bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Low Pressure and Atmospheric Pressure Plasma Interactions with Molten Metals and Liquid Droplets for Materials Processing
Authors: Sunkara Mahendra Kumar , Jaramillo-Cabanzo Daniel Felipe , Ajayi Babajide
Published: February 2020

Several grand challenges in energy storage and conversion need the discovery functional materials that many agree will be composed of complex compositions and nanoscale materials such as nanowires. In this regard, plasma based materials processing has been shown to be promising for combinatorial techniques and scalable processing. For example, our group has shown that gentle plasma excitation of gas phase will allow the use of non-catalytic, low melting metals for catalyzing nanowire growth. Furthermore, the use of plasma oxidation of liquid precursors allows for creation of metastable complex oxide particles with compositional control. A number of examples will be discussed in which the above two techniques are currently being used for accelerating the development of a variety of catalysts including electrocatalysts and materials for storage applications.

This talk will highlight our efforts to understand the role of plasmas under two categories: (a) the synergistic effects hydrogen and nitrogen plasma interactions with molten metals; and (b) the oxygen plasma-liquid droplet interactions. To gain insights into these mechanisms we have studied the interaction of hydrogen and nitrogen plasmas with low melting point metals, primarily with gallium. Absorption/desorption experiments as well as theoretical-computational calculations were performed. Experiments have shown an increment of adsorbed gaseous species into the molten metal in the presence of plasmas; furthermore, Density Functional Theory (DFT) calculations suggest a strong interaction between atomic hydrogen and molten gallium that is described as a high absorption on the surface, rapid diffusion and a steady state concentration of the gas inside the bulk. In the case of oxygen plasma-liquid droplet interactions for creating complex oxides, the role of solvated electrons and oxygen radicals will be discussed.

Acknowledgements

Author acknowledge primary funding support from NSF Solar Project (DMS 1125909), NSF EPSCoR (1355438). Acknowledge with Dr. Miran Mozetic and Dr. Uros Cvelbar for helpful technical discussions regarding measurements. The presentation includes contributions from Dr. Maria Carreon who is currently at U. of Tulsa.
(Invited) Beyond the Highs and Lows: A Selectively Colorful Yet Chilly Perspective on the Future of Dielectrics in Nanoelectronic Devices
Authors: King Sean W.
Published: February 2020

High-dielectric constant (high-k) gate oxides and low-dielectric constant (low-k) interlayer dielectrics (ILD) have dominated the nanoelectronic materials research scene over the past decade, but have recently reached a state of maturity and perhaps the limits of their scaling. Based on this, one may ponder the direction of nanoelectronic dielectric research and the future of the field. However, as we will clarify, the well has fortunately not yet run dry!

In this address, we seek to illustrate that high-k gate oxides and low-k ILDs represent just a small fraction of the numerous dielectric materials utilized in nanoelectronic products and that numerous new applications for dielectric materials are emerging as the industry transistions to novel patterning schemes and prepares for life post CMOS scaling. We will begin by briefly exploring the entirety of dielectric materials utilized in advanced nanoelectronic products with a particular focus on often ignored etch stopping, diffusion barrier, and passivation dielectrics and their more specialized requirements relative to high-k and low-k dielectrics. We will then transition to examining the various novel pitch division schemes being developed to cope with the delay of EUV lithography and the abundant new dielectric material applications these schemes create. We will specifically focus on the various new spacer and hard mask dielectrics that pitch division requires, their colorful selectivity requirements, and suggest future research needed to enable even more exotic patterning schemes.

We will further examine how what was once old can become new again and specifically explore how both high-k and low-k dielectrics are being utilized to fill the needs of future beyond CMOS devices. In particular, the application of high-k and low-k dielectrics in novel resistive switching, magnetic, and nano-electro-mechanical device and sensor applications will be surveyed along with the research needed to extend these materials into even more diverse applications. We will conclude by reviewing the unique obstacles that dielectric materials present for the realization of advanced cryogenic quantum computing architectures and the necessary associated research vectors to prevent dielectrics from becoming quantum computing’s Achilles heel.
(Invited) Reactions or No Reaction: Lithium Deposition on the Surface of Solid State Electrolyte
Authors: Xiao Jie , Wu Bingbin , Wang Shanyu , Lochala Joshua Andrew , Desrochers David , Yang Jihui
Published: February 2020

Li metal anode has regained intensive interest in recent years in order to develop high energy next-generation battery technologies. Unfortunately, Li metal suffers from poor cycling stability and low efficiency as well as the formation of dangerous Li dendrites raising safety concerns. The employment of solid state electrolyte (SSE) to prevent Li dendrite growth provides a promising approach to address the dendrite issue. However, recent studies indicate that Li dendrites easily form at elevated current densities, while the fundamental mechanisms of forming Li dendrites within SSE is still unknown. This calls for further investigation to understand, and control the detrimental observation.

The origin and evolution of Li dendrite growth through SSE will be discussed in this talk by using two different SSE membranes, garnet and phosphate-type, as the separators. During cycling, Li is repeatedly deposited on SSE. Although a good SSE should not react with the deposited Li, the reactions between Li deposits and SSE generate a self-terminating interface, which stops the fast propagation of dendritic Li through the SSE membrane. New insights are provided on the further modification and/or incorporation of interfacial layers between SSE and Li metal to enable future solid state batteries.
Electrodeposited Transition Metal Oxides As Separate Electrodes for Rechargeable Zinc-Air Batteries
Authors: Xiong Ming , Labbe Matthew , Li Na , Ivey Douglas G
Published: February 2020

The rapid growth of renewable energy production requires an economical and efficient way to store and deliver the electricity. Electrically rechargeable Zinc-air batteries have gained revived interest among the various technologies available with their high theoretical energy density and low cost1. However, the large-scale industrial deployment of zinc-air batteries has been hampered by several problems, i.e., low round-trip energy efficiency and reduced cycling stability, both of which can be primarily attributed to the degradation of the air electrodes. Unlike conventional batteries like Li-ion, the charging and discharging processes for zinc-air batteries have different requirements for the electrodes. The discharge process is driven by the oxygen reduction reaction (ORR) and requires an air electrode that is not flooded by the electrolyte. The charging process (oxygen evolution reaction, OER), on the other hand, is more favored when the electrode is submerged in the electrolyte. In addition, the ORR active sites at the electrode can be damaged by the oxidation potential of the OER process2. Therefore, a design with physically decoupled electrodes for discharge and charge can avoid these adverse effects. This approach also allows for more flexibility to optimize ORR and OER electrocatalysts individually.

In this study, ORR and OER active catalysts based on transition metal oxides are electrodeposited on different current collectors. The ORR catalyst is based on manganese oxides, while the OER catalyst is a cobalt-iron solid solution oxide. Scanning electron microscopy (SEM) reveals that both catalysts are nanostructured with high surface areas for electrochemical reactions. Electrochemical tests show that the both catalysts have comparable or even better activity than their commercial Pt-Ru catalyst counterparts. The durability of the manganese oxide catalyst is significantly enhanced by using it exclusively for ORR instead of as an ORR-OER bifunctional catalyst. The catalysts were assembled into a zinc-air battery as decoupled electrodes for discharge and charge tests. Preliminary cell testing shows that the discharge-charge efficiency was around 59% at 10 mA/cm2 current density. Both electrodes demonstrate excellent stability after 50 hours of battery testing.

References

1. E. Davari and D.G. Ivey, Sustainable Energy & Fuels, in press, 29 proof pages, DOI: 10.1039/c7se00413c (2017).

2. Y. Li and J. Lu, ACS Energy Letters,
2 (6), 1370-1377 (2017).
New Approaches to Dynamic Windows Based on Metal Electrodeposition and Dissolution
Authors: Barile Christopher J. , Islam Shakirul M. , Juarez-Rolon Jose S. , Fini Christine , Hull Troy , Kessinger Riley , Preciado Kevin , Alcaraz Geoffrey Kirk A.
Published: February 2020

Dynamic windows with electronically tunable transparency have applications in buildings, automobiles, and switchable sunglasses. By modulating solar lighting and heating flux, well-functioning dynamic windows improve the energy efficiency, comfort, and aesthetics of spaces. While most switchable windows utilize electrochromic materials, we have developed dynamic windows based on the reversible electrodeposition of metals. These windows possess clear-to-black transitions with ~80% optical contrast in 1 minute. 25 cm2 prototypes of these devices switch thousands of times without detectable deterioration.

The windows function through the electrochemical movement of metal between a transparent conducting working electrode and a counter electrode metal frame. To facilitate uniform electrodeposition over a large working electrode area, transparent conducting oxides are modified with a self-assembled monolayer of Pt nanoparticles, which serves as an inert metal seed layer for metal nucleation and improves electrodeposit morphology. An aqueous electrolyte separates the two electrodes and consists of Ag+, Cu2+, Pb2+, and/or Bi3+ ions. We investigated several electrodeposition chemistries and established relationships between electrolyte composition and device performance. In addition, by selecting appropriate electrolyte additives, we have constructed dynamic windows that switch reversibly at temperatures as low as -40°C without electrolyte freezing. Lastly, we consider how improvements in electrode design will increase the scalability and optical functionality of these devices.

Photograph of Mt. Rose, Nevada through a 25 cm2 dynamic window based on reversible metal electrodeposition as it switches in subfreezing weather:

Figure 1
ALD Al2O3 Coating of Self-Organized TiO2 Nanotubes As High Performance Anodes for Lithium Ion Batteries
Authors: Djenizian Thierry , Macak Jan M. , Sopha Hanna , Salian Girish
Published: February 2020

Alumina coatings produced by Atomic layer deposition (ALD) on electrode materials have been explored extensively. Alumina coatings generally, have been used as a protective layer for the suppression of the solid electrolyte interphase (SEI) in various electrode materials.1 But its influence on increasing the electronic conductivity of the electrode material has not been explored. TiO2 nanotubes have been recently explored due to its low volume expansion, good capacity retention even at faster kinetics.2 The utilization of anodic TiO2 nanotube layers with uniform Al2O3 coatings of different thicknesses (prepared by atomic layer deposition, ALD) as new electrode material for lithium-ion batteries (LIBs) is reported. Electrodes with very thin Al2O3 coatings (~1 nm) show a superior electrochemical performance for the use in lithium ion batteries compared to uncoated TiO2 nanotube layers. A more than two times higher capacity is received on these coated TiO2 nanotube layers (~75 µAh/cm2 vs 200 µAh/cm2 at 1 C) as well as a higher rate capability and coulombic efficiency. Reasons for this can be attributed to a better diffusion of Li+ ions within the coated nanotube layers. However, thicker ALD Al2O3 coatings result in a passivation of the electrode surface and, therefore, in a capacity decrease. Fig. 1(a) shows the influence of alumina coating with different thickness on the capacity of the TiO2 nanotube layer. Fig.1(b) shows the long term cycling of the 1 nm alumina coated and the uncoated TiO2 nanotube layers at 1C. In this work, factors influencing the increase in capacity due to the alumina coating will be discussed using results from different electrochemical characterization methods. 3

References

(1) Jung, Y. S. et al, Adv. Mater. 2010, 22, 2172-2176.

(2) Ortiz, G. F. et al, Chem. Mater. 2009, 21, 63-67.

(3) Sopha, H. et al, ACS Omega, 2, 2749 (2017)

Figure 1
Completely Aqueous Route for Metallization of Structural Polymeric Materials in Micro-Electro-Mechanical Systems
Authors: Le Xuan Tuan , Poirier Jean-Sébastien , Michel Sébastien
Published: February 2020

Recent developments in the fabrication of micro-electro-mechanical systems (MEMS) are moving away from the deposition/mask/etch paradigm and instead exploiting useful properties of polymers. Many polymeric insulating materials, such as Parylene, PMMA, HSQ, SU-8 and KMPR, have attracted attention in microfabrication lately, because of their low cost and significantly easy processing procedures [1,2]. Metallization of these polymers is required for their integration in MEMS technology. While conventional microfabrication methods for preparing metallic thin films on insulating substrates are limited to vapor deposition techniques, it has recently demonstrated that electroless deposition can be considered as an alternative and efficient approach [3,4]. Presently used process of electroless plating onto plastics requires a pretreatment based on chromic acid etching for oxidizing the surface. This pretreatment increases the surface energy and wettability for the subsequent step of surface activation with noble metal catalysts. Thus, the development of simple, cost-effective and environment friendly strategies, such as avoiding chromic acid etching and/or minimizing the gravimetric use of noble metal, to metallize the surface of insulating substrates is of huge interest. Here, we report a simple one step covalent amination of the surface of commercial structural polymers employing diazonium-based aqueous chemistry. These amine-terminated functionalities allow minimizing the quantity of palladium cations used as catalyst for the subsequent electroless nickel deposition, as well as offer excellent adhesion between the polymer substrate and the nickel film. X-ray photoelectron spectroscopy is carried out to elucidate the mechanism of surface functionalization with amine groups. We then focus our attention on the comprehensive characterization of the metallic thin film through scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy techniques.

Keywords: Metallization of plastics, diazonium chemistry, covalent grafting, environment plating process, MEMS fabrication

Reference

W. Dai et al., Sensors and Actuators A 135 (2007) 300–307.

Y. Liu et al., Progress in Polymer Science 52 (2016) 79–106.

Y. Shacham-Diamand et al. Microelectron. Eng. 132 (2015) 35–45.

G. Zeb et al., Applied Surface Science 407 (2017) 518–525.
(Invited) Manipulation of Structure and Morphology of Solid-Electrolyte Interphase Layer for High-Performance Li Metal Batteries
Authors: Wang Donghai
Published: February 2020

Lithium metal batteries are promising high-energy storage devices due to a high theoretical capacity of lithium (Li) anode. It is challenging to achieve Li anodes with high Coulombic efficiency (CE) due to poor stability of solid-electrolyte interphase (SEI) associated with excessive SEI accumulation and exacerbation of Li dendrite growth, leading to poor capacity retention and short cycling life of Li metal batteries.

In this talk, I will present strategies to reinforce the SEI with desired properties including good tolerance to the Li interface change and efficient surface passivation against electrolyte penetration. The approach works via either introducing multiple functional components bonded to the Li surface into the SEI or depositing flexible organic/inorganic hybrid coating layer. This self-forming of the reinforced SEI can be triggered once fresh Li is deposited at the interface, thus realizing a lasting formation of the stable SEI. The as-formed durable SEI layer can suppress dendritic Li growth, enhance Li plating/stripping CE, and in turn, enable Li metal batteries with long cycling life and excellent capacity retention. We demonstrate the reinforced SEI can improve Li metal efficiency in a carbonate-based electrolyte for Li-metal oxide batteries and a ether-based electrolyte for Li-sulfur batteries. This study provides a promising route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.
(Invited) Ultrathin Polymer Electrode Coatings to Stabilize Electrochemical Interfaces in Lithium-Ion Batteries
Authors: Carter Rachel E. , Parker Joseph F. , Sassin Megan B. , Long Jeffrey W. , Love Corey T
Published: February 2020

Safety and performance of Li-ion batteries lie at the electrochemical interfaces. Local surface chemistry and electrochemistry at the battery negative electrode will dictate whether stable intercalation or unstable deposition processes are favored. This talk will present the environmental, electrochemical and chemical effects, namely temperature, current density and negative electrode surface coatings, have on the nucleation, growth and morphology of electrodeposited lithium. We use initiated chemical vapor deposition (iCVD) to generate ultrathin polymer coatings with thickness control at the nanoscale [1], even on complex three-dimensional (3D) substrates [2] such as carbonaceous negative composite electrodes. The siloxane-based polymers most commonly generated by iCVD contain ether-like functionalities that support the solvation and transport of Li+ salts, such that they are readily transformed into Li-ion conductors [3]. Polymer-modified electrodes are assembled into Li-ion coin cells containing liquid electrolytes, in which we examine such properties as specific power, coulombic efficiency, cycle life, and tolerance to overcharge/overdischarge conditions. In-situ optical microscopy observation of galvanostatic plating and stripping experiments provides valuable understanding of morphology, growth behavior, and propensity to form internal short circuits. These observations are then coupled with cell impedance changes detected through electrochemical impedance spectroscopy to develop advanced diagnostic and fault detection techniques.

Tenhaeff, W.E.; Gleason, K.K. Func. Mater. 2010, 18, 979.

Sassin, M.B.; Long, J.W.; Wallace, J.M.; Rolison, D.R. Horizons
2015, 2, 502.

Reeja-Jayan, N. Chen, J. Lau, J. A. Kattirtzi, P. Moni, A. Liu, I. G. Miller, R. Kayser, A. P. Williard, B. Dunn, and K. Gleason, Macromolecules
48, 5222 (2015).
Stabilization of Electrodeposit in Soluble Lead Flow Batteries with Acetate Additive
Authors: Chen Hsun-Yi , Tang Hao-Lun , Lee Chun-Yen , Lin Yan-Ting
Published: February 2020

The emerging of renewable energy demands energy storage. Redox flow batteries are inherently suited for large-scale applications, but their market penetration is thwarted by the high materials cost. In contrast, membrane-less and single-flow soluble lead flow batteries (SLFBs) are more economical to scale up and free of expensive noble metals. However, lifespan of SLFBs reported so far is limited to approximately 200 cycles under normal flow conditions, which is insufficient for long-term operation in utility applications.

Failures of SLFBs are believed to be associated with PbO2 deposition/dissolution at the positive electrode. Although failure mechanisms are not well understood, passivation and shedding of PbO2 are suggested to decrease efficiency of SLFBs. Formation of a passivation layer of non-stoichiometric PbOx is found to be correlated to proton activities. PbO2 deposits of poor adherence and low quality are also observed to occur when the electrolyte is high in acidity. We therefore employ sodium acetate (NaOAc) as electrolyte additive, and successfully extend the cycle life of SLFBs by over 50%.

In this study, effects of acetate additive on electroplating of PbO2 are investigated. Surface morphology and mechanical strength of electroplated PbO2 via electrolyte with and without NaOAc are examined by scanning electron microscopy (SEM) and nano-indentation, respectively. Acetate-assisted electrolyte is found to substantially enhance deposited film strength and leads to a more integrated and smoother surface. Crystal structures, grain sizes, and grain orientations of plated PbO2 are analyzed via x-ray diffraction (XRD) and electron back scatter diffraction (EBSD), and very different phase distributions and grain orientations are observed for electrolyte with and without NaOAc. Electroplating and oxygen evolution kinetics are further investigated by rotating disk electrode (RDE) experiments. Our findings elucidate acetate additive effects on electroplating of PbO2 in SLFB systems and shed lights on battery life extension.
Shape Control of Electrochemically Deposited Metal Films and Nanostructures through Additive Effects
Authors: Leach Gary W. , Grayli Sasan V. , Han Yunyu J.
Published: February 2020

The use of electrolyte additives to affect nanocrystallite shape and film morphology in electroless and electrodeposited metal films is presented. Copper electrodeposited onto gold results in preferential square pyramidal copper nanostructure morphologies in the presence of the organic additive malachite green (MG). We have employed in-situ and ex situ methods to investigate the additive effects, including nonlinear optical spectroscopy, electrochemical scanning tunneling microscopy, linear sweep and cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). These shape-controlled additive effects are supported by additive adsorption energy calculations, which indicate preferential interactions, and differential growth kinetics on different facets of the film's growing nanostructures during electrodeposition. Facet-specific interactions have also been exploited in the epitaxial electroless deposition of noble metals onto single crystal Ag(100) substrates. Here, we examine the role of specific anions in determining the resulting film and nanostructure morphologies via SEM and high resolution transmission electron microscopy (HRTEM). These effects have been exploited to yield large area patterned, and shape-controlled nanoarrays of single crystal metal nanostructures for plasmonic and metamaterial applications. These approaches offer new and cost effective routes to achieve shape-controlled surface nanostructure.
Reaction Mechanisms for Long Life and Ultra-High Power Rechargeable Zn Ion Batteries
Authors: Li Yun , Wang Shanyu , Salvador James R , Wu Jinpeng , Liu Bo , Yang Wanli , Yang Jiong , Zhang Wenqing , Yang Jihui
Published: February 2020

Rechargeable aqueous Zn-ion batteries (ZIBs) are very promising for large-scale grid energy storage applications owing to their low cost, environmentally benign constituent elements, excellent safety, and relatively high-energy density. Their usage, however, is largely hampered by their fast capacity fade. The cycle stability seems to be highly rate-dependent, which poses an additional challenge, but can also play a pivotal role in uncovering the reaction mechanisms. The complexity of the reactions in this electrochmical system has resulted in long-standing ambiguity of the chemical pathways of Zn/MnO2 rechargable battery system, and has led to many controversies with regard to their nature. In this talk, we present a combined experimental and theoretical study of Zn/MnO2 cells. We found that both H+/Zn2+ intercalation and conversion reactions occur at different voltages, and that the rapid capacity fading can clearly be ascribed to the rate-limiting and irreversible conversion reactions at a lower voltage. By avoiding the irreversible conversion reactions at ~ 1.26 V, we successfully demonstrate ultra-high power and long-life Zn/MnO2 cells which, after 1000 cycles, maintain an energy density of ~ 231 Wh kg-1 and 105 Wh kg-1 at a power density of ~ 4 kW kg-1 (9C, ~ 3.1 A g-1) and ~ 15 kW kg-1 (30 C, ~ 10.3 A g-1), respectively. The excellent cycle stability and power capability are superior to most reported ZIBs or even some lithium-ion batteries. The results establish accurate electrochemical reaction mechanisms and kinetics for Zn/MnO2, and identify the interplay of the voltage window and rate determining factors for achieving excellent cycle life.
Highly Dispersed RhxSy Catalyst on Carbon Support with High Nafion Affinity for HER/HOR in HBr Solution
Authors: Li Yuanchao , Nguyen Trung Van
Published: February 2020

A cost-effective electrical energy storage system is needed to allow large-scale integration of intermittent renewable energy sources such as wind and solar into the electrical grid. The hydrogen-bromine reversible fuel cell system is a promising technology to meet this need because of its high round-trip conversion efficiency and potential low cost. Since the commonly used catalyst, platinum, is not stable in the corrosive HBr and Br2 environment, an alternative catalyst that is more durable and equally active is needed. RhxSy catalyst has been found to meet this requirement. 1,2

An aqueous-based process to synthesize RhxSy/C was developed by Allen et. al. , where XC72R is the carbon support. The catalyst synthesized by this process, however, has large particle sizes (12-40 nm). Other research groups 4,5 have shown that smaller particle size can be achieved if surface with high affinity for precipitation of Rh cation is provided. Since rhodium cation is the source of rhodium, negatively charged carbon surface is preferred to achieve higher dispersion of catalyst nanoparticles. The measured mass-specific electrochemically active surface area (ECSA) of the catalysts in 1M nitrogen-saturated H2SO4 solution with HNO3-pretreated carbon and untreated carbon substrates shown in Figure 1 supports this aspect. However, the subsequent H2-Br2 fuel cell test results given in Figure 2 show affinity issue with the catalyst with acid pretreated carbon substrate. It shows that while the negatively charged carbon surface helps to increase the catalyst dispersion, it results in poor Nafion ionomer coverage because of the electrostatic repulsion with the negatively charged Nafion ionomer 6. To improve the fuel cell performance of this high ECSA catalyst, a process to make the carbon support surface positively charge for high affinity to the Nafion ionomer is needed. This presentation will discuss the attempt to synthesize high ECSA RhxSy catalyst on carbon substrate with high affinity for Nafion ionomer and the characteristics and performance of this catalyst.

Reference

J. Masud, T. Van Nguyen, N. Singh, E. McFarland, M. Ikenberry, K. Hohn, C. J. Pan, and B. J. Hwang, Journal of the Electrochemical Society, 162, F455–F462 (2015).

A. Ivanovskaya, N. Singh, R.-F. Liu, H. Kreutzer, J. Baltrusaitis, T. Van Nguyen, H. Metiu, and E. McFarland, Langmuir, 29, 480–492 (2013).

A.F. Gulla, R.J. Allen, US Patents, US20080202923 A1 (2008).

A. Eguizabal, L. Uson, V. Sebastian, J. L. Hueso, and M. P. Pina, RSC Advances, 5, 90691–90697 (2015).

M. S. Shafeeyan, W. M. A. W. Daud, A. Houshmand, and A. Shamiri, Journal of Analytical and Applied Pyrolysis, 89, 143–151 (2010).

F. Xu, H. Zhang, J. Ilavsky, L. Stanciu, D. Ho, M. J. Justice, H. I. Petrache, and J. Xie, Langmuir, 26, 19199–19208 (2010).

Acknowledgments

The work presented herein was funded by the National Science Foundation under Grant No. EFRI-1038234 and No. 1416874, as a sub-award from Proton Onsite.

Figure 1
Optimization of the Hydrogen/Manganese Hybrid Redox Flow Battery
Authors: Rubio-Garcia Javier , Kucernak Anthony R. J. , Li Danlei , Zhao Dong , Yufit Vladimir , Gomez Gonzalez Miguel A , Fahy Kieran F. , Brandon Nigel P.
Published: February 2020

Redox flow batteries are promising candidates to facilitate the integration of renewable sources into the energy mix. This is associated to their durability, efficiency and fast response. However, deployment of existing redox flow batteries is hindered by the relatively high cost of the (typically vanadium-based) electrolyte. Manganese is an abundant and inexpensive element that is widely used in disposable alkaline batteries. However, it has hitherto been little explored for redox flow batteries due to the instability of Mn(III) leading to precipitation of MnO2 via a disproportionation reaction. By combining the facile hydrogen negative electrode reaction and electrolyte formulations that suppress Mn(III) disproportionation, it is possible to construct a hydrogen/manganese hybrid redox flow battery with high round trip energy efficiency (82% at 100 mA cm-2), and high power and energy density (1410 mW cm-2, 33 Wh L-1), at an estimated 70% cost reduction compared to vanadium redox flow batteries. In this paper we present the general concept as well as our latest single cell optimization work.
Zinc/Iron Hybrid Flow Batteries for Grid Scale Energy Storage and Regulation
Authors: Kienitz Brian
Published: February 2020

Megawatt scale energy storage that is reliable, safe, and cost effective is necessary for the integration of highly intermittent renewable energy sources and advanced grid technologies into our current electricity grid. These systems also need to show high round trip efficiency, high power, sufficient capacity, and versatile modes of operation to maximize their value. Zinc/iron (Zn/Fe) hybrid flow batteries have the promise to meet these demands due to their inexpensive, relatively safe, and abundant electrolyte chemistries. This presentation aims to discuss the merits and technical challenges of the Zn/Fe hybrid flow battery system with data from laboratory investigations, field installations, and economic analysis.

Hybrid flow batteries are similar to traditional liquid/liquid flow batteries in that they store electrolytes separately from the power conversion cells. Unlike traditional flow batteries, hybrid flow batteries involve the deposition of a solid layer on at least one of the electrodes. The Zn/Fe hybrid flow battery negative electrolyte utilizes a complexed zinc anion. Zinc metal is deposited during charge and released back into solution on discharge. The positive electrolyte is comprised of an iron salt which changes oxidation states during charge and discharge. These electrolytes are composed of commercially available commodity chemicals that can be sourced for well under $100/kWh. A cation exchange membrane is used to separate the positive and negative electrolytes in the power conversion cell. Low molecular weight cations are shuttled back and forth across the membrane on charge and discharge to balance the reactions. Electrodes are made using non-precious metals and cell housings are composed of common injection moldable plastics.

Most redox flow battery systems utilize acidic electrolytes. The ViZn Zn/Fe battery system utilizes basic electrolytes. Therefore, the redox species in the Zn/Fe system are anionic. Utilizing anionic redox species separated by a cationic exchange membrane significantly reduces susceptibility to cross over contamination. The relatively large anion species are unable to cross the membrane due to the principal of Gibbs-Donnan exclusion. This results in a battery system with high coulombic efficiency and the ability to use thin highly conductive cation exchange membranes. These membranes, when coupled with a precision engineered cell, create a hybrid flow battery system with high power and high energy efficiency.

Inexpensive electrolytes coupled with high performance operation has allowed ViZn Energy Systems, Inc. to produce a robust four-hour battery system with a near term installed battery cost of under $350/kWh for use in the MW scale grid storage and regulation markets.
Progress Toward High Voltage, High Cycle Life Non-Aqueous Flow Cells for Grid Scale Energy Storage
Authors: Davis Benjamin L , Chu Terry , Maurya Sandip , Popov Ivan A. , Batista Enrique , Yang Ping
Published: February 2020

Los Alamos National Laboratory is leveraging its resources in theoretical modeling, inorganic synthesis, and fuel cell expertise to transform the grid scale energy storage with flow cells. This talk will discuss our initial efforts at charge carrier design and flow testing, with a particular focus on multi-coordinate pyridine-amido ligands incorporating Fe and Ni.
Advanced Intermediate Temperature Sodium-Metal Halide (Na-MH) Batteries for Stationary Energy Storage Applications
Authors: Chang Hee Jung , Jung Keeyoung , Bonnett Jeff F , Canfield Nathan L , Lu Xiaochuan , Sprenkle Vincent , Li Guosheng
Published: February 2020

Recently, sodium-metal halide (Na-MH, or also called ZEBRA) batteries have been extensively investigated due to its potential application for large scale energy storage systems. Particularly, compared to the conventional high temperature (> 280oC) ZEBRA batteries, a Na-MH battery operated at intermediate temperature (IT< 200oC) presents several advantages such as longer cycle life, lower battery manufacturing cost, and easier thermal management, etc. b″-alumina (Na2O×5.33 Al2O3) is typically used for IT Na-MH batteries as Na ion conducting solid-state electrolytes. Thus, the fabricating a thinner b″-alumina solid-state electrolytes (BASE) that results in a high Na ion conductivity is critical to improve performances of IT Na-MH batteries. In here, we will present a new fabrication process for the BASE with a double-layer structure that can drastically reduce the thickness of the BASE. We have examined the conductivity and morphology of new BASEs using electrochemical impedance spectroscopy and SEM. The IT Na-MH batteries assembled using new BASEs are also tested up to 300 cycles, and show excellent energy density (~380 Wh/kg) and around trip efficiency (~95%).

Figure 1
Incremental Capacity Analysis to Recognize Ageing Variations for Liquid Metal Battery
Authors: Xu Cheng , Wang Kangli , Cheng Shijie
Published: February 2020

With dwindling fossil resources and growing environmental concerns, renewable and clean resources, such as wind and solar, are getting more and more attention from the public. Due to the inherent stochastic and unstable characteristic of renewable sources, large-scale energy storage is critical for their grid-connected usage, increasing the capacity and reliability of the future electricity grid.

Recently, many scholars focus on the research of Liquid Metal Battery (LMB), a three-liquid-layer electrochemical cell which is a prospective battery chemistry for large-scale grid-level stationary energy storage. Compared with Lithium-ion batteries, the Li||Sb-Sn LMB exhibits superior rate performance (only 13% capacity loss from 100 mA/cm2 to 1 A/cm2), low materials cost (73 $ kW/h), high energy density (200.4 W h/kg) and long cycle life (a fade rate of 0.0078% per cycle) [1]. However, as a developing battery technology, the degradation mechanism of LMBs is not sufficiently studied. To identify the ageing variations of batteries, incremental capacity analysis (ICA) and differential voltage analysis (DVA) are considered to be the two effective in situ techniques [2].

In this work, we recognize ageing variations for LMBs using ICA. The battery used for the test has a nominal capacity of 23 Ah, and voltage operation range is from 0.65 V to 1.2V. A constant current charge-discharge test profile is used to age the battery. After more than 500 charge/discharge cycles, dQ/dV curves are obtained through the voltage data recorded by NEWARE 4000. According to dQ/dV curves, we can easily recognize the ageing variations for LMBs. In addition, a capacity degradation model is established to estimate the State of Health (SOH) of LMBs. Combining with the capacity degradation model, State of Charge estimation and fault diagnosis can be implemented more precisely.

References

[1] Li H, Wang K, Cheng S, et al., High Performance Liquid Metal Battery with Environmentally Friendly Antimony–Tin Positive Electrode[J]. Acs Applied Materials & Interfaces, 2016, 8(20):12830.

[2] Z. Ma, J. Jiang, S. Wei, et al., Investigation of path dependence in commercial lithium-ion cells for pure electric bus applications: aging mechanism identification[J]. J. Power Sources, 2015, 274 (3):29-40.

Figure 1
Intermediate Temperature Sodium Batteries Enabled By an Inorganic Molten Catholyte
Authors: Small Leo J. , Percival Stephen , Lamb Joshua , Allcorn Eric , Spoerke Erik D.
Published: February 2020

As the national electrical energy grid continues to expand and evolve, there is an increasing need for safe, cost-effective and reliable large scale batteries. Current large scale battery technologies continue to suffer from limited cyclability, high cost, and potentially hazardous runaway reaction behaviors. Here, we describe a promising alternative approach to intermediate temperature molten sodium-based batteries, enabled by advanced solid state ceramic electrolytes, such as NaSICON, that offer high Na+ conductivity at temperatures well below 200 °C. Integrating molten sodium anodes, ceramic solid state electrolytes, and fully molten AlCl3-based molten salt catholytes, we create high performance, all-inorganic batteries. In particular, we explore an AlCl3-NaI molten salt catholyte, and we show that these batteries operate efficiently below 200 °C. We describe the relationships between the molten salt composition and electrochemical properties of the catholyte, revealing how these promising, intermediate temperature technologies boast coulombic efficiencies near 100% and energy efficiencies >80%. Moreover, we validate the safety of this material set using accelerated rate calorimetry to demonstrate that the system exhibits neither the runaway exothermic reactions nor hazardous pressurized gas generation that plague other large-scale battery systems. Finally, we discuss the potential benefits to long term battery reliability afforded by low-to-intermediate temperature battery operation. The encouraging performance of this emergent intermediate temperature molten salt battery shows a path to providing the reliable, safe, and cost-effective energy storage solutions demanded by our rapidly growing national electrical energy grid.

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.
New Organic Molecules for Energy Storage Applications
Authors: Webster Richard David
Published: February 2020

A range of structurally variable redox active molecules that are suitable for electrical energy storage were investigated for their potential applications in redox flow batteries. The molecules were selected based on their electron acceptor and/or donor properties, their solubility in aqueous and non-aqueous solvents, their lifetimes in reduced and oxidized states, their formal potentials, their abilities to coexist together in the catholyte and anolyte cell compartments, their resistance to degradation reactions with molecular oxygen and water, their behavior in the presence of acids and bases, and their ease of synthesis. The molecules included a number of redox active quinones and flavins, vitamins (B2, E and K1) and modified forms of the vitamins, aromatic esters, 1,4-phenylenediamines and benzidines. The performance of the molecules were evaluated using a combination of voltammetry, electrolysis under constant potential conditions and in situ spectroelectrochemical analysis (UV-vis and electron paramagnetic resonance). It was found that systems with high redox potentials, although allowing for large voltages (3 – 5 V), suffered from relatively short lifetimes in their charged states due to undesirable reactions with trace impurities including molecular oxygen and trace water (in non-aqueous solutions). Therefore, an optimal potential difference range for the redox couples was found to be between 1 – 2 V, which decreased the likelihood of decomposition reactions of the redox active components and often allowed seemingly indefinite lifetimes. Two systems that provided excellent characteristics were, (i) a modified form of vitamin K1 (as the electron acceptor) and a modified form of vitamin E (as the electron donor), and, (ii) a substituted anthraquinone (as the electron acceptor) and o-tolidine (as the electron donor).

Figure 1
Electrochemical Properties of Quinone Derivatives: First-Principles Density Functional Theory Modeling and Machine Learning Approach
Authors: Cho Byung Woo , Jang Seung Soon
Published: February 2020

Lithium-ion battery has received intensive attention as a candidate for efficient and portable electrochemical energy storage systems (EES) to be used in many applications ranging from cell phones to electric vehicles. Lithium-ion batteries not only have the high performance but also cyclic stability making them the optimal choice for recharging-discharging process. Despite the high potential, the slow diffusivity of lithium ions, which is mainly due to the intrinsic properties of the conventional cathode materials, which are mainly transition metal oxides, resulting in poor power density. Organic electrode materials have been considered as promising substitute for metallic oxide cathodes due to safety, low cost, and low density. Among various organic materials, the ones with the carbonyl functional group have been recognized to achieve high-performance redox couples with stable and reversible redox reactions. Finding cathode materials with high redox potentials is critical for organic molecules as they exhibit lower potential compared to the conventional electrode materials. The lower potential exhibited by the organic molecules compared to the metallic oxides are believed to be due to the low ionic conductivity of organic materials, despite having good electron conductivity. In this study, we characterize the electrochemical potentials of quinone-based structures in as a function of molecular structures. Quinone-based organic materials have well-defined active sites and fast electron and ionic transfer kinetics compared to other organic molecules, which is suitable for battery application. We also investigate what factors may contribute to the electrochemical properties using machine learning technique, especially artificial neural network.
Progress in the Development of Prototypes for Phosphatic Clay Electrokinetic Dewatering
Authors: Dizon Arthur , Orazem Mark E
Published: February 2020

A dilute 2-3 wt.% suspension of phosphatic clay is produced as a waste stream in the beneficiation of phosphate ore. A typical Florida phosphate mining operation produces more than 100,000 gallons/min of phosphatic clay. The suspensions are pumped into large impoundments called clay settling areas (CSA) in which separation is achieved by hindered settling and self-consolidation.

As it settles, the supernatant water is recycled for use in the beneficiation plant. A top crust is formed after a few years, but the clay beneath the crust has a large water content and a pseudo-plastic character that limits the amount of weight the settling area can support. As much as 25 -50 years are needed to reach a solids content greater than 25 wt.%. Clay settling areas cover about 30-40% of the mined land. Uses for the land are limited by the properties of the clay that leave the settling areas unstable.

Methods that employ electrokinetic phenomena have been the subject of significant research as a possible means of accelerating the dewatering process. Previous research to develop batch electrokinetic dewatering processes resulted in the determination that the electrokinetic dewatering was not economically feasible. The objective of our work was to overcome the economic hurdle through the development of continuous electrokinetic dewatering (EKD).

The previous continuous design was a single unit in which a cake was formed in the horizontal section and the cake was dewatered in the slanted section. Separation of the single-unit process into two units yielded greater throughput, but the projected cost per metric ton of dry clay was not substantially lower than that of the previous prototype. The latest prototype consists of a single unit which accepts a 10 wt.% suspension as a feed and produces up to a 38 wt.% cake. As compared to our previous prototype, the new unit has improved the viability of industrial EKD by reducing both capital and operational cost through increased throughput, reduced materials cost, and improved clay-water separation efficiency.
Effect of Impurities in Precious Metal Recovery By Electrodeposition-Redox Replacement Method from Industrial Side-Streams and Process Streams
Authors: Yliniemi Kirsi , Halli Petteri , Korolev Ivan , Wang Zulin , Hannula Pyry , Lundström Mari
Published: February 2020

The recovery of metals from industrial side-streams and process streams is typically performed by solvent extraction, cementation or precipitation, chemical reduction, or electrowinning. However, several industrial process, side- and waste streams do contain also trace amounts of valuable metals such as Ag and Au at lower than ppm scale, making the economics of the recovery challenging.

Recently, we have introduced electrodeposition-redox replacement (EDRR) method as a route to extract Ag from Zn process streams [1], where a successful recovery of Ag was possible even from ppb concentrations. In EDRR method, the base metal (such as Zn) is first deposited during the electrodeposition step, followed by a redox replacement step in the absence of applied potential or current. During this latter step, the deposited less noble metal is spontaneously replaced by a more noble metal (such as Ag) still present in the solution. As a result, Ag is enriched on the electrode.

This paper concentrates on the effect of impurities on the recovery of valuable metals (Ag and/or Au) from solutions typical for hydrometallurgical industry, such as chloride, sulfate and nitrate based solutions. The measurements were performed in simulated process solutions in which metal and impurity concentrations were close to actual solutions of sulfate based Zn process solution [1], Doré slag leaching [2], or cyanide free gold chloride leaching [3]. The morphology and quality of the recovered metal product was determined by SEM-EDS and the EDRR results showed a high selectivity towards Ag and Au in all investigated hydrometallurgical solutions despite of the impurities present in the solution. Moreover, the impurities investigated were shown to speed up EDRR reactions, regardless of the concentration of the impurity - ppb, ppm or even g/L scale.

Acknowledgements

Academy of Finland (NoWASTE - Project No: 297962), EU Framework Program for Research and Innovation Horizon 2020 (MSCA-ETN SOCRATES - Grant Agreement No: 721385) and Finnish Steel and Metal Producers (METSEK-project) are acknowledged for financial support. The research utilized “RawMatTERS Finland Infrastructure” (RAMI, funded by Academy of Finland) based at Aalto University.

References:

[1] P. Halli, H. Elomaa, B. P. Wilson, K. Yliniemi, M. Lundström, ACS Sustainable Chem. Eng.
5 (2017) 10996 - 11004.

[2] P.Halli, S. Jolivet, A. Klöfverskjöld, P. Latostenmaa, B.P. Wilson, M. Lundström(2017) Leaching of Sb from TROF Furnace Doré Slag. In: Zhang L. et al. (eds) Energy Technology 2017. The Minerals, Metals & Materials Series. Springer, Cham.

[3] M. Lampinen, S. Seisko, O. Forsström, A. Laari, J. Aromaa, M. Lundström, T. Koiranen, Hydrometallurgy
169 (2017) 103–111.