bluuebunny/crossref_metadata_2025_split huggingface dataset:
Development of Carbon-Based Cathodes for Aluminium-Ion Batteries
Authors: McKerracher Rachel , Holland Alex , Wills Richard , Cruden Andy 
Published: February 2020

The aluminium-ion battery is one of several promising post-lithium technologies under development to combat issues with lithium-ion batteries such as insecure lithium supplies, environmental impact and safety concerns associated with thermal runaway. [1,2]
Aluminium is an abundant material with an energy density of 1060 Wh.kg-1.[3] The limiting factor for the battery performance is the capacity of the cathode towards the intercalation of [AlCl4]- or Al3+ ions. Although several different cathode materials have been studied throughout the past few years, there have been few studies that compare the capacities of different cathode morphologies. Graphitic carbon materials have many features that make them ideal for aluminium-ion intercalation cathodes: they are electrically conductive, easily expandable, low density and low-cost, and are commercially available in a wide variety of morphologies.
In this work, the capacity of four forms of graphitised carbon are compared as aluminium-ion cathodes: pyrolytic graphite, carbon paper, carbon cloth and carbon felt. The materials differ in terms of their physical properties, and thus have different properties as aluminium-intercalating agents. Of all the materials examined, carbon paper had the highest energy density at 122 Wh.kg-1, and had an [AlCl4]- capacity of 70 mAh.g-1. Carbon paper had superior stability compared to pyrolytic graphite, particularly as the C-rate of cycling was increased. It undergoes no change in crystallographic structure even after cycling up to the 20C rate.
Additionally, the optimum distance between electrodes and electrolyte volume in an aluminium-ion cell was studied, and was found to be 1-2 mm in order to avoid shorting caused by eventual growth of aluminium nodules. In ionic liquid, the cell could only be charged to 2.45 V for repeated cycling, but experiments in a separator-less sealed cell showed that if the cell could be charged to 2.75 V, the capacity could be tripled.

References

M. Lin, M. Gong, B. Yu, Y. Wu, D.Y.Wang, M. Guan, M. Angell, C. Chen, J. Yang, B.J. Hwang, H. Dai, Nature, 520, 2015, 324-328.

N. Jayaprakash, S.K. Das, L.A. Archer, Chem. Commun., 47, 2011, 12610-12612.

National Laboratory, Oak Ridge, “Aluminiun-Ion Battery to Transform 21st Century Energy Storage” (pdf), retrieved 30 October 2014.

Figure 1
(Invited) Strategies to Improve Photostabilities of Visible-Emitting Nanophosphors
Authors: Isobe Tetsuhiko , Iso Yoshiki 
Published: February 2020

Nanophosphors have attracted much interest in applications to wide color gamut displays and micro LEDs. Since nanophosphors have a large ratio of surface area to volume, they are sensitive to surrounding environment such as oxygen and water, particularly under irradiation by excitation light. We therefore focus on photostabilities of doped nanosphosphors of YAG:Ce3+ [1–3], YVO4:Bi3+,Eu3+ [4–6], and Y2O3: Bi3+,Eu3+ [7,8], and those of undoped nanophosphors of quantum dots of CuInS2/ZnS [9], InP/ZnS [10], and CsPbX3 (X = Cl, Br, I) [11]. In this talk, we mainly introduce our research on strategies to improve photostabilities of visible-emitting nanophosphors.
[1] Y. Kamiyama et al., J. Electrochem. Soc., 157, J149 (2010). [2] T. Isobe, ECS J. Solid State Sci. Technol., 2, R3012 (2013). [3] Y. Sasaki et al., ECS J. Solid State Sci. Technol., 5, R3049 (2016). [4] S. Takeshita et al., J. Electrochem. Soc., 157, J74 (2010). [5] S. Takeshita et al., Opt. Mater., 33, 323 (2011). [6] H. Hara et al., Mater. Sci. Eng. B, 178, 311 (2013). [7] T. Matsunaga et al., J. Lumin., 165, 62 (2015). [8] T. Watanabe et al., RSC Adv., 7, 14107 (2017). [9] C. Wada et al., RSC Adv., 7, 7936 (2017). [10] T. Watanabe et al., ECS J. Solid State Sci. Technol., 6, R75 (2017). [11] Y. Iso et al., ECS J. Solid State Sci. Technol., 7, R3040 (2018).
(Invited) A Quantum Electrodynamics Formulation of Energy Transfer Via Electric Dipole-Magnetic Dipole and Magnetic Dipole-Magnetic Dipole Interaction of Two Optically Active Ions
Authors: Collins John , Mishra Kailash C 
Published: February 2020

The nonradiative electron transfer process between optically active ions in luminescent materials via electric dipole (ED)-magnetic dipole (MD) and magnetic dipole-magnetic dipole interaction has been investigated using a molecular quantum electrodynamics (QED) approach. The QED approach provides an intuitively simple but rigorous method of calculating the energy transfer probability through multipolar interactions such as the ED-MD and MD-MD interactions considered in this work. More details of this approach and its application to resonant energy transfer between molecules through the ED-ED interaction can be obtained from Craig and Thirunamachandran [1] and references therein.
The energy transfer process between two ions in the present study is shown schematically in Figure 1.
While the energy levels have been considered to be discrete within the QED formulation for calculating the transition probabilities, the broadening of the energy levels in solids has been processed using the spectral line shape functions without using the special normalization in the energy space used by Dexter [2]. The transition probabilities have been simplified further using experimentally observable spectroscopic parameters such radiative lifetime and absorption cross section. The final expressions for transition probability includes additional periodic functions that are meaningful only in the short wavelength regime of the electromagnetic radiation.
In this presentation, we will consider two classes of Feynman diagrams to calculate the transition rates for the energy transfer process through ED-MD and MD-MD interactions. In all the cases, the interaction between two ions is mediated by photons. In one class of diagrams, the photon is emitted first by ion A, and then absorbed by ion B at a later time. In other class of diagram, the photon is absorbed by ion B first and then emitted by ion A. The second class pertains to emission and absorption of a virtual photon. The theoretical details of calculating the transition probabilities and their significance will be presented. It will also be shown how this approach could be used in other luminescence processes to determine their plausibility and the transition rates.
[1] D. P. Craig and T. Thirunamachandran, Molecular Quantum Electrodynamics, Dover Publications, Mineola, New York (1998).
[2] D. L. Dexter, J. Chem. Phys. 21, 836 (1953).

Figure 1. A schematic diagram of energy transfer from ion A to ion B. The associated eigenstates and eigenenergies for each of these ions are indicated. The wavy line indicates transfer of energy from the ion A and B while the solid arrows indicate the electronic transitions each ion is going through simultaneously.

Figure 1
Intermediate Hopping on Flexible Cascade Surface with Electrostatic Channeling
Authors: Liu Yuanchao , Calabrese Barton Scott 
Published: February 2020

Tandem bio-catalysis is able to fully utilize the bond energy stored in complex molecule by using sequential active sites. This results in an enhanced efficiency in electrocatalytic devices, enabling biofuel cells with higher energy density and biosensors with high sensitivity. Mass transport of reaction intermediate molecules is a key factor impacting the overall kinetics, which in nature is facilitated by substrate channeling, where intermediates are directly shuttled to the next active site instead of diffusing into the bulk.1

Electrostatic channeling represents one such mechanism, where charged intermediates are transported along an oppositely charged pathway. Natural electrostatic cascades have been studied for decades, and in 2017 we reported the first cascade with artificially introduced electrostatic channeling.2 This finding highlighted a surface diffusion mechanism on a 1D channeling bridge. However, intermediate transport between the bridge and the downstream enzyme binding site occurs on a flexible 2D surface exhibiting a range of interactions with the intermediate and potentially greater leakage. This process is of great significance to further explore the channeling kinetics and also make optimization for cascade design. Here, we are going to further map the channeling pathway between the bridge and intermediate active site. Enhanced sampling methods is used to elucidate the intermediate’s ergodicity in this process. Finally, kinetic Monte Carlo method is used to quantify the overall kinetics, from which the leaking contribution from each channeling region can be evaluated.
REFERENCE

I. Wheeldon, S. D. Minteer, S. Banta, S. C. Barton, P. Atanassov and M. Sigman, "Substrate channelling as an approach to cascade reactions", Nature Chemistry, 8, 299–309 (2016). doi:10.1038/nchem.2459.

Y. Liu, D. P. Hickey, J.-Y. Guo, E. Earl, S. Abdellaoui, R. D. Milton, M. S. Sigman, S. D. Minteer and S. Calabrese Barton, "Substrate Channeling in an Artificial Metabolon: A Molecular Dynamics Blueprint for an Experimental Peptide Bridge", ACS Catalysis, 7, 2486–2493 (2017). doi:10.1021/acscatal.6b03440.

Figure 1
Nickel Oxide Thin Film Photoelectrodes Prepared By RF Magnetron Sputtering
Authors: Valdemarsson Kim , Wang Kaiying 
Published: February 2020

Out of several different promising first-row transition metals (Ni, Co, Mn and Fe) to be used for the Oxygen Evolution Reaction (OER) in a water splitting system, Nickel Oxide (NiO) turns out to be the most promising of them all, with the highest catalytic activity [1-2]. One of the key limitations on water electrolysis is that it is thermodynamically unfavorable due to demanding a significant amount of energy to make the reaction happen at an appreciable rate [2]. This further pushes the need for an efficient catalyst material to be used for anode in a photoelectrochemical (PEC) cell.
In this work, a thin film of nickel oxide (NiO) is deposited with RF magnetron sputtering technique on quartz, glass and indium tin oxide (ITO) substrates in pure argon atmosphere respectively. The thin films are characterized by Ultraviolet-visible spectroscopy (Uv-Vis), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX), X-Ray Diffraction (XRD) analysis and 4-probe resistivity measurements. Typical UV-Vis and X-ray diffraction patterns (Fig. 1a-b) show that thin film NiO are successfully fabricated on these substrates. It can be seen from Figure 1b that increase in temperature significantly increases the material crystallinity, with some peaks becoming clearly more visible. From Table 1 we can deduct that the increase in power increase oxygen in the compound. The electrical properties are to be measured at probe stations for low temperatures (5K) up to room temperature. In summary, the phase transition of thin film NiO as well as light absorption from 220 to 850 nm have been investigated on these substrates.

References

[1] P. C. K. Vesborg, B. Seger, I. Chorkendorff, Recent development in Hydrogen Evolution Reaction Catalysts and their Practical Implementation, The Journal of Physical Chemistry Letters (2015). DOI: 10.1021/acs.jpclett.5b00306
[2] Y. Cheng, S. P. Jiang, Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes, Progress in Natural Science: Materials International (2015), DOI: 10.1016/j.pnsc.2015.11.008

Figure 1
Kinetic of Metal Extraction at the Water|1,2-Dichoroethane Interface
Authors: Pérez-Zúñiga Jared A , Amador-Hernández Judith , Sánchez-Muñoz Cervando , Colunga Urbina Edith M , de la Garza Rodríguez Iliana M , Velazquez-Manzanares Miguel 
Published: February 2020

The electrochemical techniques are useful tools for the extraction of heavy metals from aqueous effluents. Between them, studies at the interface of two immiscible electrolyte solutions (ITIES) allow to understand the fundamentals that regulate the process of ionic metal extraction through hydrophobic barriers, owing to it is possible to control the equilibrium of the metal ion across the interface by applying an electrical potential. In the present work, it was studied the kinetic process of the facilitated ionic metal transfer by dibenzo-18-Crown-6 and diciclohexane-18-Crown-6 at the water/1,2-dioclhoroetane (1,2-DCE) interface
The electrochemical experiments were carried out in a 4-electrode cell (two references and two counterelectrodes) and the interface was polarized by cyclic voltammetry (CV). The rate constant (k) for the facilitated metal transfer at the water/1,2-DCE interface was evaluated from CV data through the procedure proposed by Nicholson. The peak-to-peak separation (DEp) of the transfer from the aqueous to the organic phase and from organic to the aqueous phase wave, as well as the diffusion coefficient, were considered for the calculus of k. The results showed that k is in the range of 10-3 cms-1, which is according to the values previously obtained for ion transfers at the liquid-liquid interface.
(Invited) Metal Production in CaCl2-Based Melts
Authors: Suzuki Ryosuke O. , Noguchi Hiromi , Haraguchi Yasushi , Natsui Shungo , Kikuchi Tatsuya 
Published: February 2020

Left-side elements in periodic table are stable in oxide state. In order to produce their metals from the oxides, the molten CaCl2 is useful as the media where CaO is dissolved. By applying 3.0 V above melting temperature of CaCl2 (1045 K), CaO in CaCl2 melt electrochemically decomposes into metallic Ca and oxygen. The deposited Ca at cathode can work as reductant for the stable oxides. Because of strong reducing ability of Ca, Ti can be produced directly from TiO2. This calciothermic reduction forms a lot of CaO at the cathode, but it dissolves in CaCl2 and decomposes again by electrolysis. This OS process could be applied to TiO2 or other oxides. Even if electric insulators such as Al2O3 were used, metallic Al could be obtained. V2O5 and Bi2O3 are molten oxides, but they could be reduced to metallic state. It is noted that Al and Bi are liquid metals at the operating temperature.
The trials to decrease the residual oxygen in Ti are introduced from TiO2 and CaTiO3. By optimizing the cathodic structure, CaO content in the bath, H2O removal and cooling procedures, 1500 mass ppm oxygen could be achieved.
Oxygen anions at carbon anode form CO and CO2 gas bubbles. If gas bubbles do not leave from the anodic surface, CO2 gas forms CO3
2-. Carbonate ions are reduced by Ca to carbon, or electrochemically deposite carbon on cathode. These parasite reactions decrease the current efficiency. Quick removal of CO2 gas bubbles from anode is a key.
By applying TiS2 or V3S4 as the starting materials, good quality of metallic Ti or V, respectively, could be realized because they do not form solid solution with sulfur. The sulfur gas deposited at the cold parts of reaction vessel, and can be used for sulfide formation.
Interaction of Neodymium Containing Chloride Melts with Oxygen Species
Authors: Shchetinskiy Andrey V. , Dedyukhin Alexander S. , Volkovich Vladimir A. , Kaychenkova Regina Yu. , Maltsev Dmitry S. , Polovov Ilya B. , Chukin Andrey V. 
Published: February 2020

Alkali chloride based melts can be employed as working media in spent nuclear fuels pyrochemical reprocessing. Oxygen is on of common impurities in technology and oxygen species can seriously influence speciation of metals in molten electrolytes. From the other hand, one of the possible ways of separating uranium from rare earth fission products by selective precipitation of uranium oxide. The present work was aimed at studying reactions taking place in chloride melts containing neodymium (III) and uranium (III and IV) ions upon addition of oxygen species. In particular, reactions with oxygen and oxide ions (introduced in form of lithium oxide) were considered.
Thermodynamic modeling of possible reactions was first performed to estimate the possibility of separating uranium from rare earths. The experiments were then conducted in the melts based on LiCl–KCl eutectic, NaCl–KCl equimolar mixture and individual LiCl at 550 oC (for LiCl–KCl) and 750 oC for all the melts). Reaction of the melts containing NdCl3, UCl3 or UCl4 with Li2O (at various O2– to Nd3+ (U3+, U4+) mole ratios) and with O2 was investigated.
High temperature electronic absorption spectroscopy was employed to determine the kinetics of the reactions taking place. Phase composition of the solid phases was characterized by X-ray powder diffraction analysis. Size of the particles in the precipitates formed at various conditions was also determined to assess the feasibility of subsequent separation of the solids from the technological melts.
The Effects of Excess Protic Species on Oxygen Reduction in Protic Ionic Liquids and Implications for the Use of Ionic-Liquid Electrolytes in Fuel Cells
Authors: Walsh Darren Anthony , Goodwin Sean , Smith Daniel 
Published: February 2020

The conventional polymer-electrolyte membranes used in low-temperature fuel cells are limited to operating temperatures below about 120 ºC, as they must be fully hydrated to facilitate proton transport. Protic ionic liquids (PILs) are ionic liquids formed by transferring protons from Brønsted acids to Brønsted bases, and it has recently been shown that some ammonium-based PILs inherently exhibit high proton conductivities. Consequently, PILs have been proposed for use as electrolytes in non-humidified fuel cells that can operate above 120 ºC (at intermediate temperatures). However, while they nominally consist entirely of ions, PILs can often contain a significant quantity of neutral species (either molecules or ion clusters) that can affect the physicochemical properties of the liquids.
In this contribution, we first describe an electroanalytical method for detecting and quantifying residual Brønsted acids in a series of ammonium-based PILs. Ultramicroelectrode voltammetry reveals that some of the accepted methods for synthesizing PILs can readily result in the formation of nonstoichiometric PILs containing up to 230 mmol dm−3 residual acid. We will then show that residual acid in PILs can have a drastic effect on the electrocatalytic oxygen reduction reaction (ORR; O2 + 4e−+ 4H+→ 2H2O) in the PILs. For example, the potential at which the ORR occurs at Pt in the PIL diethylmethylammonium trifluoromethanesulfonate, [dema][TfO], decreases linearly as the strength of the proton donor in the liquid decreases. In “pure” [dema][TfO], in which the proton donors during the ORR are the [dema]+ cations of the PIL (pK
a = 10), the onset potential of the ORR is the same as that of the hydrogen oxidation reaction (HOR) in the PIL. These observations have significant implications for the use of PILs as electrolytes in fuel cells and indicate that the best PILs are highly "acidic" liquids that can support oxygen reduction at high potentials.
Natural Antioxidants for Activated Carbon-Based Electrochemical Capacitors with Enhanced Energy and Cycle Life
Authors: Fic Krzysztof , Menzel Jakub , Bujewska Paulina 
Published: February 2020

Several forms of activated carbons have already been implemented and widely investigated as electrodes for electrochemical capacitors. Aqueous solutions based on inorganic salts demonstrated effective operating voltages around 1.6 V, and several interesting strategies have been furthermore implemented to improve these systems, including the redox activity of the electrolyte.
This work is focused on the electrochemical performance of the activated carbon electrodes operating in various electrolytes containing redox couple based on the ascorbic acid and sodium ascorbate. Since sulphate (SO4
2-) and nitrate (NO3
-) -based aqueous solutions have already been widely investigated, this study will discuss these electrolytes modified by the redox-active additive and their interaction with a carbon electrode. The results obtained clearly indicated that redox mediators play an important role in the charge accumulation process and has an excellent redox chemistry. Dependently on the electrolyte pH, the ionic specimen might be easily reduced or oxidized and perfectly preserves the activated carbon surface against oxidation.
A variety of electrochemical methods used in the study confirmed that a specific formulation of the electrolyte with ascorbate-based redox shuttle might remarkably enhance the electrode capacitance (up to 260 F g-1) and the operating voltage (up to 1.8 V). Moreover, operando Raman spectroscopy proved that several bonds are reversibly created while the charge transfer occurs. Furthermore, high specific energy (ca. 14 Wh kg-1) maintained at excellent power rates (1 kW kg-1) has been preserved during 8 000 charge/discharge cycles with reversibility of 94%.

Acknowledgements

European Research Council is acknowledged for financial support within the Starting Grant project (GA 759603) under European Unions’ Horizon 2020 research and innovation programme.
Bio-Derived Nanocarbons in Electrochemical Applications
Authors: Acznik Ilona , Lota Katarzyna 
Published: February 2020

Carbonaceous materials are well known and readily used in a broad range of applications. Owing to the well-developed porous structure and the presence of certain surface functional groups, these materials are commonly used as adsorbents for a wide range of contaminants from gaseous or liquids media. Currently, activated carbons are also widely used as the electrodes for electric double-layer capacitors because of their high surface area, chemical stability and acceptable price.
This work is focused on the carbon materials obtained from biopolymers such as lignin, cellulose and chitosan as precursors. The carbonisation in nitrogen atmosphere followed by chemical activation in KOH was chosen as a synthesis method. The resulting carbon materials were characterised by well-developed surface area and microporous structure, beneficial for electric double-layer capacitors (EDLC) electrodes. In parallel, graphene-like materials obtained from graphite oxidation followed by thermal reduction were also synthesised.
The main goal of performed research tasks was to compare the electrochemical properties of carbon materials applied as electrode materials in different energy storage systems - electrochemical capacitors and in hydrogen storage systems. The special example taken into the consideration were hybrid capacitors composed of a battery-type electrode and a high surface area carbon electrode. This kind of configuration allows merging the advantages and reduces the drawback of redox and capacitive based systems. Since the same electrode material can give different electrochemical response depending on the type of device in which they are employed, this work will report on the influence of the physicochemical properties of carbon-based electrodes of various origin on their electrochemical response in various energy storage systems.