bluuebunny/crossref_metadata_2025_split huggingface dataset:
Impact of Cationic Sizes on the Capacitance and Interfacial Structure of ‘Water-in-Salt’ Electrolytes on Graphene
Authors: Khan Md Sharif , Andreussi Oliviero 
Published: December 2024

Electrochemical double-layer capacitors (EDLCs), which store charge by electrostatic adsorption of the ions at the vicinity of the electrode/electrolyte interface, have become promising energy storage devices due to their high charge / discharge rates, power density, substantial energy density, and long cycling performance. However, the overall performance of an EDLC is significantly influenced by the nature of the electrolytes employed. Among the various liquid electrolytes, organic solvents and ionic liquids have complicated manufacturing processes and high safety concerns, despite their large working potential window. On the opposite, conventional aqueous electrolytes possess high ionic conductivity, higher safety, while allowing a simpler preparation process. However, the performance of the aqueous electrolytes is significantly hampered due to their low redox potential (1.23 V) for electrochemical H2O splitting. A compromise between these alternatives may be represented by water-in-salt electrolytes (WISEs), a class of superconcentrated aqueous electrolytes with water/salt mass and volume ratios greater than 1. By minimizing the presence of free water at the electrode interface, WISEs can substantially elevate the redox potential of aqueous electrolytes to as high as 4.0 V, thereby overcoming the limitations posed by traditional aqueous electrolytes and enabling enhanced performance in EDLCs.
In this study, molecular dynamics simulations in the presence of a constant applied potential were used to investigate an electrochemical cell comprising WISEs at a concentration of 20 mol/kg, situated between two single-layer graphene electrodes. Various cations, including Li+, Na+, and K+, were examined to evaluate the influence of cationic size in conjunction with the common TFSI anion. Our detailed analysis revealed that K+ exhibited a greater tendency for adsorption onto the electrodes than Li+ and Na+, resulting in the highest integral capacitance. The bigger size and lower charge density in the periphery of K+ facilitate its ability to overcome the strong ion pair interaction and accumulate more closely to the electrode surface. The atomistic level changes at the interface and the electrochemical potential window stability were also investigated using first-principles simulations and a continuum model for the electrochemical environment. Overall, our molecular dynamics and continuum model simulations provide a detailed picture of the capacitive behavior, interfacial structure, and electrochemical potential window stability of water-in-salt electrolytes of varying cationic sizes on single layer graphene electrodes. This understanding will significantly advance the future development of this type of electrolytes.
Evaluating Redox Flow Battery Field Designs with the Vanadium Acetylacetonate Chemistry
Authors: Rungta Rohit , Monroe Charles W. 
Published: December 2024

Among various battery systems, redox flow batteries (RFBs) have been shown to be a particularly promising technology for large-scale stationary energy storage applications due to their unique advantages in terms of their long cycle life and modular design. RFBs, however, are significantly different from conventional batteries in operating principle, while many engineering aspects have been carried over from similar systems such as fuel cells. This study explores flow field design, a commonly overlooked practical aspect of flow batteries, from first principles.
Countercurrent flow is commonly used for many engineering applications where large concentration or temperature gradients are to be minimized. In flow batteries, the opposite is desired. The nonaqueous flow-battery chemistry based on V(acac)3 (vanadium acetylacetonate) disproportionation [1,2] is used in a flow reactor as a test bed for assessing countercurrent vs co-current flow. Figure 1 demonstrates two flow fields that are tested to understand the impacts of high per-pass conversion and low per-pass conversion on overall cell performance and their tolerable current densities. Insights from these experiments are then used to create novel, 3D-printed flow field designs. Cell performance of the 3D-printed flow fields is assessed against the traditional serpentine and interdigitated flow fields that are ubiquitously used throughout RFB and fuel-cell applications.

References

[1] Q. Liu, A. E. S. Sleightholme, A. A. Shinkle, Y. Li, and L. T. Thompson, "Non-aqueous vanadium acetylacetonate electrolyte for redox flow batteries", Electrochem. Commun., 11 (12), Dec. 2009.
[2] J. D. Saraidaridis and C.W. Monroe, “Nonaqueous vanadium disproportionation flow batteries with porous separators cycle stably and tolerate high current density,” Journal of Power Sources
412 (2019) 384–390.

Figure 1
Preparation, Crystal Structure and Electrochemical Properties of Mg1-X
Cu2+X
O3
Authors: Uehara Kazuma , Zihan Zhou , Huang Zhicheng , Hayashi Kei , Miyazaki Yuzuru 
Published: December 2024

Magnesium copper oxide MgCu2O3 belongs to the space group Pmmn (setting 2) and has a crystal structure (GA phase) consisting of zigzag edge-sharing CuO4 planes arranged in 2D Cu2O3 layers and MgO6 octahedra. The Mg2+ between the Cu2O3 layers can be inserted and removed in the crystallographic c-axis direction as shown in Fig. 1. Hence, MgCu2O3 can be a potential cathode material for magnesium ion batteries. According to M. Paranthaman et al., the crystal structure changes depending on sintering temperature; apart from the GA phase, there are phases called GB and GX whose detailed crystal structures have not been elucidated [1]. MgCu2O3 can also be synthesized as a single-phase by partially substituting Cu for the Mg(2a) site. The detailed chemical formula is then expressed as Mg1-x
Cu2+x
O3. Such a partial substitution of Cu inhibits Mg conduction and would reduce electrical capacity, samples with higher Mg occupancy are needed. Kobayashi first investigated the electrochemical characteristics of the GA phase, and reported that the electrical capacity of 31 mAh/g and the potential of 0.7 V vs. Mg/Mg2+ [2]. Since different results for the single-phase composition of the GA phase have been reported [3], we determined the single-phase compositional range of the GA phase by varying the sintering temperature in oxygen stream. We also analyzed the crystal structure of the GA phase, in particular the Mg occupancy at the 2a site. The samples were prepared using MgO and CuO reagents, weighed in the desired ratio. Sintering was performed at 1000, 1030, and 1050℃. Powder X-ray diffraction and Rietveld analysis were used for crystal structure analysis. Battery performance was evaluated using three electrode cells by means of cyclic voltammetry (CV). When annealed at 1000℃, the lower limit value x of the single-phase region of the GA phase was 0.13. For the x=0.13 sample, the occupancy of Mg at the Mg site was 84.2%, and the occupancy of Mg decreased as x increased. The electrical capacity was 72 mAh/g and the potential was 2.0 V vs. Mg/Mg2+ for this sample. By increasing the sintering temperature, the single-phase composition range widened and the Mg occupancy at the Mg site increased. At the conference, we will also report the results of single-phase region and crystal structure analysis of samples sintered at 1030℃ and 1050℃, as well as the results of CV measurements.
Reference
[1] M. Paranthaman, K. A. David and T. B. Lindemer, Materials Research Bulletin, 32, 165 (1997).
[2] F. Kobayashi, Graduation Theses, School of Engineering, Tohoku University, (2010).
[3] K. Oh-ishi, Y. Tsuchiya, Y. Iizuka and H. Yamane, J. Solid State Chem., 160, 251 (2001).
Caption
Figure 1. Crystal structure and Mg conduction pathway (yellow-curved surface) in MgCu2O3. (blue and red circles represent Cu and O atoms, respectively)

Figure 1
Ionic Liquid As an Electrolyte Solvent for Proton Rechargeable Batteries
Authors: Shimizu Masahiro , Ichikawa Tomonori , Tsuchikane Koki 
Published: December 2024

The diversity of carrier ions in electrochemical devices has attracted much attention to the use of protons.1−3 However, the narrow potential window of acid-based aqueous solutions typically used as proton conductors limits the operation of active materials.4 In this work, we examined the applicability of ionic liquids consisting of bis(trifluoromethanesulfonyl)amide (TFSA−) combined with N-propyl-N-methylpyrrolidinium (Pyr1,3
+) or 1-ethyl-3-methylimidazolium (EMI+), as the electrolytes. Raman spectroscopic measurements revealed that protons undergo coordination by TFSA− to form anionic complex of [H(TFSA)
x
]1–x
(Figure 1a). The addition of HTFSA narrowed the electrochemical windows compared with those of neat ionic liquids. However, the electrolytes allowed electrochemical H-adsorption/desorption on Pt (working electrode) within the electrochemical windows, which was investigated using quartz crystal microbalance technique. The ionic liquid electrolytes of [HTFSA]0.1[Cation-TFSA]0.9 were applied to rutile TiO2 composite electrodes. Comparing the charge/discharge property in an aqueous electrolyte, ionic liquid decreased the irreversible H2 evolution and the resulting non-electrochemical H+-extraction to show a reversible capacity of ca. 190 mA h g–1 at the first cycle (Figure 1b).
Acknowledgement
This work was supported by a Grant-in-Aid for Scientific Research (B) (24K01601) from the Japan Society for the Promotion of Science (JSPS).
References

Wang, Y. Xie, K. Tang, C. Wang, C. Yan, Angew. Chem. Int. Ed., 57 (2018) 11569.

B. Mitchell, W. C. Lo, A. Genc, J. LeBeau, V. Augustyn, Chem. Mater., 29 (2017) 3928.

Makivić, J.-Y. Cho, K. D. Harris, J.-M. Tarascon, B. Limoges, V. Balland, Chem. Mater., 33 (2021) 3436.

Shimizu, D. Nishida, A. Kikuchi, S. Arai, J. Phys. Chem. C, 127 (2023) 17677.

Figure 1
Non-Aqueous Calcium-Based Dual-Ion Batteries with an Organic Electrode of High-Rate Performance
Authors: Jao Wen-Yang , Tai Chen-Wei , Hu Chi-Chang 
Published: December 2024

Energy issues have become one of the most critical topics in human society to maintain sustainable development. More specifically, the increasing demand for energy speeds up the evolution of energy storage devices, such as batteries and supercapacitors. Accordingly, lithium-ion batteries became the mainstream energy storage device because of the high demands of electric vehicles and diverse electronic devices. However, the subsequent concerns regarding the abundance, safety, cost, efficiency, and sustainability issues behind the vast daily energy demands initiate the research on the post-lithium-ion batteries in the recent decade. Among them, multivalent batteries based on calcium ions draws lots of attention as a promising energy storage system due to its high earth abundance and improved ionic mobility compared to magnesium ions. Nevertheless, the critical challenge is to solve the incompatibility between the metallic calcium electrode and conventional electrolytes as well as the scarcity of high-rate performance electrode materials for hosting calcium ions simultaneously to construct a practical energy storage device.
Herein, we firstly investigate a small molecular organic material, 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), as the calcium-ion host for calcium-ion batteries (CIBs) in the non-aqueous electrolyte. Spectroscopic, structural, and computational studies reveal that PTCDI with an enhanced Ca2+-storage degree can increase the solubility of reduced PTCDI due to the reduced π-π interaction, suppressed by the saturated electrolyte owing to the high redeposition rate to form a PTCDI film with strengthened hydrogen bonds, which facilitates a fast enolization reaction for Ca2+ storage. Furthermore, the compatibility issue among the metallic Ca, conventional calcium-based electrolyte, and PTCDI was unraveled by employing graphite type material, namely mesocarbon microbead (MCMB), as the positive electrodes for facilitating anion intercalation, as opposed to the utilization of calcium metal negative electrode for Ca2+ plating/stripping. Consequently, a cell assembled with the PTCDI negative electrode and carbon-based positive electrode, as illustrated in Figure 1, exhibits a high-power density >3000 W kg-1, a high energy density of ~150 Wh kg-1, and superior reversible capacity of 80 mAh g-1 at 5 A g-1. The assembled CIB even demonstrates the high-rate performance (90 mAh g-1 at 1 A g-1) and ultra-stable cyclability over 4000 cycles with negligible decay at -10 °C, suggesting the promising future as low-temperature batteries.

Figure 1
Positive Electrode Behavior of Manganese Dioxide in Alkaline Aqueous Electrolyte Solution
Authors: Okada Masaki , Morita Masayuki , Ogumi Zempachi , Abe Takeshi 
Published: December 2024

Aqueous secondary batteries that use zinc as the negative electrode are considered suitable for automotive batteries, which require high safety, high energy density, and low cost. An aqueous battery using zinc for the negative electrode has long been put into practical use as a manganese primary battery using manganese dioxide (MnO2) for the positive electrode. Since MnO2 can reduce Mn4+ to Mn2+ in an aqueous electrolyte, if this reaction can be reversibly used, it may be a promising candidate material for the high-energy-density positive electrode of aqueous zinc secondary batteries. In this presentation, we report the results of a study of charge-discharge behavior of MnO2 positive electrode in alkaline aqueous electrolyte solutions used in primary manganese batteries. In this research, positive electrode performance was measured using a three-electrode method. A mixture of commercially available electrolytic manganese dioxide (EMD), acetylene black (AB) and Polytetrafluoroethylene (PTFE) was used as the working electrode. Zinc or Platinum plate was used as counter electrode, and Hg | HgO electrode was used as the reference electrode. The structural changes of the EMD and the identification of the reaction products were investigated by ex-situ XRD measurements. From the evaluation results of several samples, it was found that the EMD with a larger amount of structural water shows a higher electrochemical capacity. Furthermore, among the EMDs evaluated, it was found that the two-electron redox reaction of Mn proceeds reversibly in EMDs with a large amount of structural water. In the presentation, we will report on changes in the crystal structure of MnO2 due to Mn redox, changes in electrolyte composition, and the effects of electrolyte composition on performance.
Acknowledgments： This research was conducted under the project "Development of Innovative Storage Batteries for Electric Vehicles (RISING3)" (JPNP21006) commissioned by the New Energy and Industrial Technology Development Organization (NEDO). We would like to express our gratitude to all parties involved.
Crafting a Reversible Zinc Metal Anode: The Impact of Organic Electrolyte Additives in Solid Electrolyte Interface Formation
Authors: Kakoty Bhaskar , V Rishikesh , Ahuja Vinita , Mukherji Srimayee , Balasubramanian Sundaram , Joseph Anjana , Narayana Chandrahas , Senguttuvan Premkumar 
Published: December 2024

Li ion batteries are appealing for their high energy density and high working potential, however, concerns regarding their expense, access to raw materials and safety have steered researchers towards exploring new sustainable, clean, cost effective and efficient energy storage system.1 Within this domain, aqueous zinc metal battery has emerged as potential candidate due to its impressive specific capacity, low redox potential, environmental sustainability, and cost-effectiveness. Nevertheless, impediments such as corrosion of Zn anode, excessive dendrite formation, hydrogen evolution and dissolution of cathodes impose constraints on their applicability.2 To tackle these challenges, numerous investigations show utilization of organic molecules (Triethyl Phosphate3, Pyridine4) as additives or cosolvents. However, the use of high concentration salt and various organic additives reduces the ionic conductivity of the electrolytes and negatively impacts the cost and energy density of the battery.
Along this line, we have delved into electrochemical properties of hybrid electrolyte composed of water and propylene carbonate, and their ability to form solid electrolyte interphase (SEI). Through this exploration, we've noted a remarkable improvement in battery characteristics such as high coulombic efficiency and stable capacity. By introducing a small amount of propylene carbonate, we have observed substitution of water molecules solvating Zn2+ ions with additives and triflate anions. This led to electrochemical reduction of solvated Zn ion species, forming a solid electrolyte interphase rich in ZnF2 as confirmed by XPS. Moreover, spectroscopic investigations indicate a significant interaction between the highly basic carbonyl oxygen moiety of propylene carbonate (PC) and water molecules, thereby mitigating the dissolution of the cathode.5 This phenomenon facilitates the attainment of remarkable specific capacity of approximately 300 mAh g-1 over the course of 900 cycles at a current density of 1 A g-1. Furthermore, we emphasize the significance of considering the dielectric constant and polarity of an additive or cosolvent in evaluating the performance of the electrolyte for aqueous zinc ion batteries.
Reference:

O. Schmidt, A. Hawkes, A. Gambhir, and I. Staffell, Nature Energy, 2, 1–8 (2017)

V. Verma, S. Kumar, W. Manalastas, Jr., and M. Srinivasan, ACS Energy Lett., 6, 1773−1785 (2021).

S. Liu, J. Mao, W. K. Pang, J. Vongsvivut, X. Zeng, L. Thomsen, Y. Wang, J. Liu, D. Li, and Z. Guo, Adv. Func. Mater., 31, 2104281 (2021).

J. Luo, L. Xu, Y. Zhou, T. Yan, Y. Shao, D. Yang, L. Zhang, Z. Xia, T. Wang, L. Zhang, T Cheng, and Y. Shao, Angew. Chem. Int. Ed., 62, e202302302, (2023).

B. Kakoty, R. Vengarathody, S. Mukherji, V. Ahuja, A. Joseph, C. Narayana, S. Balasubramanian, and P. Senguttuvan, J. Mater. Chem. A, 10, 12597–12607 (2022)
A Preliminary Study on Transcriptional Regulation of SNP Site C‐1888T in the Promoter Region of Human PLUNC Gene and Nasopharyngeal Carcinoma Susceptibility
Authors: Liu Beina , Wang Rong , He Ying 
Published: December 2024

Purpose: The transcriptional regulatory factors binding to the polymorphic site C‐1888T in the promoter region of the palate, lung, and nasal epithelium clone (PLUNC) gene were identified to investigate whether the C‐1888T polymorphic site affects the transcriptional regulation and function of PLUNC gene.Materials and Methods: Three genotypes of C‐1888T polymorphic locus were screened from established nasopharyngeal carcinoma (NPC) cells, and the mRNA expression levels of PLUNC gene in different genotypes were detected. The respective transcription factors that were more likely to bind with A or G in SNP were predicted by biological information and preliminarily verified in vitro by gel electrophoresis migration rate analysis. Ulteriorly, the NPC cell lines were analyzed through chromatin immunoprecipitation combined with PCR amplification to confirm that the transcription factors could bind to the PLUNC gene promoter.Results: The cell lines 5–8F, 6–10B, CNE1, and CNE2 were heterozygous CT type, SUNE1 was homozygous CC type, and C666‐1 was homozygous TT type. The expression of PLUNC gene was significantly different among all cell lines (F = 33.844, p < 0.001), and the gene expression level of CC type was significantly lower than TT type (p < 0.001). Gel electrophoresis mobility analysis confirmed that the transcription factors XFD3 and EVI1 could bind to the PLUNC gene promoter when the SNP was A and G, respectively. PCR amplification combined with chromatin immunoprecipitation showed that EVI1 could bind to the DNA fragment of the promoter region of PLUNC gene in SUNE1 NPC cells.Conclusion: The transcription factors XFD3 and EVI1 may be involved in the transcriptional regulation of PLUNC gene, and EVI1 can bind to the promoter region of PLUNC gene in SUNE1 NPC cells, thus associated with the susceptibility/risk of NPC.
Measurements of Objective Cyclotorsion in a Population of Healthy Children
Authors: Lin Hsu-Ying , Wu Wei-Chi , Sun Ming-Hui , Lin Jui-Yen , Huang Ping-Hsuan , Liu Chun-Hsiu 
Published: December 2024

Introduction: This study aimed to compare ocular torsion measurements to investigate normative objective cyclotorsion values in a population of healthy, full‐term and preterm children.Materials and Methods: The participants enrolled in this study had an age range of 3–12 years and were divided into two groups, full‐term (gestational age (GA) > 37 weeks) and preterm without retinopathy of prematurity (ROP) (GA ≤ 37 weeks). The disc‐center‐fovea angle (DFA) was used to evaluate ocular torsion using two different imaging modalities: optical coherence tomography (OCT) with a 55‐degree field of view (FV) and conventional fundus photography (CFP) with a 45‐degree FV. The values measured from both right and left eyes were combined to obtain a single value to compensate for the effect of head tilt during measurement.Results: A total of 86 full‐term and 145 preterm children were enrolled in this study. The DFAs measured using OCT and CFP were −11.57° ± 5.27° and −12.07° ± 5.66° in the full‐term group and −10.64° ± 5.40° and −11.25° ± 4.80° in the preterm group, respectively. There were no significant differences between the results obtained from OCT and CFP in the two groups (p = 0.109 and p = 0.512, respectively). There was a strong correlation between OCT and CFP in all patients, with a Pearson’s correlation coefficient of 0.74 and an intraclass correlation coefficient (ICC) of 0.74 (both p < 0.001). Multivariate regression analysis showed that the average axial length (AXL) was associated with DFA.Conclusions: This study found a significant correlation between DFA measured using OCT and CFP, making either measurement modality feasible in pediatric populations. There was no significant difference in the DFA between full‐term and preterm children. AXL demonstrated an association with the DFA.
Histologic and Immunologic Factors Associated with Response to Immune Checkpoint Inhibitors in Advanced Sarcoma
Authors: Lee Alex Q. , Hao Clara , Pan Minggui , Ganjoo Kristen N. , Bui Nam Q. 
Published: December 2024

Abstract

Purpose:
To characterize factors associated with response to immune checkpoint inhibitors (ICI) in advanced sarcoma.

Experimental Design:
This is a retrospective study with a cohort of 216 patients with advanced sarcoma treated with ICI between 2016 and 2023 at Stanford Health Care. Overall survival, progression-free survival (PFS), objective response rates (ORR) per RECIST criteria, and reason for ICI discontinuation were analyzed across histologic subtypes, ICI regimens, tumor mutational burden, and PD-L1 expression.

Results:
The overall ORR in the cohort was 16.7%. The histologic subtypes with the highest ORR were Kaposi sarcoma (KS, 66.7%), alveolar soft part sarcoma (ASPS, 50%), angiosarcoma (33.3%), myxofibrosarcoma (MFS, 28.6%), and undifferentiated pleomorphic sarcoma (UPS, 27.8%). The subtypes with the lowest ORR were osteosarcoma (0%), synovial sarcoma (0%), and liposarcoma (3.7%). The subtypes with the highest median PFS were KS (median not reached), ASPS (median not reached), MFS (27.4 months), and UPS (11.3 months). The ORR for sarcomas with PD-L1 ≥ 1% was 27.8% (P = 0.02), whereas the ORR for sarcomas with tumor mutational burden ≥10 mutations per megabase of DNA was 28.6% (P = 0.20).

Conclusions:
ORR and PFS were highly variable across sarcoma histologic subtypes. In this large analysis, KS, ASPS, angiosarcoma, MFS, and UPS demonstrated the highest ORR and longest PFS while osteosarcoma, synovial sarcoma, and liposarcoma had the lowest ORR and shortest PFS. PD-L1 expression was also associated with increased ORR. Our findings provide further insight into understanding the sarcoma histologic and immunologic factors that correspond with response to ICI.