bluuebunny/crossref_metadata_2025_split huggingface dataset:
High Energy Density Hydrogen/Vanadium Hybrid Redox Flow Battery Utilizing HCl As a Supporting Electrolyte
Authors: Parra-Puerto Andres , Rubio-Garcia Javier , Cui Junyi , Kucernak Anthony 
Published: December 2020

Hybrid gas-liquid hydrogen/liquid electrolyte energy storage systems known as RFCs (reversible fuel cells) replace the negative liquid electrolyte by the kinetically fast hydrogen reaction which among other advantages reduces the electrolyte cost. A significant amount of work has been devoted to the development of RFCs using halogen redox couples at the positive side, particularly bromine.[1] However, the highly corrosive environment associated with the liquid electrolyte containing halogen species leads to poor compatibility and stability of materials as well as safety issues associated with the leakage of toxic fumes. This issue can be minimized or even eradicated with the implementation of other redox couples such as organic[2] or inorganic species.[3]
We demonstrate a high energy density Hydrogen/Vanadium (6M HCl) system with increased vanadium concentration (2.5 m vs. 1 m), and standard cell potential (1.167 vs. 1.000 V) compared to previous vanadium-hydrogen systems.[4] The implementation of an Ir/C catalyst at the negative side enables a system with high energy density of ca. 45 W h L-1 at 75 mA cm-2 (assuming gas compression at 30 bar) and >67% electrolyte utilization.

References

1] K. T. Cho, M. C. Tucker, and A. Z. Weber, “A Review of Hydrogen/Halogen Flow Cells,” Energy Technol., vol. 4, no. 6, pp. 655–678, Jun. 2016, doi: 10.1002/ente.201500449.
[2] J. Rubio-Garcia, A. Kucernak, R. Liu, and B. Chakrabarti, “Hydrogen/functionalized benzoquinone for a high-performance regenerative fuel cell as a potential large-scale energy storage platform,” J. Mater. Chem. A, vol. 8, no. 7, pp. 3933–3941, Feb. 2020, doi: 10.1039/c9ta12396b.
[3] J. Rubio-Garcia et al., “Hydrogen/manganese hybrid redox flow battery,” J. Phys. Energy, vol. 1, no. 1, p. 015006, Dec. 2018, doi: 10.1088/2515-7655/aaee17.
[4] J. Rubio-Garcia, J. Cui, A. Parra-Puerto, and A. Kucernak, “High Energy Density Hydrogen/Vanadium Hybrid Redox Flow Battery Utilizing HCl as a Supporting Electrolyte for Large Scale Energy Storage Applications.” Under Review.

Figure 1
Interface Structure and Transport Properties of Thin-Film Solid-State Batteries with an Epitaxial Cathode
Authors: Shirasawa Tetsuroh , Shiraki Susumu , Nishio Kazuo , Shimizu Ryota , Hitosugi Taro 
Published: December 2020

A problem of solid-state Li ion batteries is a relatively low ionic conductivity at the interface between electrodes and electrolytes that limits the charging/discharging rate. For designing the solid-state batteries, understanding the mechanism behind the low interface conductivity is crucial. Investigation of the atomic structure of the interfaces and its relation to the ionic conductivity would be helpful for this purpose. However, atomic-scale observation of the buried interfaces is often difficult in practical batteries which consist of grain aggregates. Recent progress in thin-film deposition techniques of electrodes and electrolyteshas opened a path to study the interface quantitatively. By using an all-in-vacuum battery fabrication system [1], we succeeded in fabricating a very low solid-electrolyte/electrode interface resistance in thin film batteries with an epitaxial cathode. The well-defined crystalline interfaces allow the analysis of atomic-scale structure and its transport properties. For the structure analysis, we used X-ray crystal truncation rod (CTR) scattering which enables the atomic-scale analysis in a non-destructive manner.
The analysis of two interfaces will be presented: a solid-electrolyte/electrode interface and an electrode/current collector interface. In the former case, we studied Li(negative electrode)/Li3PO4(solid electrode)/LiCoO2(positive electrode) thin-film Li batteries with low and high (more than 10 times) interface resistances. It turned out that the low-resistance interface has an atomically well-ordered LiCoO2 surface and a disordered surface CoO2 layer can results in the high-resistance interface, demonstrating the crucial importance of the structural ordering in the interfacial layer for realizing a low-resistance interface [2]. In the second topic, we focused on electrode/current collector interface that can also affect the battery performance. We found a drastic improvement of the charging/discharging property by inserting 1.2 nm-thick band insulator LaAlO3 into the LiCoO2 (electrode)/Nb-doped SrTiO3 (current collector) interface. The CTR analysis revealed that a formation of electric dipole at the LaAlO3/Nb-doped SrTiO3 interface, which causes a energy band alignment preferable for the electronic conductance between the electrode and the current collector.

References

[1] M. Haruta, T. Hitosugi et al., Nano Lett. 15, 1498 (2015)
[2] S. Shiraki, T. Shirasawa et al., ACS Appl. Meter. Interfaces 10, 41732 (2018)

Figure 1
(Invited) Lithium Metal Polymer Batteries: State-of-the-Art of the Technology and Commercial Prospects
Authors: Lecuyer Margaud 
Published: December 2020

BlueSolutions has been commercializing all-solid state batteries since 2011. EVs, buses and stationary applications are the main targets of its research and development program. After more than 15 years, this Bolloré group subsidiary masters all the industrial processes for the production of a unique solid state battery technology. The know-how goes from the transformation of the lithium ingots to the integration of the battery packs within the applications. Importantly, a low-ecological footprint process has been stated for both the positive electrode and the polymer electrolyte manufacturing.
In order to get incomparable energy densities, today, all the industrial actors of lithium batteries are hardly working on the lithium metal technology. In this context, BlueSolutions has a unique 10 years feedback regarding both the behavior of this special anode and of the solid-state electrolyte.
After having spread the first pack generation for 8 years all-over the world, an optimized 650V battery pack is about to be delivered. It is especially designed for heavy vehicles, such as buses. To match with customers expectations this new generation offers optimized performance and a very long cyclability. In the meanwhile, BlueSolutions has already started working on its future generation products. While the current battery is LFP-based and cycles at a nominal temperature of 80°C, a lot of efforts are dedicated to improve the actual chemistry. Research programs are conducted on the development of a new positive electrode with higher energy density, new polymers that will be compatible with high-voltage materials and which have high conductivity at ambient temperature and optimized lithium electrode. In fine, the goal is to keep the intrinsic safety of the polymer solid electrolyte, while benefiting from the promising performances of new electrode materials.
Separation of Uranium and Zirconium in Alkali Chloride Melts Using Liquid Metal Cathodes
Authors: Volkovich Vladimir A. , Maltsev Dmitry , Soldatova Maria N. , Ryzhov Alexander A. , Ivanov Alexander B. 
Published: December 2020

Alkali chloride melts are considered as prospective working media for non-aqueous pyrochemical reprocessing of spent nuclear fuels (SNFs). Separation of fissile materials from fission products in pyrochemical reprocessing can be achieved electrochemically and amongst all the fission products zirconium has the closest electrochemical properties to uranium. Uranium and plutonium fission produces several zirconium isotopes (from Zr-91 to Zr-97) and depending on the reactor neutron spectrum, nuclear fuel type, burnup and cooling time SNF arriving for reprocessing can contain ca. 5–13 kg of zirconium (as the fission product excluding cladding) per ton. Electrochemical separation of uranium and zirconium in fused salts is a challenging task.
The present work was devoted to studying the electrochemical behavior of zirconium and uranium in 3LiCl–2KCl based melts using cyclic voltammetry and cathodic polarization. The experiments were performed in LiCl–KCl–ZrCl4, LiCl–KCl–UCl4, LiCl–KCl–UCl3 and LiCl–KCl–ZrCl4–UCl4 melts.
On a solid tungsten electrode zirconium(IV) ions were reduced to Zr(0) in two stages and the metal deposition potentials were between –2.17 and –2.07 V (at 532–637 oC) vs. Cl–/Cl2 couple. Changing the solid electrode to liquid zinc, gallium or gallium–zinc eutectic alloy (3.64 wt. % Zn) resulted in significant shift of zirconium deposition potential in the positive direction. Examples of the polarization curves are shown in the Fig. Polarization measurements performed in LiCl–KCl–ZrCl4–UCl4 melt on the Ga–Zn electrode showed that reduction of U(IV) to U(III) and deposition of zirconium occurred at very similar potentials and deposition potential of uranium was significantly more negative. Separation factor for uranium/zirconium couple was also determined.
Fig. Polarization of Ga–Zn eutectic alloy cathode in LiCl–KCl–UCl4 (524 oC) and LiCl–KCl–ZrCl4 (550 oC) melts.

Figure 1
Electrochemical Behavior of Silver Halogenocomplexes in an Amide-Type Ionic Liquid
Authors: Serizawa Nobuyuki , Kuwahara Suguru , Katayama Yasushi 
Published: December 2020

Silver halides, AgX (X = Cl–, Br–, and I–), are known to be typical poorly soluble salts in aqueous solution. AgX is also almost insoluble in an amide-type ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonly)amide (BMPTFSA). However, AgX has been known to dissolve in the media in the presence of X– by forming halogenocomplexes, [AgX
n
](n–1)–. Dissolution of AgCl has been reported in basic chloroaluminate ionic liquids[1] and deep eutectic solvents containing Cl–. In these reports, however, electrochemical behavior of [AgX
n
](n–1)– has not been studied in detail. We have already reported that some metal chlorides are soluble in BMPTFSA in the presence of Cl– and that electrodeposition of the metals is possible[2,3]. In the present study, dissolution of AgX has been investigated in BMPTFSA with addition of BMPX. Furthermore, electrodeposition of Ag and electrochemical preparation of Ag nanoparticles have been examined in the Lewis basic ionic liquids.
AgX was found to dissolve in BMPTFSA containing 0.5 M BMPX. The dissolved species was determined to be [AgX3]2– by potentiometric technique. The deposition and dissolution of Ag were observed in cyclic voltammetry. The redox potential of [AgX3]2–/Ag was more negative than that of [Ag(TFSA)3]–/Ag and dependent on the kind of halide. The diffusion coefficient of [AgX3]2– was determined by chlonoamperometry. The initial stage of electrodeposition of Ag on a glassy carbon electrode was regarded as progressive. Potentiostatic cathodic reduction of [AgX3]2– resulted in deposition of Ag. The morphology of Ag deposits depended on the reduction potential. Formation of Ag nanoparticles dispersed in the ionic liquid was confirmed after potentiostatic cathodic reduction at a negative potential using transmission electron microscopy[2].
References
[1] T. M. Laher and C. L. Hussey, Inorg. Chem., 22, 1279 (1983).
[2] Y. Katayama, Y. Oshino, N. Ichihashi, N. Tachikawa, K. Yoshii, and K. Toshima, Electrochim. Acta, 183, 37 (2015).
[3] M. Sano, N. Tachikawa, K. Yoshii, N. Serizawa, and Y. Katayama, Electrochemistry, 86, 260 (2018).
Electrochemical Investigation of (De-)Lithiation Behaviors of Al Anodes and the Solubility Range of β-Lial Phase at Room Temperature
Authors: Zheng Tianye , Kramer Dominik , Tahmasebi Mohammad H. , Geßwein Holger , Mönig Reiner , Boles Steven T. 
Published: December 2020

Alloy anodes have been extensively studied over past decades to replace the graphite of lithium-ion batteries (LIBs). Most efforts are made towards those anode materials with high specific capacities such as silicon and germanium. To minimize the negative impacts of the volume expansions during Li incorporation, protective coatings or specific micro- and nanostructures have been suggested, but a commercialization on a larger scale was impeded by such preparation costly procedures. Therefore, the optimal alloy anode candidate should balance the cost, capacity and manufacturing complexity rather than solely maximize the specific capacity. Aluminum, an underappreciated anode material, possesses intrinsic properties that fulfill the criteria mentioned above. The origin of the main capacity of aluminum anode is upon the formation of the β phase (LiAl; ca. 1Ah/g). However, the (de-)alloying processes of Al remain poorly understood, especially at room temperature under which LIBs usually operate.
In this study, we investigate the (de-)lithiation that occurs within the solubility range of the β phase Although this Li solubility is highlighted by multiple versions of the Li-Al phase diagrams, the solubility range at low temperatures was not specified yet due to the experimental conditions of previous phase diagram studies (> 400 °C). Various electrochemical analytic tools and methods are used to shed light on the Li solubility within the β phase. The Li solubility range of the β phase is determined to be roughly 5 at% by a potentiostatic charge counting experiment at room temperature. Moreover, the cyclic voltammetry of partially lithiated Al foils shows that the β phase can be (de-)saturated without propagating the phase front towards the α phase. If galvanostatic charge and discharge is smartly controlled by taking into consideration of the solubility range, the cycling life of β-LiAl anode can be significantly improved. Not only does this piece of work provide fundamental data for the β-LiAl phase at room temperature that complements the existing phase diagrams, but also implies that aluminum foil holds great potential as an anode material for the next generation of lithium-based batteries.
Electrocatalytic Conversion of CO2 over Bimetallic Electrocatalysts - Relationship between the Selectivity and Surface Structure of Catalysts
Authors: Gunji Takao 
Published: December 2020

Conversion reaction of CO2 by electrolysis on heterogeneous catalysts have been attractive attention due to not only decreasing the amount of CO2 of greenhouse gas but also mitigate the exhaust of energy resources. However, since CO2 is the most stable compounds in the carbon based owning to its C=O bond in CO2 molecular, it is significantly difficult to convert CO2 into other compounds such as hydrocarbons as well as HCOOH, and CO.
So far, several efforts have been made to improve both electrocatalytic activity and selectivity towards CO2 reduction reaction. It is well-known that novel metals such as Pd, Au and Ag possesses a CO-selectivity, and non-precious metals such as Pb, Bi, and Sn exhibit a formate selectivity. In particular, Cu is attracting much attention as the electrocatalyst for electrochemical CO2 reduction reaction because it is proved as a unique electrocatalyst for CO2 reduction; metallic Cu possesses organic compounds (i.e., methane, ethane, ethylene, and/or methanol) selectivity. However, formation of organic compounds from the CO2 reduction reaction requires a high overpotential when Cu is used as electrocatalyst. In order to prepare a novel electrocatalyst which shows a high selectivity for organics production with low overpotentials, we attempt to prepare Pd based atomically ordered intermetallic compounds.
Today, I present recent two topics; (i) investigating electrocatalytic selectivity of Pd-based alloys toward the CO2 reduction reaction, depending on second metals, and (2) how can be prepared the Pd-based intermetallic compounds which exhibit the organic selectivity.
Understanding the Catalytic Site in RuOx-TiOx Electrodes for Chlorine Evolution Reaction
Authors: Dong Heng , Hoffmann Michael R. 
Published: December 2020

As late as in 2017, there were still at least one third of world population suffering from water sanitation problems. Electrochemical oxidation (EO) technology, which relies on anodic generation of reactive chlorine and oxygen species as oxidants and disinfectants, has been shown feasible for human wastewater onsite treatment and recycling. Pivotal to the EO system is anodic chlorine evolution reaction (CER). Traditionally, oxides of platinum group metals (PGMs) have shown excellent catalytic activity for CER, with RuO2 identified as the golden standard. However, fast acid dissolution and prohibitive price prevents its real application. On the other hand, RuOx-TiOx binary electrodes (denoted as RTO electrodes) have demonstrated both enhanced activity and stability compared to pure RuO2, and it has been used in chloro-alkali industry for centuries as one of the dimensionally stable anodes (DSA). Previous research has ascribed the exceptional activity of RTO electrodes to Ti-Ru polarizations pairs (denoted as RuOx
𝛿
+-TiOx
𝛿
-). Nevertheless, the actual catalytic site (RuOx
𝛿
+ or TiOx
𝛿
-), as well as the specific mechanism, has remained elusive.
In this work, ultrathin sandwich electrodes were fabricated by sequentially depositing nanometer-thick uniform crystalline TiO2 and RuO2 films onto HF-treated atomically flat Si wafers to study the active sites in RTO electrodes. The electrodes were characterized with scanning electron microscope (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM), while the CER catalytic activity was probed by chronopotentiometry experiments in 5 M NaCl solution. The structure of the sandwich electrodes was varied to investigate the activity of both components, and layer thickness was varied to quantify the effective range of Ti-Ru polarizations. Density functional theory (DFT) computation was used to help understand the catalytic mechanism.
In order to promote further application of EO systems in developing countries, electrodes at lower price are essential. Not only does this work shed light on the catalytic mechanism of RTO electrodes, it also provides important guidance for design of low-PGM or PGM-free electrodes towards high-efficiency CER catalysis and wastewater treatment.
The Effect of Additives on the Performance and Failure Mechanisms of the Rechargeable, Low-Cost, Alkaline Zinc Electrode
Authors: D'Ambrose Michael Joseph , Turney Damon , Yadav Gautam Ganapati , Nyce Michael , Messinger Robert J. , Banerjee Sanjoy 
Published: December 2020

Metallic zinc (Zn) is an attractive negative electrode material for rechargeable batteries because it is a non-toxic, non-flammable, earth abundant metal that is compatible with aqueous electrolytes. Zinc metal is also energy dense, exhibiting a high gravimetric discharge capacity of 820 mAh/g, a high volumetric discharge capacity of 5850 mAh/mL, and a low equilibrium potential of -1.35 V vs. mercury-mercuric oxide (Hg|HgO) in concentrated alkaline electrolyte. Rechargeable aqueous Zn alkaline batteries have thus recently been the subject of intense investigations for safe, low-cost, stationary electrochemical energy storage. Our research aims to achieve Zn depth-of-discharge (DOD) of 20% that is sustainable for 500 or more charge-discharge cycles, corresponding to an overall battery energy density of 200 Wh/L at the cell level.
However, the cycle life of the porous Zn electrode in concentrated alkaline electrolyte is observed to decrease strongly with increasing Zn DOD. For example, we recently demonstrated that metallic Zn electrodes cycled in the range of 1% to 16% Zn DOD had an exponential decrease in cycle life with Zn DOD, which was attributed mostly to the loss of active Zn material. Here, we study the effect of additives to increase the Zn DOD and cycle life of Zn electrodes. Zinc oxide (ZnO) was used as a starting material from which metallic Zn was formed in zinc-nickel (Zn-Ni) batteries. Additives were incorporated into the ZnO electrodes for the tests done on Zn-Ni batteries and these electrodes were cycled in the range of 15% to 30% Zn DOD. The potential values of the Zn electrodes vs. Hg|HgO reference electrodes were recorded to identify failure due to Zn. At 15% Zn DOD, ZnO electrodes with certain additives or combinations of additives achieved an increased cycle life compared to Zn electrodes without additives. This highlights the need to perform electrochemical and spectroscopic studies to determine the effects of the additives on the mechanisms of the Zn electrode. These additives, with further understanding, could be implemented in low-cost, energy-dense, rechargeable Zn alkaline batteries for grid-scale energy storage.
Toward Predicting Trends in Propagating Failure and Its Mitigation for a Lithium-Ion Cell Stack
Authors: Hewson John , Kurzawski Andrew , Shurtz Randy C. , Torres-Castro Loraine , Lamb Joshua 
Published: December 2020

Thermal runaway of lithium-ion batteries is a risk that is magnified when stacks of lithium-ion cells are used for large scale energy storage. When limits of propagation can be identified so that systems can be designed to prevent large scale cascading failure even if a failure does occur, these systems will be safer. This work addresses the prediction of cell-to-cell failure propagation and the propagation limits in lithium-ion cell stacks to better understand and identify safe designs.
A thermal-runaway model is presented based on recent developments in thermochemical source terms. It is noted that propagating failure is characterized by temperatures above which calorimetry data is available. Results show high temperature propagating failure predictions are too rapid unless an intra-particle diffusion limit is included, introducing a Damkohler number limiter into the rate expression. This new model form is evaluated against cell-to-cell failure propagation where the end cell of a stack is forced into thermal runaway through a nail-induced short circuit. Limits of propagation for this configuration are identified in terms of the energy density and in terms of the thermal contact between cells. Results show cell-to-cell propagation predictions are consistent with measurements over a range of cell states of charge and with the introduction of metal plates between cells to add system heat capacity representative of structural members. This consistency extends from scenarios where propagation occurs through scenarios where propagation is prevented.
The authors gratefully acknowledge funding from the Department of Energy, Office of Electricity's Energy Storage Program, under the direction of Dr. Imre Gyuk. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.