bluuebunny/crossref_metadata_2025_split huggingface dataset:
Using Operando Mass Spectrometry to Study Room Temperature C-H Bond Activation of Propane on Pt Electrocatalyst in Aqueous Acidic Electrolyte
Authors: Bhadouria Ashutosh , Tackett Brian Michael 
Published: December 2024

C-H bond activation is an important step in order to produce industrially relevant products from readily available light alkane feedstock. Thermally, C-H activation has been hypothesized as a rate-limiting step for various reactions, such as alkane-to-alcohol conversion and alkane dehydrogenation. However, high-temperature processes, typically utilized for such endothermic activations, are energy-intensive and ultimately lead to a large carbon footprint. Therefore, there is a need to enable C-H activation at lower temperatures, and an electrochemical pathway, powered by renewable energy, is a promising alternative. An electrocatalyst can utilize potential as a driving force to initialize the reactivity of light alkanes via activating a C-H bond. Electrochemically, Pt has shown activity towards functionalizing alkanes, although producing an undesired byproduct - CO2 - with high faradaic efficiency. Furthermore, little is known about the adsorption mechanism, identity of adsorbate species, and potential conditions suitable for enabling selective oxidation to valuable intermediates.
Our work uses Electrochemical Mass Spectrometry (ECMS) to elucidate the potential dependence of propane activation on a Pt electrocatalyst. Potentiodynamic profiles enable quantification of charge involved in the proposed faradaic pathway while mass spectrum analysis reveals the identity and quantity of gas-phase species produced. We found that the adsorption of a neutral, non-polar alkane – propane – is dependent on the potential applied at the Pt electrocatalyst in aqueous acidic electrolyte. When propane is introduced in the cell at varying adsorption potential holds, we found that the propane-derived adsorbates reached a maximum coverage at an adsorption potential of 0.3 VvsRHE. An oxidative charge transience was observed when propane was introduced to the cell, which is consistent with a dissociative chemisorption mechanism – via a C-H bond activation. Additionally, the identity of propane-derived adsorbate species was determined via a combination of coulometry and mass spectrometry to quantify the extent of dehydrogenation of C3
* adsorbates.
These results show that propane is activated well within the electrochemical stability of water, and propane-derived adsorbate species preserve the three-carbon propane backbone. Therefore, the adsorbate species can be further functionalized by varying the potential at the electrocatalyst, after the initial adsorption, to make valuable oxidative intermediates. Our findings can be directly applied to tune electrocatalysts in order to selectively activate paraffinic C-H bond at room temperature, aqueous conditions, for decarbonized chemical manufacturing.

Figure 1
Electrochemical Aptasensor for Progesterone Detection
Authors: Carroll Emily , Winterholler Elizabeth , Sparks Taylor D , Minteer Shelley D. 
Published: December 2024

Electrochemical biosensors have revolutionized point-of-care diagnostics through commercial accessibility while maintaining detection specificity and sensitivity. Medical biosensors are designed to detect biomarkers in bodily fluids (blood, urine, saliva, sweat) and commonly use enzymes, antibodies, or nucleic acids to bind biomarker targets. An emerging method of biomarker detection uses aptamers which are short, single-stranded DNA or RNA molecules that bind to specific target molecules with high affinity and selectivity. Aptamer sensors are an affordable alternative to antibody-based sensors, have a wider target scope compared to antibody- or enzyme-based assays, and inherently have high structure flexibility and design for redox robe modification. In particular, electrochemical aptamer biosensors (E-AB) represent a promising device architecture wherein an aptamer sequence with a redox probe is tethered to an alkane thiol self-assembled monolayer on a gold electrode (Au-SAM). Upon substrate binding, the conformational changes in the aptamer then enable fast electron transfer to the redox probe and allow rapid and continuous signal transduction of analyte concentrations. E-ABs have been used to target various biomarkers (cocaine, thrombin, tobramycin, vancomycin, etc.) and operate well in vivo, making them an attractive technology for point-of-care diagnostics.
In this work, an E-AB is designed for progesterone monitoring. Progesterone is a key biomarker for monitoring reproductive health, as irregular levels are predictive of unsuccessful pregnancy, abnormal uterine bleeding, early embryonic mortality, or ectopic pregnancy. However, there are no continuous, non-invasive methods for progesterone detection. Current methods are limited to laboratory blood samples, ovulation prediction kits, and cycle tracking, but these methods fall short of achieving continuous, accurate, reliable, non-invasive, accessible, and comprehensive detection. Here, we develop an E-AB with a specific affinity for progesterone using the established Au-SAM architecture, a methylene blue redox reporter, and an aptamer sequence with a high affinity for progesterone. These experiments show proof of concept that an immobilized aptamer with methylene blue can detect progesterone electrochemically and is a promising platform for continuous monitoring of progesterone in vivo.
LIOVIX® Printable Lithium Technology for Roll-to-Roll Lithium Anode Manufacturing
Authors: Xia Jian , Fitch Brian , Yakovleva Marina 
Published: December 2024

Arcadium Lithium Corporation has developed LIOVIX®printable lithium technology; a formulation which combines Stabilized Lithium Metal Powder (SLMP®) and rheology modifiers in a stable suspension that can be printed on most common substrates where a controlled amount of lithium metal is needed. For example, LIOVIX® can be printed on the surface of a pre-fabricated electrode. We have successfully demonstrated this technology in pre-lithiating SiO/Graphite anodes in the range of 0% to 100% of SiO content. LIOVIX® can also be printed as a thin lithium layer on the current collectors, separators, and even solid electrolytes to be used for lithium metal anode applications. The advantage of this technology is that the thickness of the printed lithium layer can be easily controlled. We have demonstrated printed lithium layer thickness in the range of 5µm to 50µm on a variety of substrates. LIOVIX® printable lithium technology is easily scalable using standard battery industry coating and printing equipment. We will present recent progress using R2R pilot equipment development as well as performance data in large format cells that have our technology incorporated.
Figure 1. Pilot scale R2R coater demonstration for production of the 20 µm lithium foil

Figure 1
Understanding Degradation Modes in High-Temperature 18650 Cylindrical Cells to Project Low-Temperature Lifetimes
Authors: Floras Claire , Tuul Kenneth , Martin Maher Sasha , Metzger Michael , Dahn Jeff R. 
Published: December 2024

With advances in Li-ion batteries allowing for decades of cycling, there is an incentive to produce accurate lifetime predictions without waiting for the cell to reach end of life1. Since failure mechanisms become apparent more rapidly when cycling at elevated temperatures2, comparing the performance of cells cycling up to 100 °C to ambient temperature cells of the same chemistry and electrolyte composition is useful. Single crystal NMC/artificial graphite chemistries of 60% Ni and low Co concentrations were combined with varying electrolytes which are operable over a wide temperature range without exhibiting significant gassing and while maintaining good capacity retention3.
By reducing and eliminating degradation modes, such as electrolyte permeation through the cell seal at high temperature, impedance growth, salt consumption, and gas generation, an experiment can be designed wherein the primary degradation mode is Li inventory loss. Once this is the case, and using ultra-high precision coulometry (UHPC) to collect data like that shown in Figure 1, lifetime predictions can be made and validated in combination with long-term CCCV results. Post-mortem analyses of cells can also provide insight into these degradation mechanisms and their implications for lifetime predictions.
Figure 1. fractional capacity vs cycle for NMC 640 pouch cells (black diamonds) and varying 18650 cylindrical cells (NMC640 red circles, NMC60:35:5 blue squares, NMC631 green triangles). The pouch cells and the 18650 cylindrical cells were cycled at C/20 from 3.0-4.0 V on a UHPC instrument. The negative electrode was artificial graphite.
References
[1] C. P. Aiken et al., J. Electrochem. Soc., 169, 050512 (2022).
[2] T. Taskovic, A. Eldesoky, W. Song, M. Bauer, and J. R. Dahn, J. Electrochem. Soc., 169, 040538 (2022).
[3] K. Tuul, S. Martin Maher, C. Floras, W. Black, T. Taskovic, S. Chisholm, A. Clarke, E. Lust, and J. R. Dahn, J. Electrochem. Soc., Under review (2024)

Figure 1
Three-Layer Electrorefining of Molten Zinc Held on Porous Carbon or Silica Sheets in Molten LiCl–KCl–ZnCl2
Authors: Yasuda Kouji , Yamada Shoya , Uda Tetsuya 
Published: December 2024

A three-layer electrolysis process utilizing porous holding materials with the impermeability to liquid metals due to the poor wettability but permeability to molten salt electrolytes was investigated, which enables to establish a three-layer configuration of metal(l)/electrolyte(l)/metal(l) by holding metals above the electrolyte regardless of their densities. Porous carbon or silica sheets were selected as the holding materials of liquid Zn, and upper electrode to hold liquid Zn was prepared. Electrorefining experiments was carried out in molten LiCl–KCl–ZnCl2 at 723 K. Three types of experiments were carried out focusing on anodic polarization, electrorefining with cathodic carbon, and three-layer electrolysis using liquid Zn as cathode.
Anodic polarization experiments clarified that evolution of a large amount of Cl2 gas was observed from the graphite components of the upper electrode when a more positive potential than the Cl2/Cl− was applied. The use of insulating silica fiber sheets and holding material allowed for dissolution of Zn at higher current density without gas evolution. In the electrorefining experiments, synthesized crude zinc and ISP crude zinc were electrolyzed to obtain purified Zn at the cathode. The concentration of impurity elements in the cathode Zn was reduced by a factor of 8 to 200 compared to the value in the crude zinc, highlighting the purification effectiveness of the method. In the Zn(l)/electrolyte(l)/Zn(l) three-layer electrolysis, it was verified that the upper electrode was applicable as either an anode or cathode. Current efficiencies were close to 100% in all electrorefining and three-layer electrolysis experiments. From the results obtained, challenges associated with the three-layer electrolysis process were identified, and countermeasures to solve them were proposed.
Acknowledgement: This work is conducted as a collaboration research of Laboratory of Design of Sustainable Materials and Processing, and Laboratory of Non-ferrous Extractive Metallurgy, Department of Materials Science and Engineering, Graduate School of Engineering, Kyoto University. Laboratory of Non-ferrous Extractive Metallurgy is an endowed chair by Mitsubishi Material Corp. We would like to acknowledge Prof. Hisaaki Fukushima at Kyushu University, Prof. Takashi Nakamura at Tohoku University, and Dr. Akihiro Kishimoto at Kyoto University for their valuable discussion. We also acknowledge Mitsui Mining & Smelting Co., Ltd., for supplying the prime western grade metal zinc (ISP crude zinc).
A Leading Role of I'MSEP for Carbon Negative Technologies by Molten Salt Electrochemical Research
Authors: Terada Seiji , Hyodo Yoshikazu , Nakanishi Ryo , Koyama Akira , Sah Santosh Prasad , Nomura Yohei , Kunihiro Takao 
Published: December 2024

I’MSEP Co., Ltd is a brainchild of the late Prof. Yasuhiko Ito who passed away last year at the age of 82. Prof. Ito was a fellow member of The Electrochemical Society. Prof. Ito focused on working and developing electrochemical processes in molten salts throughout his career at Kyoto University and Doshisha University (Japan). Fig. 1 illustrates the themes of research on which I’MSEP is now working. In this meeting, the authors will briefly talk on formation of carbon particles by plasma-induced discharge electrolysis (PiDE) and the conventional electrolysis, and also reckon up their merit. The produced carbon materials can be used for next-generation secondary batteries and fuel cells.
In PiDE, carbon submicron-particles are produced under plasma discharge in a molten salt bath containing carbonate ions. The plasma is generated at the W (tungsten) cathode placed just above the molten salt while a specific anode was dipping into the melt. The molten salt was the eutectic mixture of 58.5LiCl–41.5KCl (mol%) (m. p. 352°C), and was used at 450°C under argon atmosphere. The molten salt contained 2 mol% K2CO3 dissolved within it, acting as the carbon source. Extremely fine carbon particles (size <1 μm) can be produced with PiDE.
Carbon particles produced with PiDE showed high electrochemical performance. Downsizing carbon particles beyond 1 μm is difficult with the conventional electrolysis. On the other hand, the conventional electrolysis can produce carbon of different morphology like granular, filamentous, flaky, columnar, membrane-like (both dense and porous). Finer carbon particles were successfully formed in Li-free molten salt, and work is going in this direction.

Figure 1
Acetylene Synthesis from CO2 and H2O Via Electrochemical Formation of Metal Carbides in High-Temperature Chloride Melt
Authors: Suzuki Yuta , Tanaka Seiya , Watanabe Takashi , Tsuchii Takane , Isogai Tomohiro , Yamauchi Akiyoshi , Kishikawa Yosuke , Goto Takuya 
Published: December 2024

Research on CO2 conversion into valuable materials has attracted much attention, aiming to realize carbon neutrality and carbon-negative emission technology. It has been reported that the unique physicochemical properties of high-temperature molten salt, such as high conductivity and wide electrochemical window, make it possible to obtain solid carbon directly from CO2 and metal carbides.
In this study, we focused on the electrochemical formation of CaC2 from CO2 in high-temperature chloride melt. CaC2 is the raw material for acetylene, the starting material for various chemical products. This study demonstrated the selective formation of CaC2 from CO2 by an electrochemical process in NaCl-KCl-CaCl2-CaO melt at 823 K to produce C2H2 with high current efficiency. When the inert material for oxygen evolution in the high-temperature melts was used as the anode, the formation of acetylene and oxygen from carbon dioxide and water can be realized as the total reaction.
2CO2 + H2O → C2H2 + 5/2O2

On the metal cathode, the CaC2 was formed through two reactions: the carbon electrodeposition from CO2-derived CO3
2− (Step 1) and the electrochemical reduction of Ca(II) ion on the carbon (Step 2). These two reactions could be controlled by conducting potentiostatic electrolysis under CO2 and Ar atmospheres, resulting in acetylene synthesis with a maximum current efficiency of 92%. The electrolysis on carbon electrodes revealed that the higher the crystallinity of carbon, the more selectively CaC2 was formed. The CaC2 formation was induced by the reduction of Ca(II) ions on the basal plane of the graphite layer rather than the edge plane. The unique interfacial phenomenon between high-temperature melt and a carbon electrode surface will contribute to realizing a highly efficient CO2 conversion process to acetylene. It was found that the electrochemical formation of CaC2 tends to proceed at the basal plane of the graphite layer. This reaction mechanism is entirely different from the interlayer reactions that tend to occur in LIBs and is unique to this electrolytic system at the carbon/molten salt interface. The obtained data will provide a highly efficient process for CO2 resource conversion and physicochemical insights into new carbon surface reactions.
Ternary Ionic Liquid Analogues for Ambient and Low-Temperature Rechargeable Aluminum Batteries
Authors: Wang Jonah , Schoetz Theresa , Gordon Leo W. , Biddinger Elizabeth J. , Messinger Robert J. 
Published: December 2024

Many issues surround lithium, such as scarcity, safety, and ethical extraction. One promising alternative to lithium-ion batteries are aluminum batteries, which offer the earth abundance, inherent safety, high theoretical capacity, and low cost of aluminum metal. Additionally, batteries for transportation, space, or defense applications may often need to operate at low temperatures, where electrolytes exhibit lower ionic conductivity and are prone to freezing. The state-of-the-art electrolytes for aluminum batteries, Lewis acidic AlCl3 (aluminum chloride)-[EMIm]Cl (1-ethyl-3-methyl-imidazolium chloride) ionic liquids (ILs), are not cost effective and exhibit low ionic mobilities and conductivities below 0 oC. Their electrochemical and thermophysical properties can be tuned by adding a third species, such as urea. The AlCl3-urea ionic liquid analogue has also been investigated as a lower cost alternative. However, little research has been done on ternary mixtures of AlCl3-urea-[EMIm]Cl, including investigations of their physical properties and ability to reversibly electrodeposit Al metal from ambient to low temperatures.
In this work, AlCl3-urea-[EMIm]Cl mixtures with molar ratios of 1.3:X:(1-X) molar ratios were synthesized, where X = 0, 0.125, 0.25, 0.5, 0.75, and 1. Physical and electrochemical properties were characterized from ambient to low temperatures (down to -70 oC) with spectroscopic, thermoanalytical, and electrochemical measurements. Differential scanning calorimetry (DSC) was utilized to observe the thermal behavior of the electrolytes and determine their liquid-phase temperature windows. Quantitative liquid-state 27Al and 1H single-pulse nuclear magnetic resonance (NMR) experiments revealed how the types and populations of the polyatomic aluminum complexes changed based on urea concentration, as well as understand how the local environments of the EMIm+ cations and urea change across different compositions. The Al electrodeposition capability of the electrolyte mixtures were tested from 25 to -70 oC, both galvanostatically (two-electrode cells) and potentiodynamically (three-electrode cells). Subsequently, the most promising electrolyte compositions were tested in Al-graphite batteries to determine their technological feasibility and electrochemical properties, particularly at lower temperatures. The results indicate that AlCl3-urea-[EMIm]Cl in a 1.3:0.25:0.75 molar ratio can be used to enhance the electrochemical performance, reduce the cost, and expand the operating temperature window of rechargeable aluminum batteries compared to the AlCl3-[EMIm]Cl standard.
Development of Dual-Carbon Batteries with Amide-Based Ionic Liquid Electrolytes
Authors: Yamamoto Takayuki , Oe Riku , Uehara Keigo , Ishio Yoshifumi , Yadav Alisha , Nohira Toshiyuki 
Published: December 2024

Increasing demands for large-scale energy storage systems have driven us to the development of various next-generation batteries as alternatives of lithium-ion batteries (LIBs). Current LIBs potentially possess a major concern about the supply instability of scarce cobalt resources used in positive electrode materials. Dual-carbon batteries (DCBs) are considered as one of the promising solutions because DCBs are composed of carbon-based materials for both positive and negative electrodes, and thus they are free from the utilization of rare metals. We have focused on ionic liquids (ILs) as electrolytes for DCBs [1,2]. In contrast to so-called rocking-chair-type batteries like practical LIBs, the charge carrier ions are reserved in the electrolytes at the initial (discharged) state of DCBs, which is expressed as reserve-type batteries and requires large charge carrier densities in the electrolytes. Typical ILs are composed of only cations and anions without neutral solvents [3], indicating the eligibility of DCB electrolytes.
We recently conducted a systematic study on the charge–discharge behavior of graphite positive electrode in FSA- and FTA-based ILs (FSA = bis(fluorosulfonyl)amide, FTA = (trifluoromethylsulfonyl)(fluorosulfonyl)amide) [1]. Although the graphite positive electrodes showed higher reversible capacities in FTA-based ILs compared to FSA counterparts, Na[FSA]-based IL specifically gave moderate discharge capacities of approximately 80 mAh g−1. Furthermore, we selected K[FTA]-based IL as a promising electrolyte and demonstrated the graphite/graphite full-cell operation [2]. This IL-based DCBs exhibited reasonably high performance for 300 cycles in terms of capacity retention ratio and coulombic efficiency.
In the present study, we will comprehensively discuss the charge–discharge behavior of graphite positive electrode in amide-based IL electrolytes including further investigation of the specific phenomena in the Na[FSA]-based IL.

Acknowledgments

This study was partly supported by JSPS KAKENHI grants (JP21K14718 and JP24K01602) and a research grant from the Murata Science and Education Foundation.

References

[1] T. Nikaido, A. Yadav, T. Yamamoto, and T. Nohira, J. Electrochem. Soc., 170, 020526 (2023).
[2] A. Yadav, H. Kobayashi, T. Nikaido, T. Yamamoto, and T. Nohira, J. Power Sources, 585, 233628 (2023).
[3] T. Yamamoto and T. Nohira, Chem. Rec., 23, e202300169 (2023).
Redox Reaction of Some Nitroxyl Radicals in 1-Butyl-1-Methylpyrrolidinium Bis(fluorosulfonyl)amide in the Presence and Absence of Lithium Ion
Authors: Katayama Yasushi , Kato Shodai , Serizawa Nobuyuki 
Published: December 2024

Ionic liquids composed of bis(fluorosulfonyl)amide (FSA–) have been investigated as the promising electrolytes for rechargeable lithium batteries due to their high conductivity and low viscosity dependence on the Li salt concentration. Despite many reports on FSA–-based ionic liquids as the electrolytes for rechargeable lithium and sodium batteries, a few studies have been reported on the electrode reactions of redox species. The redox reactions of Ag+/Ag and ferrocenium (Fc+)/ferrocene (Fc) were investigated in BMPFSA (BMP+ = 1-butyl-1-methylpyrrolidinium)[1]. It was reported that the donor ability of FSA– was found to be lower than that of bis(trifluoromethylsulfonyl)amide (TFSA–) from the potential difference between Ag+/Ag and Fc+/Fc. 2,2,6,6,-Tetramethylpiperidine-1-oxyl (TEMPO) is one of the typical niroxyl radicals with redox activity. In the present study, the redox reactions of TEMPO and 4-oxo-TEMPO were investigated in BMPFSA in the presence and absence of lithium ion.
The redox reactions of TEMPO+/TEMPO and 4-oxo-TEMPO+/4-oxo-TEMPO were observed on a Pt electrode in BMPFSA by cyclic voltammetry. The formal potential of TEMPO+/TEMPO was lower than that of 4-oxo-TEMPO+/4-oxo-TEMPO. The formal potential of TEMPO+/TEMPO in the presence of Li+ was higher than that in the absence of Li+, suggesting that the interaction between TEMPO and Li+ affected the thermodynamic properties of the redox species. The diffusion coefficients and the standard rate constants were evaluated by chronoamperometry and electrochemical impedance spectroscopy, respectively. The diffusion coefficient and the standard rate constant were suggested to be controlled not only by the viscosity but also by the interaction between the nitroxyl radicals and Li+.
Reference
[1] S. Kato, N. Serizawa, and Y. Katayama, J. Electrochem. Soc., 170, 046504 (2023).