bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Novel Ceramic-Polymer Hybrid Electrolyte for Lithium Batteries
Authors: Zekoll Stefanie , Marriner-Edwards Cassian , Hekselman Aleksandra K. , Kasemchainan Jitti , Kuss Christian , Armstrong David , Cai Dongyu , Wallace Robert , Richter Felix Herrmann , Thijssen Job H. J. , Bruce Peter G. 
Published: February 2020

Lithium (Li) metal is being intensively pursued as a negative electrode due to its high specific capacity. Yet, irreversible Li loss, dendrite formation of plated Li metal, and short circuiting, when being cycled as an electrode in battery cells presently impede its use. Furthermore, the flammability of liquid electrolytes poses a severe safety hazard. Replacement of organic liquids by solid electrolytes could pave the way for using Li metal, simultaneously improving specific energy and battery safety.
Significant attention has been paid to ceramic electrolytes due to their high Li-ion conductivity at room temperature and robustness. Nevertheless, processing and manufacturing of the ceramics into sufficiently thin, highly dense, pinhole-free sheets, required for high specific energy and power devices, remains an active challenge. Additionally, the electrolyte must maintain contact with the solid electrodes while simultaneously inhibiting Li dendrites as well as be durable towards electrode volume changes and to external shock.
Polymer electrolytes have been developed for a number of years. The advantages include good adhesion and contact to the electrodes. Still, their low conductivity at room temperature, especially in solid polymer electrolytes, along with their limited capability of suppressing Li dendrite formation, are persistent drawbacks.[i]
To date, ceramic and polymer electrolytes remain a challenge. Hybrids with particulate ceramics embedded in polymer electrolytes have been investigated to improve the conductivity and mechanical properties.
[ii]
Our approach is to create continuously ordered hybrid electrolytes, which allows modification of the mechanical properties of the hybrid while retaining a high ionic conductivity through the ceramic phase.
The ionic conductivity of the hybrid electrolyte is 1.5 x 10-4S/cm at 25 °C. The results of different ceramic-polymer compositions indicate that the mechanical properties of the hybrids can be adjusted by the presented approach. Electrochemical, mechanical, and microstructural characterizations of the hybrid will be reported.

[i] G. M. Stone, S. A. Mullin, A. A. Teran, D. T. Hallinan Jr., A. M. Minor, A. Hexemer, N. P. Balsara, J. Electrochem. Soc., 2012, 159, A222–A227.
[ii] Y.-C. Jung, S.-M. Lee, J.-H. Choi, S. S. Jang and D.-W. Kim, J. Electrochem. Soc., 2015, 162, A704–A710.
Electrocatalytic Properties of Vanadate Glass for Metal-Air Rechargeable Battery
Authors: Miyamoto Hajime , Yuasa Masayoshi , Nishida Tetsuaki , Oka Nobuto 
Published: February 2020

A metal-air battery has a high energy density because they can use atmospheric oxygen as the electrode active material. It is expected that the battery could be used for the electric vehicle which demands power sources with a high energy-density. This rechargeable battery needs bifunctional catalytic materials, which involve effective oxygen reduction/evolution at the air electrode at the discharge/charge process. In this study, a new bifunctional catalytic material for the air electrode has been developed using a conductive vanadate glass. Conductivity of vanadate glass, 20BaO·10Fe2O3·70V2O5, was reported to be easily tunable over a wide range (10-7 - 10-1 S･cm-1) when the local distortion of the glass skeleton was removed by means of the annealing [1]. Utilizing these characteristics, new catalytic materials have been prepared by adding MnO2 and NiO for the oxygen reduction and evolution, respectively.
20BaO·5MnO2·5NiO·70V2O5 glass was synthesized by melting the mixture composed of BaCO3, MnO2, NiO, and V2O5 at 1100 °C for 2 hours. The vanadate glass was annealed at 450 °C for various times (0, 30, 60, and 300 min.). Pulverized vanadate glass was utilized for the preparation of the air electrode by mixing the powder with 7.5 mass% of poly (tetrafluoroethylene) (PTFE), which was hot-pressed on a gas diffusion layer over a Ni metal mesh.
The electrode connected to a Cu wire was mounted onto the window of Teflon-made cell. 8M KOH aqueous solution and a Pt mesh were placed inside the Teflon cell as the electrolyte and the counter electrode, respectively. The temperature of the Teflon cell was held constant by soaking it into a water tank kept at 60 °C. Anodic and cathodic polarization measurements were carried out using a potentiostat. An Hg/HgO electrode was used as the reference electrode.
The electrical conductivity of the as-prepared vanadate glass was 5.4 × 10 -6 S cm-1 at RT. After the annealing at 450 oC for 300 min, it increased to 1.1 × 10 -2 S cm-1. Figure shows the anodic and cathodic polarization curves of 20BaO·5MnO2·5NiO·70V2O5 glass electrodes. The vanadate electrode showed an excellent bifunctional oxygen reduction/evolution activity, being comparable to that of the materials reported in the literature, like polycrystalline LaNiO3 [2]. This vanadate glass could be a highly potential candidate for the bifunctional catalytic material for the rechargeable metal-air battery.
References:
1) K. Matsuda, S. Kubuki, and T. Nishida, AIP Conf. Proc.
(msms2014)
1622, 3-7 (2014).
2) M. Yuasa, M. Nishida, T. Kida, N. Yamazoe, and K. Shimanoe, ECS
158, A605-A610 (2011).

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The Electrochemistry & Corrosion of Zn-Al-Mg Alloys: Quantifying the Contribution of Elemental Components and Individual Phases with Atomic Emission Spectroelectrochemistry
Authors: Ogle Kevin , Han Junsoo 
Published: February 2020

In this work, we address the question of how various elements and various phases interact with each other during short term corrosion of complex alloys? For multi-phase alloys such as Zn-Al-Mg used here, predicting the corrosion behavior over a range of conditions is difficult because the solubility of the corrosion products of each element and the electrochemical activity of the alloy components differ markedly with one another as a function of pH. The electrochemistry of the Zn-Al-Mg system is further complicated by the distribution of the elements into a complex multiphase structure1.
To answer this question, we have applied the atomic emission spectroelectrochemistry (AESEC) technique. This allows us to measure directly the dissolution rate of each element during either a spontaneous, open circuit corrosion experiment (dissolution-corrosion profile), or to decompose the polarization curve into elemental currents (elemental polarization curve). Examples of the later are shown in the Figure below. We also use AC polarization so as to measure charge transfer resistance for each element around the open circuit potential.
The approach is to compare the dissolution-corrosion profile with the elemental polarization curve and the AC elemental polarization to see to what extent the corrosion rate of each element may be predicted from the polarization techniques. The question of microstructure is addressed directly by analyzing the role of phase structure on the dissolution of the coating. This is done by performing experiments on pure phases, intermetallic compounds, and a multiphase Zn-Al-Mg alloy galvanized steel coating. Nominally pure materials include: Zn, Al, and Mg; synthetic η-phase (Zn 0.7-Al), β-phase Al (Zn-22Al), and α-Al phase (Zn-68Al); and synthetic Zn2Mg intermetallic compound. The results are interpreted in terms of the mixed potential theory on an element by element basis, which allows prediction of the corrosion behavior of a system over a wide range of experimental conditions.
Fig.1. Elemental AESEC polarization curves of pure metals, Zn2Mg, and alloy coating in deaerated 10 mM NaCl solution at pH=10.1 at 25 °C.

References

1. T. Prosek, J. Hagstrom, D Persson, N. Fuertes, F. Lindberg, Ondrej Chocholaty, C. Taxén, J. Serák, D Thierry, Effect of microstructure of Zn-Al and Zn-Al-Mg model alloys on corrosion stability, Corrosion Science
110 (2016) 71-81.

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Novel Corrosion Inhibitor Pigments Based on Benzotriazolium Cation Exchanged Resin
Authors: McMurray Hamilton Neil , Richards Calvin , Williams Geraint 
Published: February 2020

A novel corrosion-inhibitor pigment is described which is prepared by the reaction of benzotriazole (BTA) with a crosslinked polystyrene sulfonic acid resin (Amberlite 120H). This pigment is completely insoluble in water and may readily be ground to sub-micron particle size. The formation reaction relies on the resin sulfonic acid functions (pKa -2.8) being significantly more acidic than BTA (pKa 1.1) so that proton transfer produces the benzotriazolium cation ( BTAH+) in an exchangeable form. The kinetics of BTA uptake from aqueous solution at 60oC are followed spectrophotometrically. It is thus shown that uptake is rapid (complete in minutes) and results in a BTAH+ exchange capacity of 143 milli-equivalents per100g. The BTAH+ pigment is evaluated as a corrosion inhibitor by dispersion in an ethanolic solution of polyvinylbutyral (PVB) which is then coated onto the cleaned surface of zinc-coated (hot dip galvanized) steel to produce a dry film thickness of ca. 30 microns. The BTAH+ pigmented PVB coatings thus prepared had BTAH+ pigment volume fractions of between zero and 0.2. A corrosive electrolyte solution (5% w/w aqueous NaCl) was introduced into a penetrative defect in the organic coating and the subsequent process corrosion-driven cathodic coating disbondment was followed using a scanning Kelvin probe (SKP) instrument in a “Stratmann type”experiment at 96% R.H. The SKP data show that increasing BTAH+ pigment volume fraction produces two well defined effects. First the potential of the intact (undisbonded) coated surface becomes depressed by up to 0.3 V versus the unpigmented case. Second the kinetics of cathodic disbondment are profoundly inhibited, becoming immeasurably slow for pigment volume fractions greater than 0.1. These results are interpreted in terms of two phenomena. First the “etching” of the zinc surface by the acidic resin with a consequent release of Zn2+ cations and neutral BTA. Second the inhibition of underfilm cathodic O2 reduction(COR) by surface adsorbed BTA or BTA-zinc complex. The inhibition of COR by BTA in solution is systematically investigated using a zinc rotating disk electrode (RDE) in conjunction with potentiodynamic polarization. The polarization data show that, although BTA profoundly inhibits COR on zinc, BTA is actually a mixed inhibitor and inhibits both anodic zinc dissolution and the COR.
Computational and Experimental Analyses of Galvanic Corrosion of AA7075-T6 Induced By Dissimilar Metal Fasteners and Mitigated By Sol-Gel Coatings
Authors: Tattersall Colin 
Published: February 2020

In modern aircraft, there is a need to protect aluminum structures from galvanic corrosion due to dissimilar metals used in complex aerospace structures. Galvanic corrosion between corrosion resistant fasteners (e.g., stainless steel or titanium alloys) and aluminum alloy structures represent a recurring problem. One means of mitigating such attack is via the application of surface treatments to the fasteners designed to limit their cathodic current density. Detailed measurements and modeling of these effects are important to optimization of the surface treatment and estimates of the level of improvement likely to be achieved. The present work combines experimental measurements of galvanic corrosion damage and computational modeling of galvanic current distributions. The goal is quantitatively connect observations of decreased galvanic corrosion damage on AA7075-T6 coupons due to the presence of stainless steel fasteners under thin electrolyte films as would be present in aerospace service. In particular, sol-gel surface treatments were applied to stainless steel and titanium alloy fasteners which were then placed in AA7075-T6 panels before exposure to salt spray testing. Experimental analyses of corrosion damage were performed using white light interferometry generated depth profiles. These data were used to create data for total volume mass loss (TVML). Computational modeling of galvanic current distributions was performed using a commercial FEM package for thin electrolyte film conditions with experimentally-derived electrochemical kinetics as boundary conditions. The polarization curves used and the current distributions for a 0.1 mm electrolyte layer are shown in Figure 1. Integration of the anodic current densities on the AA7075 over the surface produces a corrosion damage metric, the total anodic current (TAC). The effects of sample geometry, including spacing between fasteners and their location relative to the edges of the sample, as well as water layer thickness and solution concentration on the TAC will be reported. The TVML and TAC can be correlated to one another and to total measured mass loss via Faraday’s Law. Comparisons between the TVML and the TAC will be discussed in detail. Of particular importance will be analyses of the effective throwing power of the fasteners as a function of fastener material and the presence or absence of sol gel surface treatments.
Figure 1: (a) Polarization curves in 0.6 M NaCl of the materials of interest. (b) False color plot of anodic (positive) and cathodic (negative) current distribution (A/m2) for a 0.1 mm electrolyte layer of 0.6 M NaCl
Acknowledgements: The financial support of the Office of Naval Research through Contract # N68335-16-C-0121 (William Nickerson, PM) via Luna Innovations (Adam Goff) is gratefully acknowledged.

Figure 1
(Keynote) Leaching of Inhibitor Particles Followed By 4D X-Ray Tomography
Authors: Liu Yanwen , Zhou Xiaorong , Gibbon Simon R , Graham Derek , Burnett Tim , Lyon Stuart B 
Published: February 2020

Coil-coated zinc-alloy steel is a widely used commodity from white-goods manufacture to architectural claddings. Corrosion protection is generally provided to the substrate, and to any exposed cut edges, by a primer coating using an inhibitive pigme that, conventionally, consists of strontium chromate. However, chromate-free formulations containing phosphate-type pigments are now preferred. A common primer formulation contains strontium aluminium polyphosphate (SAPP) and, in previous work, it has been determined that the solubility of such inhibitors has two conflicting effects. On the one hand, free ions released from the inhibitor migrate to the metal substrate and reduce/inhibit corrosion by formation of a thin precipitated salt film containing zinc, phosphorous and oxygen. On the other hand, the dissolution of the inhibitor results in an increased porosity in the coatings, consequently creating more obvious pathways for aggressive species to reach the metal surface and for the transport of corrosion products. Further, insoluble corrosion products, or precipitated inhibitive salt films, in some cases appear to fill the cavities left by the dissolution of the SAPP inhibitor and, consequently, provide potentially improved barrier protection to the metal substrate.
In the present study the leaching behaviour of nano- to micron scale corrosion inhibitor pigment, of strontium aluminium polyphosphate from a polymer coating was followed over 14 days by 4D x-ray nano tomography. It is apparent that SAPP is not a homogeneous material and contains both strontium-rich components, which leach extensively, and aluminium-rich components, which are more resistant to dissolution. Through the investigation of individual pigment particles and their 3D spatial connections in the polymer matrix, the transport routes of the leaching particles in the polymer matrix may be explored.
The figure shows the evolution of an organic coating pigmented with SAPP corrosion inhibitor over the course of immersion in sodium chloride solution: (a) before immersion; (b) after immersion for 1 day; (c) after immersion for 7 days; (d) after immersion for 14 days. The oval regions highlight the dissolution of strontium-rich particles while the square region highlight the aluminium-rich components of the SAP.

Figure 1
Development of Probe Electrode to Investigate Condition of Concrete By EIS
Authors: Okamoto Tatsuki , Tokieda Hiroyuki , Hoshi Yoshinao , Shitanda Isao , Itagaki Masayuki 
Published: February 2020

An electrochemical technique to obtain real-time information related to the condition of reinforced concrete is essential for assessing durability and safety. Dawson et al. [1] investigated the condition of reinforcing steel in concrete by an electrochemical impedance spectroscopy (EIS). They [1] emphasized that the EIS can be employed for the evaluation of the corrosion rate of rebar in concrete. Nòvoa [2] reported an application of EIS to investigate the microstructure of cementitious cover, transport of chlorides in concrete, and the steel-concrete interface.
In the present study, we developed a new method to determine the degradation of concrete using the cylindrical steel probes by EIS. Figure 1 shows the cylindrical steel probes developed in the present study. These probes have 10 mm diameter and 8 mm thick. These probes are embedded in concreate and the electrochemical impedance is monitored. We expect that the degradation of concreate can be determined by monitoring of the electrochemical impedance of the cylindrical steel probes. In order to establish the proposed monitoring method, the electrochemical impedance of the cylindrical steel probes embedded in concreate was measured. The size of concrete specimen was 100 mm × 100 mm × 200 mm. The two holes were drilled on the concrete surface of 100 mm × 200 mm. The diameter of each hole was 10 mm. The distance between both probes was 50 mm. The probes were embedded in these holes and fixed by the epoxy resin. The depth of the probes embedded in concrete specimen was 2.0 mm, 5.0 mm and 10 mm. The concrete specimen was immersed in 10 % sodium chloride aqueous solution. Figure 2 shows a schematic diagram of the measurement system. The air was continuously provided by pump during the immersion of the concrete. The electrochemical impedance was automatically monitored at 10 kHz and 10 mHz using a corrosion monitor (Corp. i-pec, CEM-100A) by two electrode system. The potential amplitude was 10 mV.
The charge transfer resistance R
ct was estimated from the impedance of the cylindrical steel probes measured at 10 kHz and 10 mHz. The degradation of concreate was discussed based on the changes of values of R
ct with time.

Reference

[1]　J. L. Dawson, L. M. Callow, K. Hladky and J. A. Richardson, Corrosion/78, No-125 (1978).
[2]　X. R. Nòvoa, J Solid State Electrochem, 20, (2016) 2113-2125.

Figure 1
Mass Transfer Mechanisms in Solid Electro Deposition
Authors: Narui Yuka , Hoshi Yoshinao , Shitanda Isao , Itagaki Masayuki , Yanagimoto Hiroshi , Hiraoka Motoki , Iisaka Hirofumi 
Published: February 2020

Copper plating is generally used for the fabrication of printed circuit boards of electronic devices. The patterning is carried out by masking with insulator for the partial plating on the substrate. It is desirable to develop a new alternative technology that takes environmental issues into consideration because the partial plating with a mask involves very complicated processes and wastewater treatment. Solid Electro Deposition (SED) method with the solid electrolyte membrane was reported by Yanagimoto et al.1) as the way to resolve the problem. The SED can be performed by a simple electrochemical cell in which the solid electrolyte membrane is sandwiched by counter and working electrodes. Imposition of voltage between two electrodes enables electrodeposition on the working electrode. The advantages of SED are written as follows.
・The electrochemical cell is very simple because the electrolyte is solid.
・The post-processing is also simple．
・It can be high-rate plating because the driving force of mass transfer of reactant is migration.
Among these advantages, the principle for high-rate plating by SED is explained below. Figure 1 shows the conceptual diagrams of mass transfer of cupric ions on electrode surface in two electrolytes. The charge transfer rate increases depending on the overvoltage in the case of plating in liquid electrolyte. However, the concentration polarization occurs on the electrode surface when the charge transfer rate is higher than the mass transfer rate of reactant. In this case, the driving force of mass transfer in electrolyte is normally diffusion. On the other hand, the mass transfer of reactant is dominated by migration in the SED if the transport ratio of metal ions in the solid electrolyte is unity. In this condition, the charge transfer rate becomes equal to the migration rate and the concentration polarization of reactant in the vicinity of the electrode does not occur, even if the charge transfer rate is increased. Therefore, it is possible to realize high-rate plating because diffusion is not rate-limiting process. We report the relationship between mass transfer mechanisms in solid electrolyte membrane and potential-current curves and establish the theory of high-rate copper plating by the SED. Reference:
1) K. Akamatsu, Y. Fukumoto, T. Taniyama, T. Tsuruoka, H. Yanagimoto, H. Nawafune, Langumuir, 27, 11761-11766 (2011).

Figure 1
Thermoelectric Properties & Characterizations of Surmof Thin Films
Authors: Chen Xin , Hassan Zeinab Mohamed , Redel Engelbert , Baumgart Helmut 
Published: February 2020

A new class of thermoelectric materials termed surface-anchored (metal-organic frameworks and coordination network compounds) SURMOFs thin films materials will be introduced. SURMOFs thin films demonstrates promising application potential of organic porous thin films in future thermoelectric and electronic devices working highly efficient in the RT (Room Temperature) region. In our first studies we have characterized the Seebeck coefficient of polycrystalline and highly-ordered SURMOF thin films.1,2

Since SURMOFs are highly porous and the size of their pores are highly adjustable, they can be further functionalized and tailored due to their electrical and thermal conductivity properties. SURMOFs can be therefore regarded as tailorable organic Thermoelectric Material of the future. An outlook will be given on their further electronic characterization, Hall measurements and thermal conductivity as well as on first ZT Chip measurements.

References:
1) X. Chen, Z. Wang, P. Lin, K. Zhang, H. Baumgart, E. Redel, C. Wӧll, ECS Trans.,75, 119-126 (2016)
2) X. Chen, Z. Wang, Z. M. Hassan, P. Lin, K. Zhang, H. Baumgart, E. Redel, ECS Journal of Solid State Science and Technology, 6, P150-P153 (2017).

Figure 1