bluuebunny/crossref_metadata_2025_split huggingface dataset:
Molybdenum-Catalyzed Electrochemical Ammonia Synthesis Using Zero-Gap Electrolysis Cell
Authors: Kiyota Yasuhiro , Tamura Jun , Oki Mitsuhiro , Yoshiki Masahiko , Arashiba Kazuya , Nishibayashi Yoshiaki , Sugano Yoshitsune 
Published: December 2024

Ammonia, which is a valuable material not only as a fertilizer but also as a potential alternative to fossil fuels has been conventionally synthesized under high temperature and pressure conditions by the Haber-Bosch method. Recently, an innovative method for the synthesis of ammonia from water and nitrogen under ambient conditions using Mo complexes has been reported.[1] In this study, a cathode supported by the Mo complex was prepared and the electrochemical production of ammonia was demonstrated using a zero-gap electrolysis cell.
A catalyst layer consisting of porous carbon was spray coated on carbon paper. The Mo complex [MoI3(PCP)] (PCP: 1,3-bis((di-tert-butylphosphino)methyl)benzimidazol-2-ylidene) was supported on the carbon substrate by immersion. A 4-cm2 zero-gap electrolysis cell was constructed using the cathode, an ion-exchange membrane and IrOx-loaded Ti nonwoven fabric as the anode.
The nitrogen reduction reaction (NRR) was performed at constant current by supplying nitrogen gas to the cathode and K2SO4 electrolyte to the anode. Ammonia produced at the cathode was collected by a H2SO4 trap at the cathode outlet, which was changed every 5 minutes. When 50 mA/cm2 was applied, the ammonia production rate was maximized in the 10-15 minutes, with an ammonia production partial current density of 2.9 mA/cm2, a Faraday efficiency of 5.7%, and a cell voltage of 3.1 V. A high ammonia production rates (over 1000 µg mg-1 h-1) was achieved among aqueous electrochemical NRR.[2] Further improvements of the NRR electrolyzer and results of XAFS analysis of Mo complexes are also presented.
This paper is based on results obtained from a project, JPNP21020, commissioned by the New Energy and Industrial Technology Development Organization (NEDO).
[1] Y. Ashida, K. Arashiba, K. Nakajima et al., Nature
568, 536 (2019).
[2] H. Shen, C. Choi, J. Masa et al., Chem
7, 1708 (2021).

Figure 1
(Digital Presentation) Performance of a Paper-Based Microfluidic Fuel Cell Using Eco-Friendly LaFeO3 and CaFe2O4 Nanoparticles as Anode
Authors: Prado Hernandez Victor Manuel , Castellanos Bernal Cindy Vanessa , Gómez Lara Kevin Steven , Dector Andrés , Morales Jimmy 
Published: December 2024

Renewable energy generation is an innovative approach that uses the electrochemical properties of substances that can be used as fuels, for example, urine and in addition to mixed metal oxides for the generation of energy from fuel cells based on synthetic urine. In this study, energy generation was carried out in a synthetic urine sample, using ferrites of the CaFe2O4 and LaFeO3 type as anode. These materials act as sensors that react with the analytes present in the urine sample, producing a detectable electrical signal. In the study, a cell with two electrodes was used, one made of platinum (cathode) and another made of synthesized material (anode). The synthesized materials were prepared using a mixture of nitrates, and the synthetic urine sample, which was deposited on a paper microfluidic fuel cell design. Six assemblies were carried out and the results were satisfactory for the study.
References

Saputra, H. A. (2023). Electrochemical sensors: basic principles, engineering, and state of the art. Monatshefte Fur Chemie, 154(10), 1083–1100

Salih, S.J.; Mahmood W.M. Review on magnetic spinel ferrite (MFe2O4) nanoparticles: From synthesis to application, Heliyon 2023, 9, e16601

Pandiyan, R., Vinothkumar, V., Chen, S. M., Sangili, A., & Kim, T. H. (2023). Integrated LaFeO3/rGO nanocomposite for the sensitive electrochemical detection of antibiotic drug metronidazole in urine and milk samples. Applied Surface Science, 635, 157672

Nemati, S. S., Salemi-Seresht, M., Abdi, Y., & Dehghan, G. (2024). Highly sensitive and label-free detection of naproxen using mixed metal oxide-based field effect transistor as a biosensor for in-vitro analysis of urine. Materials Science in Semiconductor Processing, 179, 108487
Geometrical and Electronic Structures of Red Phosphors Doped with 3d Transition Metals
Authors: Yamamoto Tomoyuki , Hirano Moe , Nematov Dilshod , Burkhonzoda Amondulloi , Umar Zafari , Brik Mikhail G. 
Published: December 2024

Phosphors have become increasingly important in our lives with the spread of white LEDs in recent years. The most basic structure of a white LED is a combination of a blue LED and a yellow phosphor, but this combination results in a white color with a high color temperature that leans toward bluish-white. Therefore, red and green phosphors are demanding in order to adjust the color temperature and improve color rendering property. In addition to the demands of high efficiency and long-term stability for such phosphors, it is also important that the raw materials are low-priced. Many red phosphors achieve red fluorescence by adding a few percent or less concentration of rare earth elements. However, their supply may become unstable, since rare earth elements are unevenly distributed in certain regions of the earth. Therefore, it is requested that the phosphors without rare-earth elements. Recently we have reported stable rare-earth free res phosphors using 3d transition metals with 3d3 configuration, such as Cr3+ and Mn4+, to replace rare-earth elements [1-3]. In the current study, geometrical and electronic structures of phosphor materials doped with Cr3+ and Mn4+ are demonstrated both experimentally and theoretically. Especially, we focus upon the local environment of doped 3d transition element, which are studied in detail by X-ray absorption near edge structure (XANES) and electron spin resonance (ESR) analysis with the aid of the first-principles calculations.
References
[1] M.S. Kurboniyon et al., Phys. Status Solidi B260 (2023) 2200575.
[2] U. Zafari et al., Opt. Mater.: X 16 (2022) 100197.
[3] M. Sagayama et al., ECS J. Solid State Sci. Tech. 10 (2021) 076004.
First-Principles Analysis of the Influence of the Valence on the Optical Spectra of Uranium Ions in Oxide Crystals
Authors: Masago Toshiki , Ogasawara Kazuyoshi 
Published: December 2024

Recently U6+-doped oxide green phosphors are attracting attentions for the white LED application. However, the absorption and emission mechanisms in some of these materials are still unclear. For the development of the novel uranium-doped phosphors, clarification of the origins of the peaks in the absorption and emission spectra of these materials is indispensable.
In our previous research, we investigated the origin of the peaks in the optical spectra of uranium ions in some oxide crystals by comparing the experimental spectra with the theoretical ones obtained by first-principles calculations. The results indicated that there is a U-doped phosphor whose spectrum seems to originate from 5f-6d transitions of U3+ instead of LMCT transitions of U6+. In this work, in order to investigate the influence of the valence of uranium ions, we created some hypothetical model clusters representing uranium ions in oxides and performed first-principles calculations for the LMCT transitions of U6+ and the 5f-6d transitions of U3+ using the relativistic discrete-variational multi-electron (DVME) code which is a configuration-interaction calculation program based on the four-component fully relativistic wave functions obtained by the relativistic discrete-variational Xα (DV-Xα) molecular orbital method. The effects of coordination numbers and bond distances on valence of uranium ions were also investigated in detail by performing calculations using model clusters with coordination numbers from 6 to 12.
An Investigation of Cell Death Induced By Electrochemical Stimulation in Ovarian Cancer
Authors: Yang Zongyu , Wang Fu-Ming 
Published: December 2024

Recent research has focused on ion-permeable channels in cancer, aiming to reduce proliferation and induce apoptosis in cells. Voltage-gated calcium channel blockers [1] and ligand-gated ion/calcium channels [2,3] have been explored. By maintaining low cytoplasmic calcium concentrations at rest and mobilizing calcium in response to stimuli, calcium ions serve as second messengers, regulating diverse cellular stimulus-response reactions [4]. Disruptions in intracellular calcium homeostasis can impact cell proliferation and trigger programmed cell death.
In our study, we cultured ovarian cancer (ES-2 cells) on indium tin oxide (ITO)-coated glass as a working electrode. We optimized parameters, including membrane potential amplitude (±60 mV), pulse frequency (1 to 36 times), and duration (2 to 60 seconds). Fig. 1a shows that a single depolarization pulse increases the highest intracellular calcium levels in ES-2 cells. After 24 hours of depolarizing stimulation, the survival rate of ES-2 cells is 66.0±6.2% for single pulses and 74.7±3.7% for multiple pulses. In contrast, the survival rate following hyperpolarization electrical stimulation is 86.3±5.6% for single pulses and 76.5±2.0% for multiple pulses. Fig. 1b indicates that sequential alternating depolarizing and hyperpolarizing stimulation can further induce cell death. Within a possible consideration, the activation of voltage-dependent calcium channels during depolarization stimulation following a stimulation causes calcium influx, and each hyperpolarization stimulation increases permeability of voltage-dependent anion channels to calcium ions between cytosol and mitochondria. This reaction ultimately affects mitochondrial calcium homeostasis and causes cell death. This study of electrical stimulation may have highly possibility for clinical value on therapy method.

Reference

[1] Int J Mol Sci. 2020 Apr; 21(7): 2327.
[2] Front Physiol. 2022 Mar 8;13: 839437.
[3] Cancers (Basel). 2020 Aug; 12(8): 2232.
[4] J Pharmacol Sci. 2006;100(5):519-24.

Figure 1
Lithium Plating on Graphite Electrodes in Lithium-Ion Batteries
Authors: Yeh Che-Ning , Rose Justin , Thaman Harry , Narasimhan Swati , Huang Wei-Yi , Sun Wen , Huang William , Zhang Zewen , Chueh William C. 
Published: December 2024

Fast charging of lithium-ion batteries is a critical advancement in achieving more efficient and sustainable energy storage, particularly in electric vehicles. However, fast charging often leads to lithium plating, significantly impacting battery performance and longevity. While it is essential to reduce the amount of lithium plating, characterization of lithium plating is challenging due to high sensitivity of lithium to oxygen and water, small feature sizes, and the complex morphology of the porous electrode and the deposits (dendrites with solid-electrolyte interphase, SEI). Consequently, understanding the mechanism of lithium plating and SEI's influence on it remains elusive.
In our study, we utilize operando atomic force microscopy (operando-AFM) to investigate the dynamic behaviors during lithium plating and stripping on graphite nanoplatelets. This technique allows real-time, nanoscale observation of lithium plating and stripping, providing insights into lithium nucleation, growth, and distribution on the anode surface. Notably, we observe graphite exfoliation during plating and stripping, indicating the loss of active materials and its implications for battery capacity and cycling stability. Additionally, our research explores the interaction between SEI and lithium plating. Understanding how SEI influences lithium plating dynamics is essential for developing strategies to optimize fast charging capabilities.
By gaining insights from our investigations, we aim to inform the design of electrode materials, artificial SEI materials, and electrolyte additives that promote and facilitate fast charging in lithium-ion batteries. These strategies hold promise for enhancing battery safety, reliability, and overall performance, thereby accelerating the adoption of electric vehicles and other energy-intensive applications.
A Novel Approach to Electrode Delamination for Mechanism Analysis and Signal Detection: Fault-Simulated Li-Ion Batteries
Authors: Kim Suhwan , Choi Seungyeop , Jin Dahee , Kim Kyung-Geun , Lee Mingyu , Lee Hongkyung , Lee Yong Min 
Published: December 2024

The demand for increasing energy density of lithium-ion batteries (LIBs) continues to drive research into new compositions and designs. Some prominent strategies are to reduce the content of inactive materials, such as binders and conductive materials, and to increase a thickness of electrodes. However, these approaches can lead to uneven binder distribution and delamination of electrode layers due to the continuous volumetric expansion of the active material reducing the capacity and lifespan of the LIBs. Therefore, binder content and distribution analysis plays a critical role in evaluating battery performance. However, most extensive research has focused on improving the properties and distribution of binders, and systematic analysis and non-destructive detection of defects by binders remain largely unexplored. This research also is crucial for evaluating the remaining life of the battery and determining its suitability for reuse.
In this study, we fabricated a fault-simulated electrodes which can be easily delaminated during electrochemical reactions. When the morphology and composition of the electrode were analyzed, there were no significant morphological differences compared to a normal electrode, but it was observed that the binder compositions were different. As a result of the adhesive strength measurement of the defected electrode at different thicknesses, it was demonstrated that the adhesive strength at the electrode layers and interfaces decreased compared to normal electrodes. The electrochemical signals such as capacity fading and resistance characteristics by the electrode delamination were confirmed. Through the post-mortem analysis, the composition change in the cathode-electrolyte interphase (CEI) inside the electrode was compared and analyzed in relation to the change in current density distribution based on simulation. Furthermore, in order to nondestructively detect the electrode delamination defects, a magnetic field imaging and simulation analyses were conducted, and it was confirmed that the detection of defect spots was possible through this method. By systematically analyzing the electrode delamination, the main cause of electrode degradation was elucidated.
Structural and Grain-Growth Evolution during Synthesis of Layered Li(Ni,Co,Mn)O2 Oxides through Co-Precipitation Process
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Chen Yu-Hsuan , Chen Yu-Fan , Fung Kenneth 
Published: December 2024

For meeting 2050 zero carbon goals, the renewable energy/electricity including solar cells and wind mills need to be stored in a good energy storage system such as Li ion batteries. Furthermore, the electrification of transportation such as electric vehicles also need Li ion batteries in a very large scale. In recent years, µm-sized layered oxides, namely single crystals, received great attention due to its enhanced cycled-electrochemical performance.
For conventional/commercial NMC layered oxides, integrated co-precipitation process is commonly used. In additions, “single-crystal” process typically requires more heat energy at higher temperatures. Therefore, the main objective of this study is to develop a cost-effective process for the synthesis of single-crystal Ni-rich layered oxides electrode. For instance, the synthesis of layered oxides may adopt the simple solid state reaction routes. The heating procedures may be optimized through the understanding of calcination and grain-growth processes. Ni-rich layered oxides, namely NCA and NMC 811 are selected and prepared. The crystal structure and microstructure of cathodes were examined using XRD and SEM. The electrochemical properties are monitored using CV, EIS and charge/discharge tests.
Carbon Based Conductive Additives for Dry Coated Cathodes
Authors: Damnali Serkan , Woehrle Thomas 
Published: December 2024

In the course of climate change, electromobility is one of the biggest driving forces to reduce the CO2-emissions caused by humans. According to estimates, about 60 % of the total emissions from humans are caused by vehicles powered by internal combustion engines.[1] Thus, it is expected that the demand for lithium-ion batteries will increase from 700 GWh in 2022 to 4.7 TWh in 2030.[2] On the other hand, it must be stated that during the manufacturing of lithium-ion batteries cells, a considerable amount of energy is consumed. Estimations using publicly available data of two large-scale battery cell factories state that around 50 – 65 kWh of electricity is consumed per kWh of battery capacity.[3] Besides the operation of the dry room in battery manufacturing, the evaporation of the casting solvent in the electrode drying process consumes the most energy.[4,5,6] In a dry coating process, the casting solvent used for the conventional electrode production is eliminated.[7] Thus, this process provides a more sustainable battery manufacturing process.[8] One of the most promising approaches in this regard is the application of Polytetrafluoroethylene (PTFE) as an electrode binder which forms fibrils that anchor to active material particles and the conductive carbon additives.
The general aim of this work is to establish a fundamental understanding of processing cathodes via a dry process in a lab-scale following this route. Electrically conductive additives play a crucial role for processing, mechanical properties, and electrochemical performance of the electrode. Thus, various conductive additives (like carbon blacks, conductive graphite, and porous carbons) are characterized and their influences on process steps (like mixing and calendaring) and electrochemical performance of the cathodes is investigated to obtain structure-impact-relations for dry cathode manufacturing. Here, the focus will be on the interaction of the various carbons with the binder PTFE used in the dry coating process.
References:
[1] Golovanov, N., Marinescu, A., 8th International Conference on Modern Power System, 2019.

[2] https://www.mckinsey.com/industries/automotive-and-assembly/our-insights/battery-2030-resilient-sustainable-and-circular#/ (opened: 09.04.2024).
[3] Kurland, S.D., Environ. Res. Commun., 2020, 2.
[4] Sliz, R. et al., ACS Appl. Energy Mater., 2022, 5, 4047 – 4058.
[5] Yuan, C., Deng, Y., Li, T., Yang, F., CIRP Annals Manufacturing Technology, 2017, 66, 53 – 56.
[6] Ahmed, S. Nelson, P.A., Gallagher, K.G., Dees, D. W., Journal of Power Sources, 2016, 322, 169 – 178.
[7] Ludwig, B., Zheng, Z., Shou, W., Wang, Y., Pan, H., Scientific Reports, 2016, 6.
[8] Li, Y. et al., Materials Today, 2022, 55, 92 – 109.
Enhancing Power Density of Lithium-Ion Batteries through Controlled Reaction Mechanism of Lithium Insertion Material of LiNi0.5Mn1.5O4
Authors: Ariyoshi Kingo , Hiroshima Shinya , Masuda Shumpei , Sugawa Jun 
Published: December 2024

Throughout the last two decades, numerous studies have been performed to improve the power capability of LiNi0.5Mn1.5O4 (LNMO), such as via element substitution, surface modification, and particle morphology control. The reaction mechanism is another factor affecting rate capability; single-phase homogeneous versus two-phase coexistence reactions. In this study, to improve the rate capability of LNMO by controlling the reaction mechanism, we synthesized LiNi0.5Mn1.3Ti0.2O4 (Ti-LNMO), in which a part of Mn4+ in LNMO was replaced by Ti4+ [1].
During charging, the cubic lattice constant of Ti-LNMO decreased linearly from 8.20 Å to 8.05 Å (Fig. a). This result reveals that the lithium extraction of Ti-LNMO proceeds in a single-phase reaction over the entire range, while LNMO proceeds two-phase reaction [2].
To evaluate the inherent rate capability of LNMOs, the diluted electrode method [3,4], in which replacing a part of the active material with an inactive material makes the Li-ion transport process in the solid phase rate-determining, was applied to rate-capability tests (Fig. b). The Ti-LNMO exhibited superior rate capability than the LNMO without Ti-substitution, which demonstrated that high-power capabilities could be achieved by controlling the reaction mechanism.
Furthermore, the solid-state Li-ion diffusion coefficient in the LNMOs was determined from the relationship between the discharge capacity and the current density using following equation [5],

Q = (a
2
j
W)/(15D
Li)
where a is the particle radius, and D
Li is the diffusion coefficient of Li ions in the particle. From the linear relationship between the discharge capacity and current density (Fig. c), D
Li of Ti-LNMO and LNMO was calculated to be 9.5 × 10−11 and 3.6 × 10−11 cm2 s−1, respectively. This is the reason that the rate-capability of Ti-LNMO was more than three times greater than that of the LNMO. These results reveal that the lithium insertion mechanism is important for the kinetics of lithium insertion reaction.

References

[1] K. Ariyoshi and J. Sugawa, Electrochim. Acta, 455, 142425 (2023).
[2] K. Ariyoshi et al., J. Electrochem. Soc., 151, A296–A303 (2004).
[4] K. Ariyoshi et al., J. Electrochem. Soc., 167, 140517 (2020).
[3] K. Ariyoshi et al., J. Power Sources, 509, 230349 (2021).
[5] K. Ariyoshi and J. Sugawa, Electrochemistry, 89, 157–161 (2021).

Figure 1