bluuebunny/crossref_metadata_2025_split huggingface dataset:
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.
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.
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.
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.
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.
Electrochemical Decontamination Process an Effective Alternative to Treat Textile Effluents
Authors: Hussain Sajjad , Rehman Gohar Abdur , Ali Khan Abbas , Bilal Muhammad , Ahmad Qazi 
Published: February 2020

Keeping in view the growing concern regarding aquatic pollution by effluent water from textile industries containing complex compounds, the present study was under taken with the view to study the efficiency of the removal by electrochemical oxidation. In recent year the use of electrochemistry for the investigation of environmental pollution is being thoroughly investigated. Reactive dye mainly composed of complex organic molecules are highly stable to decomposition in normal condition. Textile industry wastewater containing dyes poses a chronic and synergistic effects to environment. This study examines the electrochemical oxidation of the organic dyes. All the experiments were performed using a Filter Press Flow Cell Reactor containing Ti/Ti0.7Ru0.3O2 anode and stainless steel as cathode in which impact of the current density (5 – 20 mA cm-2), electrolytes (NaCl, Na2SO4, H2SO4), Sodium chloride concentration (0.02 – 0.10 mol L-1) were studied. The electrode used were characterized by the cyclic voltammetry experiments. The Reaction Kinetics and energy consumption parameters were studied of the electrochemical process. Results obtained in this research clearly demonstrated that the effect of the electro generated strong oxidant species active chlorine, depends on electro catalytic mechanism followed on surface of Ti/Ti0.7Ru0.3O2 resulting in the improvement of the color. Results also confirmed a high removal efficiency according to environment and electrolyte used in the process. However, there is a limit of NaCl for treating real effluents avoiding the formation of organochloride compounds; and it is a subject of critical importance, from the environmental point of view, to apply this alternative treatment.
Keyword: textile effluents, contaminants, electrochemical process, Kinetics
(Invited) Experimentally and Theoretically Determining Reaction Pathways for the Alkaline Hydrogen Electrode and Their Implications on Catalyst Design
Authors: Tang Maureen Han-Mei , Snyder Joshua David , Intikhab Saad 
Published: February 2020

Even though hydrogen electrocatalysis has been studied for almost a century, it remains to be explained why higher pH slows the hydrogen evolution and oxidation reactions (HER/HOR) by a factor of 200, even on platinum [1]. This lack of understanding has serious implications not only for industrial electrolysis and next-generation energy storage, but for all electrocatalytic reactions in which pH may play a role. In this work, we investigate possible explanations for the effect of pH by combining microkinetic modeling with traditional electroanalytical methods. We specifically determine the viability of the proposed `bifunctional mechanism’, in which slow water dissociation is overcome by mediation of adsorbed hydroxide [2].
Our calculations [3] show that either a direct (hydroxide-as-spectator) or indirect (hydroxide-mediated) Volmer step can describe the reaction thermodynamics as revealed by slow-scan experimental cyclic voltammetry, but that only the direct Volmer step yields adsorption values consistent with literature. Modulating hydroxide adsorption strength via the electrolyte cation provides additional support for the direct mechanism. Experimentally, stronger hydroxide binding decreases kinetics, as observed by the dependence of peak-potential splitting on scan rate. Comparison with the model shows that this observation is consistent only with the direct mechanism.
Altogether, these results strongly suggest that adsorbed hydroxide serves as a competitive spectator in the alkaline Volmer step, and that the bifunctional HOR/HER mechanism plays only a minor role at best. This study contributes to resolving a long-standing paradox in electrocatalysis and surface science by determining that oxophilicity is not an accurate descriptor for alkaline hydrogen electrocatalysts. Other parameters, such as water orientation and non-covalent interactions, must play a greater role in overall activity. Efforts to identify and measure these parameters are ongoing.
[1] Durst et al. Energy Environ. Sci. 2014, 2255.
[2] Li et al. Angew. Chem. Int. Ed. 2017, in press.
[3] Intikhab et al, ACS Catal., 2017, in press.