impedance spectroscopy. We found that ionic conductivity strongly depends on the chemical composition and conductivity is maximized at x = 0.15. The ionic conductivity at room temperature in the bulk and at the grain boundary at x = 0.15 were σbulk = 1.01 × 10-4 S cm-1 and σGB = 4.80 × 10-5 S cm-1, respectively [4].
Acknowledgement:
This presentation is based on results obtained from a project, JPNP21006, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).
References:
[1] M. A. Reddy, et al., J. Mater. Chem. 21, 17059 (2011).
[2] F. Gschwind, et al., J. Fluorine Chem. 182, 76 (2016).
[3] K. Kawahara, et al., J. Power Sour. 483, 229173 (2021).
[4] K. Kawahara, et al., J. Electrochem. Soc. 170, 020528 (2023).
Charge-Discharge Behavior of Spinel-Type Manganese Dioxide for Positive Electrode Materials for Aqueous Proton Batteries
Authors: Kida Yusuke , Ikezawa Atsunori , Okajima Takeyoshi , Arai Hajime 
Published: December 2024

Introduction

Rechargeable aqueous proton batteries function with proton insertion and extraction between two electrodes in acidic aqueous electrolytes. Since protons with small ionic radius and light molar mass are used as mobile ions, the battery has attracted attention for its possible high-rate charging performance. So far, a full cell of an aqueous proton battery with a voltage of 0.47 V class has been found using MoO3, an insertion-extraction type active material, in both electrodes. [1] It has been also reported that LiV3O8 works as a positive electrode material in proton cells. [2] On the other hand, it is desirable to find inexpensive electrode materials for practical use.
In this study, λ-MnO2, which is inexpensive and has high redox potential, was synthesized using a soft chemistry method, and its potential as a proton battery positive electrode was examined mainly through constant-current charge-discharge tests. We also attempted to elucidate the reaction mechanism by operando X-ray diffraction measurements.

Experiment

LiMn2O4 was synthesized by solid phase method using MnO and Li2CO3 as precursors. The active material, λ-MnO2, was obtained by chemical treatment of LiMn2O4 with H2SO4 solution prepared at pH=1. A composite electrode was prepared by coating and drying a slurry of active material (80 wt%), carbon black (10 wt%), and polyvinylidene difluoride (10 wt%) in N-methyl-2-pyrrolidone on a graphite sheet. A three-electrode cell was constructed using the prepared composite electrode as the working electrode, platinum mesh as the counter electrode, Ag/AgCl electrode as the reference electrode, and 50 wt% H2SO4 aqueous solution as the electrolyte solution, and charge-discharge tests were performed. Powder XRD measurements were performed for active material and electrode characterization.

R
esults and discussion

Fig. 1 shows the results of a constant-current charge-discharge test at 0.1 C. The material was found to be operated at potentials between 1.2 V and 1.7 V (vs. SHE) and has the potential to be cycled stably with a capacity of 200 mAh g-1. These results show that an electromotive force of more than 1 V, the highest value ever achieved for proton cells, can be achieved by using 50 wt% H2SO4 as the electrolyte and MoO3 as a negative electrode.
[1] A. Ikezawa, Y. Koyama, T. Nishizawa, and H. Arai, J. Mater. Chem. A . 11, 2360.(2023)
[2] A. Ikezawa, H. Xing, T. Hiramatsu, Y. Koyama, T. Nishizawa, T. Okajima and H. Arai, Abst. Asian Conf. Electrochem. Power Sources (2024).

Figure 1
Preparation and Electrochemical Properties of α-MgCu2O3
Authors: Miyazaki Yuzuru , Uehara Kazuma , Zihan Zhou , Huang Zhicheng , Hayashi Kei 
Published: December 2024

Magnesium cuprate MgCu2O3 (knowa as Guggenite) consists of undulated Cu-O networks, wherein square-planar CuO4 units share their edges to form Cu2O3 zigzag ladders. The Mg ions are situated between the Cu2O3 ladders and can be migrated two-dimensionally. Among the three known Guggenite-derivatives, the title compound usually involves off-stoichiometry; the Mg site is partially occupied by Cu and the chemical formula is thus represented as (Mg1-xCux)Cu2O3 [1,2]. In such a compound, the smooth migration of Mg ions could be prevented by the partially occupied Cu ions. Kobayashi [3] first investigated electrochemical properties of the samples prepared at 1000°C in oxygen. According to his thesis, Mg-extraction/insertion behaviour was observed at least three cycles. We have investigated the preparation conditions in detail and discovered that the single-phase region can be expanded by preparing samples above 1000°C in oxygen. Rietvled analyses using lab X-ray diffraction (XRD) have revealed that the x value can be lowered down to x < 0.10. Cyclic voltammetry (CV) measurements were performed using three electrode cells and 0.5 mol/L Mg(ClO4)2-acetonitrlie (AN) solutions. Working electrodes were prepared by mixing N-Methyl-2-Pyrrolidone (NMP) and the well-mixed powders of the cuprate samples, acetylene black (AN) and poly vinylidene fluoride (PVDF). Mg metal rods were used as counter and reference electrodes. Fig. 1 represents a partial cyclic voltammogram recorded at 20°C. The Mg extraction/insertion from/to the structure is clearly recognised at E~2.0-2.1 V vs. Mg2+/Mg even at around room temperature. Such charge/discharge reactions were reproducibly observed. More details of the preparation conditions, crystal structure and electrochemical properties will be presented in the conference.

References

[1] M. Winkelmann, H. A. Anderson, T. Zeiske, D. Hohlwein, Z. Kristallogr., 209 (1994) 870.
[2] K. Oh-ishi, Y. Tsuchiya, Y. Iizuka, H. Yamane, J. Solid State Chem., 160 (2001) 251.
[3] Fumiya Kobayashi, Graduation Thesis, School of Engineering, Tohoku University, (2010), (in Japanese).

Figure 1
Detection of Vitiligo Through Machine Learning and Computer‐Aided Techniques: A Systematic Review
Authors: Tanvir Sania , Syed Sidra Abid , Hussain Samreen , Zia Razia , Rashid Munaf , Zahid Hira 
Published: December 2024

Background and Objective: Vitiligo is a chronic skin damage disease, triggered by differential melanocyte death. Vitiligo (0.5%–1% of the population) is one of the most severe skin conditions. In general, the foundation of the condition of vitiligo remains gradual patchy loss of skin pigmentation, overlying blood, and sometimes mucus. This paper provides a systematic review of the relevant publications and conference papers based on the subject of vitiligo diagnosis and confirmation through computer‐aided machine learning (ML) techniques.Materials and Methods: A search was conducted using a predetermined set of keywords across three databases, namely, Science Direct, PubMed, and IEEE Xplore. The selection process involved the application of eligibility criteria, which led to the inclusion of research published in reputable journals and conference proceedings up until June 2024. These selected papers were then subjected to full‐text screening for additional analysis. Research publications that involved application of ML techniques with targeted population of vitiligo were selected for further systematic review.Results: Ten selected and screened studies are included in this systematic review after applying eligibility criteria along with inclusion and exclusion criteria applied on initial search result which was 244 studies based on vitiligo. Priority is given to those studies only which use ML techniques to perform detection and diagnosis on vitiligo‐targeted population. Data analysis was carried out only from the selected and screened research articles that were published in authentic journals and conference proceedings.Conclusion: The importance of applying ML techniques in the clinical diagnosis of vitiligo can give more accurate results and at the same also eliminate the need of biased human judgement. Based on a comprehensive examination of the research, encompassing the methodologies employed and the metrics utilized to assess outcomes, it was determined that there is a need for further research and investigation regarding the application of ML algorithm for the detection and diagnosis of vitiligo with different datasets and more feature extraction.
Effectiveness of Posterior Decompression and Internal Fixation in Emergency Management of Thoracolumbar Fractures Complicated by Spinal Cord Injury
Authors: Li Jian , Zhou Tao , Lin Sen , Wang Hongliang 
Published: December 2024

Objective: This study evaluates the effectiveness and timeliness of posterior decompression and internal fixation in the emergency management of thoracolumbar fractures complicated by spinal cord injuries.Methods: We retrospectively analyzed 40 patients treated at our hospital from January 2019 to February 2022. Each patient underwent posterior decompression and internal fixation, with preoperative and postoperative assessments including vertebral body height, American Spinal Injury Association (ASIA) score, Visual Analog Scale (VAS) score, and urodynamic indices.Results: Postoperative improvements were noted in vertebral body height, with anterior and posterior heights increasing to 12.82 (± 1.23) mm and 3.21 (± 0.64) mm, respectively, and kyphosis angle improving to 14.26 (± 0.32). Significant enhancements were also observed in motor (from 40.78 [± 4.32] to 59.86 [± 1.37]) and sensory (from 45.98 [± 3.20] to 66.92 [± 1.28]) function scores, and a reduction in VAS score from 6.89 (± 0.78) to 1.78 (± 0.32). Urodynamic measurements showed increased maximum urine flow and detrusor pressure postintervention. All surgical wounds healed within two weeks without significant complications.Conclusion: Posterior decompression and internal fixation significantly improve spinal stability, pain, motor, and sensory functions in patients with thoracolumbar fractures and spinal cord injuries, demonstrating its effectiveness and clinical utility.
Bmal1-Mediated Circadian MELK Expression Potentiates MELK Inhibitor Chronotherapy for Esophageal Cancer
Authors: Zeng Boning , Sun Chao , Tang Qian , Li Nan , Chen Siying , Yang Yili , Wang Xiao , Wang Shaoxiang 
Published: December 2024

Abstract
Esophageal squamous cell carcinoma (ESCC) remains a global health challenge. Circadian clock and maternal embryonic leucine zipper kinase (MELK) play a key role in tumorigenesis. However, a link between circadian clock dysregulation and MELK function in the occurrence and development of ESCC remains elusive. Here, In the in vivo and in vitro systems, we found for the first time that MELK exhibits pronounced circadian rhythms expression in mice esophageal tissue, xenograft model, and human ESCC cells. The diurnal differences expression between peak (ZT0) and trough (ZT12) points in normal esophageal tissue is nearly 10-fold. Circadian expression of MELK in ESCC cells was regulated by Bmal1 through binding to the MELK promoter. Supporting this, the levels of MELK were increased significantly in patients with ESCC and were accompanied by altered expression of core clock genes, especially, since Bmal1 is prominently upregulated. Most importantly, Bmal1-deleted eliminated the rhythmic expression of MELK, whereas the knockdown of other core genes had no effect on MELK expression. Furthermore, in nude mice with transplanted tumors, the anticancer effect of OTS167 at ZT0 administration is twice that of ZT12.
Implications: Our findings suggest that MELK represents a therapeutic target, and can as a regulator of circadian control ESCC growth, with these findings advance our understanding of the clinical potential of chronotherapy and the importance of time-based MELK inhibition in cancer treatment.
Do Languages Have Exclusive Disjunctions?
Authors: Nicolae Andreea C. , Petrenco Aliona , Tsilia Anastasia , Marty Paul 
Published: December 2024

Abstract
Most natural languages have more than one linguistic form available to express disjunction. One of these forms is often reported by native speakers to be more exclusive than the other(s) and, in recent years, it has been claimed that some languages may in fact have dedicated exclusive disjunctions. In this paper, we report on a series of experiments testing this claim across five languages of primary interest. Results show important variation in the rates of exclusive interpretation associated with the different particles used to express disjunction in these languages. Crucially, our findings show that, while complex disjunctions are usually perceived as more exclusive than their simple counterparts cross-linguistically, even the most exclusive disjunctions remain ambiguous between an inclusive and an exclusive interpretation. We discuss what factors may play a role in accounting for the gradient exclusivity effects observed in our data and how to model these effects in pragmatic and grammatical accounts of scalar implicatures.