bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of Surface Fluorination on LaNiO3 Perovskite-Type Oxides for Oxygen Evolution Reactions
Authors: Sugimura Ayane , Shibata Daisuke , Inada Yasuhiro , Zhong Chengchao , Shimoda Keiji , Okazaki Ken-ichi , Orikasa Yuki 
Published: December 2024

The technology of hydrogen production by alkaline water electrolysis using renewable energy has the advantages of abundant energy sources and minimal environmental pollution. However, the oxygen evolution reaction (OER) catalyst in water electrolysis faces several challenges. One problem is the unstable supply of renewable energy, which leads to frequent starting and stopping of the electrolyzer. This intermittency exposes the anode catalyst to drastic potential changes that generate reverse currents, resulting in anode catalyst degradation. Therefore, there is a critical need for research on more durable electrocatalysts. In this study, we attempted to improve the stability of perovskite-type oxides by using fluorination chemistry for surface treatment. We prepared fluorine-treated LaNiO3 by calcination with polyvinylidene fluoride (PVDF) and analyzed the electronic structures of the prepared samples by X-ray absorption spectroscopy.
LaNiO3 and PVDF, a fluorine additive, were mixed using a mortar. The mixture was then pelletized and sintered in a sealed vessel at 350 °C for 12 hours. This experimental condition was based on the fluorination reaction of HfO2
[1]. Four different PVDF-to-LaNiO3 mixing ratios were synthesized: 0% (pure LaNiO3), 2.5%, 5%, and 10% by weight. To confirm whether the catalyst surfaces were fluorinated, XRD and XAFS measurements were performed to analyze the changes in the crystal structure and the valence changes by the introduction of fluorine. For electrochemical measurements, a measuring cell for electrolysis was used[2], which is reported to be analyzable only with powder catalysts.
A comparison of the X-ray diffraction (XRD) patterns of pure LaNiO3 and LaNiO3 treated with PVDF showed that the addition of PVDF shifted the XRD peak to lower angles. This shift confirms a structural expansion in the LaNiO3 crystal lattice due to the PVDF treatment. For a more detailed investigation, XAFS measurements were performed. Analysis in the F K-edge XAFS identified a distinct fluorine peak in the PVDF-treated LaNiO3 sample, indicating successful introduction of fluorine into the structure. In addition, in the Ni K-edge X-ray absorption near edge structure, the spectrum of the PVDF-added sample shifted to a lower energy compared to pure LaNiO3, indicating a reduction in nickel valence, likely due to fluorine incorporation. However, electrochemical measurements indicated a decrease in the initial OER activity of LaNiO3 treated with PVDF.
[1] Steven Flynn, Chi Zhang, Kent J. Griffith, Jiahong Shen, Christopher Wolverton, Vinayak P. Dravid, and Kenneth R. Poeppelmeier, Inorganic Chemistry, 60(7), 4463-4474 (2021)
[2] K. Nagasawa, T. Ishida, H. Kashiwagi, Y. Sano, and S. Mitsushima, Int. J. Hydrogen Energy, 46, 36619 (2021)
Evaluation of the Anode Characteristics of a Solid Oxide Fuel Cell for Electric Aircraft Propulsion
Authors: Wada Shuya , Nakajima Hironori , Okai Keiichi , Kojima Takayuki 
Published: December 2024

We focus on the characteristics of a pressurized solid oxide fuel cell for a hybrid system with gas turbine (jet engine) electric generation for the propulsion of electric aircraft1). In this study, we electrochemically characterize the anode, evaluating the dependence of the exchange current density on hydrogen partial pressure2). The exchange current density is used for numerical modeling as an electrochemical kinetic parameter3). Such numerical models are useful for optimizing the cell/stack designs and operating conditions4). An electrolyte-supported
(YSZ) symmetrical cell with Ni-YSZ electrodes was prepared to measure the single-electrode reaction resistance, which gives the exchange current density, by using electrochemical impedance spectroscopy under various partial pressures of humidified hydrogen. The hydrogen partial pressure with diluting nitrogen under atomospheric pressure gave a different reaction order for the exchange current density from that without nitrogen under pressurized conditions.
Acknowledgement
Thanks are offered to Professor Kohei Ito and Associate Professor Tatsumi Kitahara of Kyushu University for their valuable discussions.
References
1) T. Kojima and K. Okai, AIAA (2023) 2023-1325. https://doi.org/10.2514/6.2023-1325
2) Yonekura, Y. Tachikawa, T. Yoshizumi, Y. Shiratori, K. Ito, K. Sasaki, ECS Trans, 35 (1) (2011) 1007-1014. https://doi.org/10.1149/1.3570081
3) Ö. Aydın, T. Ochiai, H. Nakajima, T. Kitahara, K. Ito, Y. Ogura, and J. Shimano, Int. J. Hydrogen Energy, 43 (36) (2018) 17420-17430. https://doi.org/10.1016/j.ijhydene.2018.07.030
4) H. Nakajima, J. Yamashita, K. Okai, and T. Kojima, 243rd ECS Meeting with the 18th International Symposium on Solid Oxide Fuel Cells (SOFC-XVIII) (2023). https://doi.org/10.1149/MA2023-01562726mtgabs
Chemical Versus Electrochemical Oxidation of Triclosan: Reaction Yield and Selectivity
Authors: Lewis Tyra , Martic Sanela 
Published: December 2024

Phenolic compounds are generally known for their benefits toward human health. Triclosan (5-chloro-2-(2,4-dichlorophenoxy) phenol) plays a role as an antibacterial agent and is often found in personal care products such as toothpaste, disinfecting products, and cosmetics amongst others.1 However, despite the named health benefits, several concerns have arisen due to the compound’s potential environmental toxicity, for instance, as a result of its transportation to wastewater treatment plants.1-2 Therefore, the development of methods for efficient removal of triclosan from such streams is vital for maintaining environmental health. A variety of methods including adsorption, photolysis, chemical oxidation and biodegradation processes have been used for removing or degrading the wastewater pollutant. However, these techniques may require highly trained, sample preparation, specialized reagents etc. As an alternative solution, the electrochemistry offers multiple advantages. 1 Herein, we utilized electrochemical methods for selective electrochemical oxidation/reduction of triclosan toward the formation of dechlorinated and oxidized products.3 The electrochemical reactions and were monitored by UV-Vis spectroscopy and GC-MS which suggested that the reaction yield and selectivity was potential-dependent. The electrochemical conversion of triclosan was also compared to the traditional chemical conversion method. Data indicate that the electrochemical process allows for higher yield of the products within a shorter reaction time. Hence, electrosynthesis provides an alternative way of bond breaking and bond making, with applications in green chemistry, synthesis of value-added chemicals or bioremediation.
1 Knust K.N., Foley M.P., Mubarak M.S., Skljarevski S., Raghavachari K., Peters D.G. Electrochemical reduction of 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan) in dimethylformamide, J. Electroanal. Chem., 2010, 638, 100-108.
2 Zhang H., Huang C-H. Oxidative transformation of triclosan and chlorophene by manganese oxides, Environ. Sci. Technol.,
2003, 37, 2421-2430.
3 Zabik, N et al. Selective Electrochemical versus Chemical Oxidation of Bulky Phenol. J. Phys. Chem. B.
2016, 120, 8914-8924.

Figure 1
One-Pot Solution Synthesis of Bulk and Surface Simultaneously Optimized BiVO4 Photoanode with Enhanced Photoelectrochemical Water-Splitting Activity
Authors: Hwang Sung Won , Jeong Yoo Jae , Cho In Sun 
Published: December 2024

Bismuth vanadate (BiVO4, BVO) with a monoclinic crystal structure has attracted significant interest in photoelectrochemical (PEC) and photocatalytic (PC) oxidation that are utmost critical processes to producing clean hydrogen fuels from solar energy. BVO has a suitable bandgap (2.4 eV), which enables it to absorb sunlight up to a wavelength of 520 nm. Furthermore, it possesses a suitable location of the valence band edge for water oxidation, decent photoelectrochemical/photochemical activity, and moderate stability in neutral electrolytes. Nevertheless, PEC performance is hindered by diverse inherent drawbacks, including inadequate conductivity and mobility, limited light absorption, and significant charge recombination at the bulk and surface 1,2.
This study demonstrates a novel one-pot solution method to synthesize high-performance BVO photoanodes for photoelectrochemical (PEC) water-splitting. We designed a stepwise dual reaction (SDR) to optimize the bulk and surface characteristics via texturing and surface reconstruction. The key innovation lies in controlling precursor concentration, ethylene glycol (EG), and manipulating growth kinetics and surface reconstruction. EG plays a crucial role in achieving this texture and surface reconstruction. Compared to conventional BVO (non-textured and non-surface-reconstructed), the optimally synthesized textured and surface-reconstructed BVO (ts-BVO) exhibits significantly improved charge transport (70% vs. 8%) and surface charge transfer efficiencies (85% vs. 9%). Furthermore, by depositing the CoBi oxygen evolution electrocatalysts, the ts-BVO achieved a steady photocurrent density of 4.3 mA/cm2 at 1.23 V vs. the reversible hydrogen electrode (RHE) and an almost unity Faradaic efficiency of 98% under simulated sunlight illumination (1 sun). Our findings highlight the effectiveness of solution chemistry in controlling the texture and surface characteristics of photoanode for efficient photoelectrochemical water-splitting 3,4.

Keywords: One-pot hydrothermal, ethylene glycol, BiVO4, texture, surface activation, photoelectrochemical water-splitting

Reference

1 H. S. Han, S. Shin, D. H. Kim, I. J. Park, J. S. Kim, P. S. Huang, J. K. Lee, I. S. Cho and X. Zheng, Energy Environ Sci, 2018, 11, 1299–1306.
2 Y. J. Jeong, S. W. Hwang, S. Chaikasetsin, H. S. Han and I. S. Cho, Chemical Engineering Journal, 2022, 435, 135183.
3 I. S. Cho, H. S. Han, M. Logar, J. Park and X. Zheng, Adv Energy Mater, 2016, 6, 1–9.
4 I. S. Cho, Z. Chen, A. J. Forman, D. R. Kim, P. M. Rao, T. F. Jaramillo and X. Zheng, Nano Lett, 2011, 11, 4978–4984.
(Invited) Quantifying Li Plating on Graphite during Fast Charging of Li-Ion Batteries
Authors: McCloskey Bryan D. 
Published: December 2024

Li-ion battery fast charge is limited due to challenges posed by lithium plating on the graphite anode, whereby the large overvoltage necessary to drive high Li+ insertion rates instead results in favorable thermodynamic conditions for Li metal deposition on the graphite surface. Li plating is difficult to detect, particularly in small quantities, and results in safety risks and capacity fade due to lithium metal’s high reactivity with conventional electrolytes. Here, we present our efforts to develop both chemical and electrochemical methods to precisely quantify Li plating and detect the state-of-charge (SOC) onset of lithium plating on graphite electrodes during constant current fast charging. We will discuss titration mass spectrometry (TiMS), a highly sensitive (~20 nmol resolution, or 0.5 µAh of plated Li) chemical analysis where gases evolved from harvested graphite electrodes immersed in acid are used to quantify various solid electrolyte interphase species, including electrically isolated (inactive) Li metal.1 TiMS is then used to determine the precise onset of Li plating and to distinguish between the various capacity fade mechanisms that arise during fast charge.2 We then will discuss the use of simple electrochemical cycling techniques to quantify irreversible Li plating in Li|Graphite half-cells as a function of energy density (electrode thickness), charge rate, temperature, and SOC.3 Similar methods are developed to quantify in-situ Li plating for commercially relevant Graphite|LiNi0.5Mn0.3Co0.2O2 (NMC) cells. In combination, all of these techniques provide a highly accurate measure of the onset of Li plating and quantitative insight into capacity losses during fast charging.
1. McShane, E. J.; Colclasure, A. M.; Brown, D. E.; Konz, Z. M.; Smith, K.; McCloskey, B. D., Quantification of inactive lithium and solid–electrolyte interphase species on graphite electrodes after fast charging. ACS Energy Lett. 2020, 5 (6), 2045-2051.
2. McShane, E. J.; Bergstrom, H. K.; Weddle, P. J.; Brown, D. E.; Colclasure, A. M.; McCloskey, B. D., Quantifying graphite solid-electrolyte interphase chemistry and its impact on fast charging. ACS Energy Lett. 2022, 7 (8), 2734-2744.
3. Konz, Z. M.; Wirtz, B. M.; Verma, A.; Huang, T.-Y.; Bergstrom, H. K.; Crafton, M. J.; Brown, D. E.; McShane, E. J.; Colclasure, A. M.; McCloskey, B. D., High-throughput Li plating quantification for fast-charging battery design. Nature Energy 2023, 8 (5), 450-461.
Reassessing the Quantity of Lithium in Metal Batteries: The Less Is More Philosophy from Metal-Free to Metal Anode
Authors: Wang Di , Qiu Jie , Inui Naoki , Hagiwara Rika , Hwang Jinkwang , Matsumoto Kazuhiko 
Published: December 2024

Lithium metal-free batteries (LMFBs, often called anode-free batteries), characterized by the absence of pre-loaded lithium metal or host materials at the anode, have emerged as a focal point in battery research due to their theoretically highest energy density.[1] However, LMFBs face significant challenges: their practical energy density and cycle performance are severely limited by lithium inventory loss during initial charging and the limited reversibility of lithium plating/stripping during battery cycles.[2] We reassess the impact of lithium metal quantity at the anode on battery performance.[3] By incorporating a minimal amount of lithium, lean lithium metal batteries (LLMBs) slightly compromise energy density (the 'less') but, as demonstrated in Figure 1, achieve higher practical energy densities and longer lifespans than LMFBs (the 'more') with an N/P ratio of 0.2, an average lithium Coulombic efficiency of 99.9%, and considering an initial capacity loss of 5%. This makes LLMBs a pragmatic choice even under lenient technical conditions.
It is important to note that this discussion does not endorse one over the other; LMFBs and LLMBs inherently share many similarities and overlapping technologies, such as benefits derived from advanced electrolytes and protocol management. Moreover, LMFBs offer manufacturing advantages by avoiding strict measures required for handling fragile lithium metal, presenting distinct benefits. Additionally, performance metrics derived from LLMBs are invaluable for guiding future LMFB evaluations. Certain LMFB enhancements, like the creation of artificial SEI layers or the use of 3D current collectors, might inadvertently increase battery weight and size, negating the foundational purpose of LMFBs. In such scenarios, the energy density and battery performance of LLMBs, under comparable conditions, can serve as benchmarks to assess the tangible impact of such interventions on LMFBs, ultimately aiming to genuinely elevate battery efficacy.

References

[1] S. Nanda, A. Gupta, A. Manthiram, Adv. Energy Mater. 11 (2021) 2000804.
[2] C. Heubner, S. Maletti, H. Auer, J. Hüttl, K. Voigt, O. Lohrberg, K. Nikolowski, M. Partsch, A. Michaelis, Adv. Funct. Mater. 31 (2021) 2106608.
[3] D. Wang, J. Qiu, N. Inui, R. Hagiwara, J. Hwang, K. Matsumoto, ACS Energy Lett. 8 (2023) 5248.
Importance of Fluorine in Non-Flammable High Voltage Electrolytes for LNMO||SiGr Cell Chemistry
Authors: Leopold Maike , Woelke Christian , Winter Martin , Cekic-Laskovic Isidora 
Published: December 2024

Due to their high energy density and long cycle life, lithium-ion batteries are becoming increasingly important in energy storage and electric vehicle applications. On the cathode side, the high voltage LiNi0.5Mn1.5O4 (LNMO) electrode has emerged as a promising candidate enabling a high reversible specific capacity of 147 mAh g-1 and high theoretical energy density of 650 Wh kg-1. The complete elimination of Co as a critical raw material is also important with regards to the fluctuating costs and environmental impact.1 Combined with silicon-based electrodes and the roughly ten-fold increase in specific capacity of Si compared to the state-of-the-art graphite, achievable energy density of the resulting cell chemistry can be significantly improved.2

In this work a flame retarded high voltage electrolyte formulation for 250 mAh LNMO||SiGr pouch cells, was designed and comprehensively characterised. Next to the electrochemically stability up to 5 V vs. Li|Li+, suppression of Mn and Ni dissolution and the ability of enabling formation of effective SEI and CEI layers are standing out as the electrolytes key features. By using fluorinated solvents and co-solvents in comparison to non-fluorinated solvents, a high voltage oxidative stability up to 5.0 V vs. Li|Li+ and effective interphases (SEI and CEI) formation could be achieved. Likewise, the galvanostatic cycling performance and the accumulated discharge energy was increased by approximately 62 %, while the roll over failure was suppressed for more than 500 charge/discharge cycles. The addition of a flame-retardant additive in amount of only 1 wt.% to the fluorinated solvents mixture resulted in a non-flammable electrolyte with sufficiently good cycle life.
References:
[1] T. Fu, D. Lu, Z. Yao, Y. Li, C. Luo, T. Yang, S. Liu, Y. Chen, Q. Guo, C. Zheng, W. Sun, J. Mater. Chem.,
11, 13889-13915 (2023). DOI: 10.1039/D3TA01777J
[2] C. Wölke, B. Sadeghi, G. Eshetu, E. Figgemeier, M. Winter, I. Cekic-Laskovic, Adv. Mater. Interfaces,

9
, 2101898 (2022). DOI:10.1002/admi.202101898
Impact of Graphite Materials on the Consumption of Prop-1-Ene-1,3-Sultone and Vinylene Carbonate in Lithium-Ion Cells
Authors: Adamson Anu , Tuul Kenneth , Metzger Michael 
Published: December 2024

It has been shown that electrolyte additives can be highly beneficial to the performance and lifetime of lithium-ion cells.1,2 However, many additives are consumed in the early cycles, which will affect the cycling performance of the cell over long-term operation. It has been shown that most electrolyte additives are consumed relatively early. For example, when ≤2 wt% vinylene carbonate is used in Li[Ni0.33Mn0.33Co0.33]O2/graphite cells, most of it is consumed during the first 200 h of cell operation.3

Prop-1-ene-1,3-sultone (PES) and vinylene carbonate (VC) are among the most used electrolyte additives in lithium-ion cells. PES is useful for suppressing gas formation, and VC has been found to form a stable solid-electrolyte interphase (SEI), preventing further electrolyte decomposition on the negative electrode. The SEI formed by the decomposition of both additives on the negative electrode surface has been thoroughly characterized.4 However, the dependence between the consumption of these additives and the choice of negative electrode has not been thoroughly examined.
In this work, the consumption of PES and VC was investigated in Li[Ni0.8Mn0.1Co0.1]O2/artificial graphite (NMC811/AG) or Li[Ni0.83Mn0.06Co0.11]O2/artificial graphite (Ni83/AG) pouch cells with four different artificial graphites. The physical properties of these graphite materials were reported by Eldesoky et al.5 Various amounts of VC and PES (alone or in combination with each other) between weight percentages of 0.5 to 2% were used. The cells were formed, after which the electrolytes were extracted and analyzed with quantitative GC-MS to find the amount of additives consumed.
This study demonstrates the significant effect the choice of artificial graphite has on PES and VC consumption rates. In addition, the impact of varying additive amounts and using graphites with different physical properties on formation parameters such as first-cycle efficiency (FCE), charge transfer resistance (Rct), and gas production will be shown.

References

E. R. Logan et al., J. Electrochem. Soc., 167, 130543 (2020).

T. Taskovic, L. M. Thompson, A. Eldesoky, M. D. Lumsden, and J. R. Dahn, J. Electrochem. Soc., 168, 010514 (2021).

R. Petibon, J. Xia, J. C. Burns, and J. R. Dahn, J. Electrochem. Soc., 161, A1618–A1624 (2014).

L. Madec et al., J. Electrochem. Soc., 162, A2635 (2015).

A. Eldesoky et al., J. Electrochem. Soc., 169, 010501 (2022).
(Invited) Redefined Battery Science and Engineering after 100 Years of Debye-Hückel Theory
Authors: Yamada Atsuo 
Published: December 2024

In any electrochemical system, electrode potential is the central variable that regulates the driving force of redox reactions. However, quantitative understanding of the electrolyte dependence has been limited to the classic Debye-Hückel theory that approximates the Coulombic interactions in the electrolyte under the dilute limit conditions. Therefore, accurate expression of electrode potential for most of practical electrochemical systems has been a holy grail of electrochemistry research for over a century. Here we show that the ‘liquid Madelung potential’ based on the conventional explicit treatment of solid-state Coulombic interactions enables quantitatively accurate expression of the electrode potential, with the Madelung shift obtained from molecular dynamics reproducing a hitherto-unexplained huge experimental shift for several battery electrode. Furthermore, incorporating the effects of entropy and polarization dynamics could polish the theoretical model to perfectly fit the experimental data. Thus, a long-awaited method for the description of the electrode potential in any electrochemical system is now available after 100 years of classical Debye-Hückel theory.
[1] P. Debye & E. Hückel, Physikalische Zeitschrift, 24, 185 (1923), [2] N. Takanaka, et al., and A. Yamada, Denki Kagaku, 91, 140 (2023) [3] S.Ko, et al., and A. Yamada, Next Energy, 100014 (2023), [4] S. Ko, et al.,and A. Yamada, Nature Sustain., 6, 1705 (2023), [5] N. Takenaka, et al., and A.Yamada, Nature Comm., 15, 1319 (2024)