bluuebunny/crossref_metadata_2025 huggingface dataset:
A Simple and Fast Analysis of LSD By Cyclic Voltammetry in Aqueous Medium
Authors: de Oliveira Marcelo Firmino , Oiye Erica Naomi , Ribeiro Maria Fernanda Muzetti , Katayama Juliana Midori Toya
Published: February 2020

Once the drug is apprehended, forensic laboratories must follow a procedure with chemical analysis aiming a confirmatory result. The application of electrochemical analysis inside forensic scenario has been widely explored, mainly in the analysis of illicit drug, due to the sensitivity and specificity acquired in a voltammetric measurement. Among these drugs, the psychedelic LSD (lysergic acid diethylamide) appears in seized blotters, and its apprehension is constant in global scale. LSD is a hallucinogenic drug, which concentration in blotter may show a discrepancy from 20 to 150 µg.

In this context, the development of a fast voltammetric method for quantification of LSD is proposed in the present study. It is important to highlight the use of an aqueous medium for the analysis, once the literature related to voltammetric studies for LSD, englobes organic medium in its majority.

In a conventional system with glassy carbon as the working electrode, the measurements were taken in KClO4 0.05 M as the supporting electrolyte. After an optimization study, the parameters fixed for the Cyclic Voltammetry were: potential range from 0.0 to 1.4 V and scan rate of 250 mV s-1. No pre concentration step was required.

The choice of KClO4 is based on a comparing study between others perchlorates salts (LiClO4, NH4ClO4, NaClO4) as supporting electrolyte. In addition, the pH of the solution was also verified, and the best condition for these measurements was pH 7.

The anodic peak observed in approximately potential of 0.9 V (Figure 01) is proportional to the concentration of LSD, what enables to stablish a linear equation y = 0.091 A L mol-1 x + 1.15x10-7 A for the quantification of LSD, in a linear range from 2.46 to 13.78 µmol L-1. The limits of detection and quantification are 0.73 and 2.46 µmol L-1, respectively, what enables detecting LSD in a concentration level of 4 µg per mL of the extraction solution. Besides, the use of an aqueous solution characterizes a less pollutant and less toxic methodology.

Then, the present work purposes a new methodology for quantification of LSD by Cyclic Votammetry, with an aqueous medium and also englobes a study about the electrochemical behavior of this drug under various experimental conditions.
Textile Fiber Electrode to Monitor Uric Acid and for Assessing Wound Chronicity
Authors: Pierre Michelle , RoyChoudhury Sohini , Umasankar Yogeswaran , Manickam Pandiaraj , Fernandez Renny E , Munroe Norman , Bhansali Shekhar
Published: February 2020

A nanocomposite textile fiber electrode functionalized with uricase has been integrated in a wearable platform for uric acid monitoring. Uric acid is a metabolic product of purines which exerts role in tissue healing by initiating the inflammatory process.1 Throughout the healing process, the uric acid levels are elevated in the wound fluids with relative concentrations correlating with wound chronicity.2, 3 Though sensors embedded in the point of care devices allowed rapid wound diagnostics, still there are no wearable technology for continuous monitoring. In this work, a three-dimensional high aspect ratio nanocomposite textile based electrode was investigated. The unique structure of the electrode provided larger surface area for enzyme immobilization, and an excellent platform for electron transfer from enzymatic reaction. The enzyme immobilization was carried out by entrapping uricase in a cationic polymer on the fiber surface. The uricase reaction mechanism involves the hydrolysis of uric acid in presence of oxygen, and release of hydrogen peroxide as a byproduct. The redox electron shuttle, ferrocene carboxylic acid (FCA) enabled electron transfer between the byproduct of uric acid and the fiber, generating the signal. The voltammogram result shows a stable electrochemical response at an onset potential of 0.25V with a limiting current of 0.6 µA. The 0.25V onset potential is ideal for any hydrogen peroxide measurement without interference from oxygen reduction reaction. This functionalized fiber electrode enabled the possibility of textile based wearable sensor for monitoring wound chronicity.

References

C.-T. Huang, M.-L. Chen, L.-L. Huang, and I.-F. Mao, Chin. J. Physiol., 45, 109–115 (2015).

T. R. Dargaville, B. L. Farrugia, J. A. Broadbent, S. Pace, Z. Upton, and N. H. Voelcker, Biosens. Bioelectron.
41, 30–42 (2013).

M. L. Fernandez, Z. Upton, H. Edwards, K. Finlayson, and G. K. Shooter, Int. Wound J., 9, 139–49 (2012).
Simple Solution Deposition of Co3O4 on FTO for Rapid and Selective Nonenzymatic Glucose Detection
Authors: Chowdhury Mahabubur , Aliwa Maelsand
Published: February 2020

There is no permanent treatment for diabetes mellitus yet. This condition is managed by regularly checking blood glucose levels and taking appropriate measures accordingly. Hence, a significant amount of research efforts have been made to develop highly sensitive and affordable glucose sensor. It is well known that the performance of any sensor is highly dependent on the nature and fabrication techniques used for the preparation of the electrodes. Various electrode fabrication techniques such as pulsed laser deposition (PLD), plasma sputtering, atomic layer deposition (ALD), hydrothermal, electrodeposition, electrospinning have been used to fabricate various metal oxide based electrodes for glucose sensing applications. These techniques are not suitable for commercial scale production of economical nonenzymatic glucose sensor.

In this study a simple chemical solution deposition process has been used to fabricate Co3O4 electrode as an electrocatalyst for nonenzymatic oxidation of glucose. Several physical and chemical characterisation techniques such as XRD, HRSEM, HRTEM,AFM, EIS, EELS, EDS was used to elucidate the phyiscal and chemical characteristics of the Co3O4 electrode. The as prepared electrode showed fast response time (< 7s), good sensitivity (504.1 µA mM-1cm-2), high selectivity towards glucose at an applied potential of +0.60V in 0.1 M NaOH solution. A detection limit of 3 µM (S/N = 3) was measured for the Co3O4 electrode. The electrode retained 85% of initial current response after 2 months of application. Figure 1 presents the electrochemical performance of the Co3O4 electrode in the presence and absence of 1mM glucose at a scan rate of 25 mVs-1.

Figure 1
Carbon Monoxide Gas Sensing Study Using Hydrothermally Prepared NiO/Graphene Nanosheets Electrode
Authors: Khaleed Abubakar Abubakar , Bello Abdulhakeem , Dangbegnon Julien Koudio , Olaniyan Okikiola , Mwakikunga Bonex W. , Manyala Ncholu
Published: February 2020

Monitoring trace concentrations of harmful gaseous chemical species is increasingly needed in different areas such as indoor, outdoor, vehicle air control, mining and manufacturing sites. Hence, the fabrication of highly sensitive and selective chemical gas sensors are imperative. Chemi-resistive gas sensors based on semiconducting transition metal oxide are potential candidates due to their ease of operation, low cost of manufacturing, microscale miniaturization and good thermal and long-term stabilities [1–3]. In this work, spherical NiO/graphene foam (GF) composite with flowerlike structures were successfully synthesized for their application as CO reducing gas sensor via a hydrothermal reflux process. X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and gas sorption analysis were used to characterize the structure and morphology of the samples. The results obtained from the SEM micrographs showed that the flowerlike NiO spheres successfully coated the entire surface area of the GF. The performance of the composite towards CO gas sensing was studied. The results reveal that the incorporation of graphene into flowerlike NiO spheres not only improved the conductivity and surface area of NiO/GF composite, but also enhanced the performance of the composite towards CO sensing. These results suggest that the composite could be a potential active material for CO reducing sensors.

References

[1] Gogotsi, Y., CRC Press, (2006).

[2] Huang, X.-J.; Choi, Y.-K., Sensors Actuators B Chem., 122 (2007), 659–671.

[3] Lu, J. G.; Chang, P.; Fan, Z., Mater. Sci. Eng. R Reports, 52 (2006), 49–91

Figure 1
Mg-Based Spinel Nanocrystals: Phase, Size, Electrochemical Properties
Authors: Hu Linhua , Kim Soojeong , Fister Timothy T , Freeland John W , Nolis Gene M , Yoo Hyun Deog , Cabana Jordi
Published: February 2020

Li-ion batteries are the top choice in electrochemical energy storage for portable devices and mobile vehicles. However, the limited storage capacities do not quite yet meet the emerging energy demands in transportation and grid markets. Multivalent batteries based on divalent cations have attracted wide attention with high energy density/capacity in different framework of oxide cathodes. For instance, spinel structure M2O4, has been theoretically predicted as one of the most suitable oxide cathode for the reversible intercalation with Mg2+ [1]. Further, reversible, yet sluggish Mg intercalation into Mn2O4 host, prepared from de-lithiated LiMn2O4 electrode, was reported in aqueous electrolyte environments [2]. In order to enhance kinetics, reduction of particles to the smallest possible sizes is desired. Further, spinel-type Mn­2O4 can only be prepared by delithiation of LiMn2O4. Therefore, the direct synthesis of the parent spinel oxide, MgMn2O4, in the form nanocrystals would be desirable to investigate the fundamental limits of Mg intercalation within the spinel oxide framework, preferably in non-aqueous electrolytes.

Here, we report a series of Mg-based spinel nanocrystals with different phase (MgxMn3-xO4 and MgxCr3-xO4), size (5nm~50nm), and shape (cube and sheet) via a low temperature hydrothermal process, followed by calcination (Figure 1). All samples were characterized with X-ray diffraction and spectroscopy, as well as electron microscopy in order to define the products of electrochemical reactions in non-aqueous cells. Our goal was to explore spinel oxide nanocrystals with optimal size, phase, and shape and establish size-structure-property relationship for the experimental realization of Mg reversible intercalation in spinel oxide hosts.

1. Liu, M., et al.,
Energy Environ. Sci. 2015, 8, 964.

2. Kim, C. et al., Adv.
Mater. 2015, 27, 3377.

Figure 1 (a) Representative STEM image of 50nm MgMn­2O4 nanocubes (b) Representative STEM image of 2~5nm thickness MgMn­2O4 nanosheets

Figure 1
Impurity-Driven Anode Surface Chemistry in Organic Electrolytes for Multivalent Ion Batteries
Authors: Connell Justin Grant , Genorio Bostjan , Lopes Pietro Papa , Strmcnik Dusan , Stamenkovic Vojislav , Markovic Nenad M
Published: February 2020

One the biggest challenges facing the development of Mg-ion battery technology is the fact that many promising Mg electrolytes are incompatible with either the metallic Mg anode or with the high voltage oxide cathode materials that are required to compete with existing Li-ion technologies. Understanding the role of the many impurity species present in Mg electrolytes is crucial to understanding how to design new electrolytes that can stabilize Mg metal without using Cl-, and therefore enable its use with oxide cathodes in full cells. In light of these complexities, we introduce a surface science-based approach for rationalizing, and ultimately understanding, the impurity-driven electrochemical processes that take place during the electrodeposition of Mg ions, focusing in particular on the technologically-relevant Mg bis-(trifluoromethane sulfonyl) imide (MgTFSI2) in diglyme electrolyte system. Using a combination of electrochemical and spectroscopic methods, it was found that trace amounts of water (≤ 3 ppm) strongly impact both the kinetics of Mg deposition and the reversibility of Mg stripping, with the formation of passive surface films taking place only after Mg deposition ceases and the extent of passivation determining the electrochemical response and resulting Coulombic efficiency. A complex and dynamic competition between H2O and Cl- species present at the interface was also observed that results in dramatic changes to the surface chemistry and the resulting deposition/stripping kinetics. We anticipate that this surface science-based approach is relevant well beyond Mg deposition/stripping, and can be applied to the deposition/stripping of Li and other mono/multivalent metals, intercalation/deintercalation processes in multivalent cathode materials, and many other systems.
Synthesis and Characterization of NaAlTi3O8 As a Novel Intercalation Anode Material for Sodium Ion Batteries
Authors: Ma Xuetian , Bai Jianming , An Ke , Chen Hailong
Published: February 2020

Sodium ion batteries are being considered as an alternative to lithium ion batteries in large scale energy storage applications owing to the low cost. A novel titanate compound NaAlTi3O8 was successfully synthesized and tested as a promising intercalation anode material for sodium ion batteries. Powder X-ray diffraction (XRD) and refinement were used to analyze the crystal structure. Electrochemical cycling tests under a C/10 rate between 0.01-2.5 V showed that ~83 mAh/g capacity can be achieved in the second cycle, with ~75% of which retained after 100 cycles, which corresponds to 0.75 Na+ insertion and extraction per formula unit. The influence of synthesis conditions on electrochemical performances was investigated and discussed. NaAlTi3O8 not only presents a new anode material with low average voltage of ~0.5 V, but also provides a new type of intercalation anode with a crystal structure that differentiates from previously reported intercalation anode materials.

Figure 1
Sodium-Ion Intercalation in Bilayered V2O5 Modified Aerogel: Thermodynamic Characteristics of NaxV2O5 (0 ≤ x ≤ 4, and beyond)
Authors: Smyrl William H , Guillaume Francis
Published: February 2020

Sodium-ion batteries are candidates to replace lithium-ion analogs for energy storage, because of sustainability advantages. The technologies are similar, but the lithium system is much more advanced after two decades of development. A recent review on Na systems is available [Yabuuchi, et al. 2014], which documents the renewed interest for sodium after several years of intermittent research attention. The present study is for vanadium pentoxide modified-aerogel (V2O5/m-ARG) as an electrode material to host Na ion insertion and release. We have discovered that the capacity for sodium to be more than 4 moles of sodium per mole of V2O5, with a flat voltage plateau for 1= x = 4. This corresponds to a specific capacity of about 560 mAh/(g host) for x=4. The Equilibrium Potential vs Composition of Na+ ions was measured with the Galvanostatic Intermittent Titration Technique (GITT). The experimental specific energy is about 1600 WH/kg of the host. Further, the intercalation thermodynamics of Na+ ions has near-ideal behavior. The high specific capacity and the high specific energy makes the host an attractive cathode material for Na-ion systems.
Passivation of Si-CNT Anode in Li-O2 Full Cell
Authors: Kwak Won-Jin , Sun Yang-Kook
Published: February 2020

For years, Lithium oxygen battery has been attractive which can make high energy density for next generation. However, even if the many researches have been progressed for years,1-4 the works about substitution of Li metal which has inherent limitation of stability and long term cycling property was terribly deficient.

Here in, our group clearly demonstrate the ambiguously unsolved problem of lithium oxygen full cell system using alternative anode (lithiated Si-CNT composite) for lithium metal by XRD and SEM analysis. The amount of lithium source in alternative anode is limited compared to quasi infinite amount of Li source in Li metal. The returning lithium ion at the charge forms the lithium hydroxide which passivates the anode by side reaction with moisture in electrolyte and from outside. Side reactions, leading to the formation of LIOH at the anode site caused loss of the Li source, resulting in decreased potential and poor cycle of the Li-O2 full-cell system.

Although the Li-O2 full-cell without lithium metal could be a good area for practical Li-O2 battery work in terms of safety, it is not viable without solving the Li loss problem. Our results could be helpful for further research into Li-O2 full-cell systems, and this issue could constitute a fundamental theme for future practical Li-O2 battery systems.

Reference
s

1. M. M. O. Thotiyl, S. A. Freunberger, Z. Peng, P. G. Bruce, J. Am. Chem. Soc., 2013, 135, 494-500.

2. B. M. Gallant, R. R. Mitchell, D. G. Kwabi, J. Zhou, L. Zuin, C. V. Thompson, Y. S. Horn, J. Phys. Chem. C, 2012, 116, 20800-20805.

3. V. S. Bryantsev, V. Giordani, W. Walker, M. Blanco, S. Zecevic, K. Sasaki, J. Uddin, D. Addison, G. V. Chase, J. Phys. Chem. A, 2011, 115, 12399-12409.

4. D. Sharon, V. Etacheri, A. Garsuch, M. Afri, A. A. Frimer, D. Aurbach, J. Phys. Chem. Lett., 2013, 4, 127-131.
Incorporation of Nickel Sulfide into Sulfur Cathode for Li–S Battery
Authors: LI Zhe , Ueno Kazuhide , Dokko Kaoru , Watanabe Masayoshi
Published: February 2020

The lithium–sulfur (Li–S) battery has been attracting tremendous interest as a promising “beyond Li-ion” device, because of its high theoretical specific capacity and energy density [1-4]. However, its widespread applications, such as electric vehicles and large-scale grid-based energy storage systems, are still plagued with several issues and challenges. For example, the intrinsic insulating nature of sulfur makes it difficult to achieve high active material utilization. Additionally, the polysulfide intermediates are highly soluble in the benchmarked ether-based electrolytes, resulting in a severe redox shuttle effect between the sulfur cathode and Li anode. This undesired shuttle phenomenon can lead to a significant loss of active material, fast capacity fading and low Coulombic efficiency.

In this work, we incorporated nickel sulfide into the sulfur cathode design through a facile two-step strategy. Note that nickel sulfide here can trap the polysulfide intermediates and inhibit the shuttle effect owing to its binding interactions with polysulfide. Moreover, the low resistivity of nickel sulfide is expected to facilitate the redox kinetics of the adsorbed polysulfides. As a result, this hybrid cathode with a sulfur loading of 4.0 mg/cm2 could manifest an excellent electrochemical performance at a high current density.

References

[1] S. Zhang, K. Ueno, K. Dokko, M. Watanabe, Adv. Energy Mater., 5 (2015) 1500117.

[2] K. Dokko, N. Tachikawa, K. Yamauchi, M. Tsuchiya, A. Yamazaki, E. Takashima, J.W. Park, K. Ueno, S. Seki, N. Serizawa, M. Watanabe, J. Electrochem. Soc., 160 (2013) A1304-A1310.

[3] Z. Li, S. Zhang, C. Zhang, K. Ueno, T. Yasuda, R. Tatara, K. Dokko, M. Watanabe, Nanoscale, 7 (2015) 14385-14392.

[4] Z. Li, S. Zhang, S. Terada, X. Ma, K. Ikeda, Y. Kamei, C. Zhang, K. Dokko, M. Watanabe, ACS Appl. Mater. Interfaces, 8 (2016) 16053-16062.
Novel Strategies for Lithium Metal Anode Protection Based on Nitride Materials Chemistry: Insight from First Principle Calculations
Authors: Zhu Yizhou , He Xingfeng , Mo Yifei
Published: February 2020

Lithium metal is most attractive anode material for high-energy-density Li-ion battery. However, the strong reducing nature of lithium metal results in poor stability and low coulombic efficiency in lithium batteries. Despite decades of research efforts to stabilize lithium metal anode, the development of lithium battery is still greatly impeded by the lack of knowledge about lithium-stable materials chemistry. So far, only a few materials are known to be stable against Li metal.

Here, I will present our recent work, which provides novel strategies of using nitrides to stabilize lithium metal anode. We uncovered many lithium-stable materials out of chemistry across the periodic table, by using first-principles calculations based on large materials database. We found that most oxides, sulfides, and halides, which were commonly studied as protection materials, are reduced by lithium metal due to the reduction of metal cations. On the contrary, nitride anion chemistry exhibits unique stability against Li metal, which is either thermodynamically intrinsic or a result of stable passivation. Many nitrides materials, which were rarely investigated as lithium metal protection materials before, can be promising candidate lithium metal protection materials to achieve long-term stability.

Our work established essential guidelines for selecting, designing, and discovering materials for lithium metal protection. In addition, we also proposed multiple novel strategies of using nitride materials and high nitrogen doping to form stable solid-electrolyte-interphase for lithium metal anode. Our computation results provide novel guidance and strategies for stabilizing lithium metal anode and would contribute to the development of high-energy-density rechargeable lithium batteries.
Effect of Nickel and Iron on Structural and Electrochemical Properties of O3-Type Nickel-Iron-Manganese Based Cathodes for Sodium-Ion Batteries
Authors: Yu Taeyeon , Sun Yang-Kook , Kim Un-Hyuck , Ryu Hoon-Hee
Published: February 2020

To address the depletion of fossil fuels and air pollution problems many green energy systems have been explored over the past few decades. We investigate that the effect of Ni and Fe contents on structural and electrochemical properties of O3- type layered Na[Ni0.75-xFexMn0.25]O2 (x= 0.4, 0.45, 0.5, and 0.55) in which Mn is fixed at 25%. As increasing the Ni contents, the capacities are gradually higher while the capacity retention and thermal properties are inferior. When Fe contents are increased, by contrast, the electrode exhibits stable capacity retention and satisfactory thermal stability although the resulting capacity slightly decreases. Structural investigation of post cycled electrodes indicate that lattice variation is greatly suppressed from x=0.5 in Na[Ni0.71-5xFexMn0.25]O2. This indicates that an appropriate amount of Fe into the Na[Ni0.75-xFexMn0.25]O2 stabilizes the crystal structure and this leads to the good cycling performances. Also, the better structural stability obtained by Fe addition is responsible for the less heat generation at elevated temperature for the desodiated Na[Ni0.75-xFexMn0.25]O2 (x = 0.4, 0.45, 0.5, and 0.55) caused by less evaporation of oxygen from the crystal structure.
Phosphate-Based Cathode Frameworks for Potassium-Ion Battery
Authors: Masese Titus , Sano Hikaru , Senoh Hiroshi , Shikano Masahiro
Published: February 2020

Lithium-ion battery has remained as the dominant energy storage system due to its high energy density and electrochemical reversibility for the last few decades, albeit its cost and resource restrictions remain prohibitive for largescale applications. With this imminent concern, a great deal of attention has been devoted recently to the development of lower cost and more abundant alternative chemistries such as potassium-ion battery (PIB) [1].

Intensive research on a number of potentially economical potassium-containing host materials as cathode materials for PIB have been reported recently, but most of the potassium-based materials are still not able to meet industrial standards. This mainly stems from the structural instability posed during the electrochemical extraction of the large potassium ion, and also the electrochemical inactivity of some of the host materials. Therefore, at this juncture, it is necessary to identify potassium-containing host materials that can reversibly (de)insert potassium.

During the course of our investigation, we have identified K-rich phosphate-based cathode frameworks that can facilitate reversible (de)insertion of potassium-ion. In this presentation, we will briefly introduce our current research progresses on phosphate-based polyanion cathode materials (such as K
x
MP2O7 pyrophosphates (some of the phases of which are shown in Fig. 1), K
x
MPO4F fluorophosphates and K
x
MPO4 monophosphates (x=1,2)) and provide preliminary results about their electrochemical activity.

 

Reference
s
:

[1] A. Eftekhari, J. Power Sources,
126 (2004) 221-228.

Figure 1
Enabling Storage of Divalent Cations in Layered Vanadium Pentoxide through Controlled Interlayer Interactions
Authors: Rhodes Christopher , Niu Sibo , Cox Peyton
Published: February 2020

Cathode materials that store divalent cations (Mg2+, Zn2+, Ca2+) can provide batteries with high capacities, lower costs, and improved safety. However obtaining cathode materials that store divalent cations and have high voltages, high capacities, and high reversbilities remains a key challenge due to the high charge densities and polarizabilities of divalent cations which results in strong interactions with the host lattice and low diffusion coefficients. Our group has investigated layered vanadium pentoxide (V2O5) as a model host material for divalent cation charge storage. Recent work by our group has shown that incorporation of poly(ethylene oxide) between the V2O5 layers alters the interlayer structure and dynamics and improves the transport and storage of divalent Mg2+.1 Based on the importance of the characterizing the structure of the interlayer region, we have used changes in Raman-active acoutic phonon modes to probe interaction of solvents and ions with the V2O5 layers. The effects of altering polymer composition within the interlayer and the electrolyte composition on the storage of divalent cations have been recently explored, and results of this work will be presented. The design of layered materials with controlled interlayer compositions provides an approach to significantly improve charge storage and transport of divalent cations.

References

Perera, S.D.; Archer, R.; Damin, C.A.; Mendoza-Cruz, R.; Rhodes, C.P. Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage, Journal of Power Sources,
2017, 343, 580-591. DOI:10.1016/j.jpowsour.2017.01.052.
Zirconia Support for the Stabilization of Discharged Product of Lithium-Oxygen Battery
Authors: Bae Seongjun , Yoo Young Geun , Park Jongseok , Park Soomin , Nam Inho , Song Hyeon don , Han Jeong Woo , Yi Jongheop
Published: February 2020

A demand for lithium-oxygen (Li-O­2) batteries with high storage capacity is increasing due to its application for the energy storage systems and electric vehicles. However, there are still critical bottlenecks for fabrication of a commercial Li-O2 battery. The cyclability of Li-O2 battery is very poor compared to lithium-ion battery. The main reasons for this problem are a variety of side reactions during the battery operation, which inactivate the lithium anode and cathode catalyst. To solve this problem, reversible charge/discharge reactions should be presented. During discharge reaction of Li-O2 battery, various superoxide and peroxide species, such as O2
-, LiO2 and Li2O2 appear. These nucleophilic molecules could react with electrolyte and carbon electrode. A dominant portions of side-reactions originate from this process. Therefore, we adopted a catalyst support with surface oxygen-defects to stabilize the nucleophilic molecules. In this study, we used zirconia as a support and observed that electrocatalyst with zirconia support exhibits better cyclability compared to that without support. Experimental and computational approaches are exploited to understand this phenomenon and we found that the reactivity of superoxide and peroxide species decrease with the oxygen-defective support. Our concept proposed in this study could be the clue for the design of cathode catalyst for reversible charge/discharge reactions.
Fully Dense Sintering of Li Garnet Materials for All Solid State Li Ion Batteries
Authors: Zhang Lei , Gong Yunhui , Fu Zhezhen , McOwen Dennis W. , Gritton Jack E. , Godbey Griffin L. , Wachsman Eric D.
Published: February 2020

Traditional lithium (Li)-ion batteries with liquid electrolytes suffer the problems of poor safety, limited voltage, unstable solid-electrolyte interphase formation and poor cycling performance, all of which can potentially be solved by solid-state lithium batteries (SSLiBs). The widely studied solid-state electrolytes (SSEs) includes LiSICON [1], NASICON-type Li conductors [2], perovskites [3] and garnets [4]. Garnet electrolytes are especially attractive for SSLiBs [4], since it has high total Li-ion conductivity, chemical stability with high voltage Li cathodes, chemical stability with Li anode. Aside from these good electrochemical property, developing an inexpensive and environmentally friendly thin-film preparation methods is critical for its application in SSLiBs. Such a thin film should have very high relative density, in order to prevent Li dendrite growth as well as to further improve total Li conductivity.

Li garnet materials are known to be difficult to sinter, due to Li evaporation at high temperature. Traditional die-pressing and ambient pressure sintering products garnet pellets with low relative density (<96%) and bad grain-grain connection. Currently there are only several papers reporting fully dense garnet (relative density >99%). These works require either high pressure sintering [5] or specially synthesized garnet nano powders [6]. These requirements hinder the cost-effective mass production of garnet thin film. Here in this work, we use a cost-effective tape-casting and sintering method to fabricate fully dense garnet thin films. The thinness of the thin film can be varied from as thin as 20 um to as thick as 1mm. The size of the thin film can be controlled by trimming before or after sintering. Figure 1(insert) shows the transparency of sintered garnet thin wafer. It high relative density is confirmed by SEM in figure 1.

The mechanism behind the fully dense sintering is studied. It is found that a good powder packing in the green tape and garnet particle surface modification by moisture and carbon dioxide during sintering contributes.

Reference:

[1] Xu, X. et al. Chem. Mater. 23, 3798-3804 (2011).

[2] Feng, J. K. et al. Mater. Technol. 28, 276-279 (2013).

[3] Ihlefeld, J. F. et al. Adv. Mater. 23, 5663-5667 (2011).

[4] Thangadurai, V. et al. Chem. Soc. Rev. 43, 4714-4727 (2014).

[5] Sharafi, A. et al. J. of Power Sources 302, 135-139 (2016).

[6] Yi, E. et al. J. of Power Sources 352, 156-164 (2017).

Figure 1: Fully dense garnet thin film has seamless cross section, indicating a very strong grain-grain connection. The insert shows its transparency.

Figure 1
Ferroelectric Coupled c-Sulfur Composite Cathode for High Rate Performance of Li-S Battery
Authors: Tripathi Balram , Katiyar Rajesh , Katiyar Ram S
Published: February 2020

Lithium sulfur batteries with high charge-discharge rate capabilities are in great demand for hybrid vehicles, electric vehicles and portable electronic products. However uptill now its real applications are still plagued by rapid capacity fade mainly stemming from the polysulfide shuttle. High rate capability can be often enhanced by downsizing cathode materials to the nanoscale which increases the reaction surface to volume ratio but downsizing to less than 100 nm reduces the capacity. Ferroelectric materials have attracted much attention due to their unique ferroelectric, piezoelectric and ferroelastic properties. Coupling of highly polarized ferroelectric (BiFeO3) layer is an approach that can be used to enhance the higher rate characteristics and trapping of shuttle mechanism because ferroelectrics provides higher polarization which help to build up an internal electric field and induces macroscopic charges on the surface of the cathode. In Li-S batteries during discharge polysulfide shuttle causes capacity fade of the battery. We can speculate that polysulfide’s are heteropolar in which spontaneous polarization of ferroelectrics (BiFeO3) may solve the shuttle effect and can trap its formation for high rate performance Li-S batteries.
(Invited) Enabling Global Impact of Amperometric Gas Sensors
Authors: Stetter Joseph R , Carter Michael T , Findlay Melvin W
Published: February 2020

The enabling technology needed to catch the integrated “sensing-computing-communicating” economic engine of the early 21st century is that of environmental sensing. Human exposure to the environment [air, water, food, biologicals] is responsible for a major part of the disease burden of global populations and WHO predicts at least 6M premature deaths this year. A major route of exposure is inhalation and we all breathe the same air, and air pollution sensors that target the EPA priority pollutants of CO, NO2, Ozone, and SO2 are of increasing importance. One must measure something in order to understand and mitigate its effects and gas sensors do this job. Disruptive technologies, i.e. those that bridge the cost-performance gap, are required to field measurement capability globally. The amperometric gas sensor1,2 is an important contributor to environmental measurement capability. Recent advances have used printed electronics and semiconductor fabrication approaches to enable new commercialization opportunities. The ability to develop new sensor designs and to use advanced materials is key to setting up supply chain capability that has led to ever larger deployments of these sensors for breath/health measurements, environmental measurements, and safety. These new sensors exemplify a path to commercialization for high volume low-cost sensing with potential for high global societal impacts.

1] M. T. Carter, J. R. Stetter, M. W. Findlay and V. Patel, “Printed Amperometric Gas Sensors,” ECS Transactions, 50(12), 211-220 (2012). DOI 10.1149/0512.0211ecst.

2] Joseph R. Stetter and Jing Li, in Modern Topics in Chemical Sensing: Chapter 4, “Amperometric Gas Sensors – A Review,” Chemical Reviews, 108 (2), 2008, pp352-366.
(Keynote) The Importance of Open Science in a Changing Scholarly Communications Paradigm
Authors: Farley Ashley
Published: February 2020

As the scientific community continues to shift towards open access, it becomes more concrete the future will indeed be “open”. However, there exists numerous nuanced obstacles in this paradigm shift that holds science back from fully being open. This talk will cover how the Bill & Melinda Gates Foundation is driving efforts to overcome these obstacles to establish an environment where Open Science can flourish. From the perspective of a funder, Open Science practices have the potential to help us reach our vision rapidly and more effectively. How can policy drive this shift towards open science? What can individual stakeholders do to drive and effect change?
Open Your Data
Authors: Morovati Meredith
Published: February 2020

There has been much talk about the reproducibility and re-use crisis: scientists from various fields are losing faith in the ability to replicate previous research and many have complained of the difficulty of accessing repository data. This is occurring during a time when local, national, and international governments, which develop public policy, should be relying on the outputs of research. Yet, there is increasing noise about what truly comprises these outputs and what the value of the research really is. There is a lot of work to be done to improve the public’s trust in science, to better communicate about science to non-scientists, and to continue to build upon reputable, quality research.

Open access to all outputs of science can improve the relationship between scientists and the public, and provide opportunities for the development of new research. Shoring up published scholarly articles with open data is an essential starting place. Opening your data to publish it alongside your article will increase public confidence in research and allow others to re-use your data to pursue new directions in order to advance science.

At Dryad, we have been encouraged by recent changes in fields previously resistant to open access, which are now implementing open data practices. The Dryad repository has over 18,000 packages of data, with over 56,000 separate data files that link out to over 600 different journals. We encourage researchers from all fields to take advantage of data repositories to help make their data discoverable, freely reusable, and citable.
Soft Materials for the Lithium-Air Battery Electrode
Authors: Gould Emily Margaret , Clegg Paul S
Published: February 2020

Lithium-air batteries provide a promising high-energy-density alternative to traditional Lithium-ion technologies, particularly for use in electric vehicles. Current Li-air batteries can be recharged, but their usefulness is limited by their short lifetime. The discharge capacity of the battery is dictated by the build-up of reaction products, which choke the cathode by blocking further reactions between the electrolyte and the air [1]. As the breakdown of these reaction products during charging is never fully complete, subsequent charging cycles reduce the discharge capacity until the battery is no longer useful.

We investigate the use of soft materials to create a Li-air cathode that brings the three key components: electrolyte, electrode and air, into close contact with each other, increasing the contact area between the components and thereby reducing the likelihood of the reaction product keeping the electrolyte and air apart from each other. We use high internal phase Pickering emulsions (Pickering HIPE) (Fig. 1) to create a ‘tricontinuous’ structure (Fig. 2), in which the conducting particles on the interface and both liquid phases are all continuous in 3D space [2]. When fully realised, this structure should allow us to create a cathode where the build-up of reaction product over repeated charge cycles has very little effect on the ability of the electrolyte to react with oxygen from the air during discharge.

[1] J. Read, J. Electrochem. Soc. 149 (2002) A1190.

[2] D. Cai, J.H.J. Thijssen, P.S. Clegg, Appl. Mater. Interfaces 6 (2014) 9214 – 9219.

Figure 1
The Design and Investigation Zinc-Air Flow Battery with Automatic Control System
Authors: Si Jingyu , Zheng Dong , Wang Gongwei , Liu Dan , Harris Joshua , Qu Deyang
Published: February 2020

The zinc-air rechargeable battery are considered as promising candidate for application in electromobility and large-scale stationary energy storage due to its high energy density , inexpensive and safety. However, the traditional battery structure limits the capacity of zinc-air battery due to ZnO generated and slow down the electrochemical reaction after discharge. A zinc-air flow battery with automatic control system is designed and manufactured, in which the flowing KOH electrolyte carries the anode electrode - zinc powder. Experiments investigated that the zinc morphology changes during the charge and discharge.The results show that several factors affect the performance and life of the battery, include the KOH concentration ,viscosity of the fluid，depth of discharge and discharge current.

Figure 1
Effect of Frequency on Structure of Porous Alumina Formed By Indirect Oxidation
Authors: Ishino Mami , Hashimoto Hideki , Asoh Hidetaka
Published: February 2020

In general, industrial anodization based on direct current or alternating current (AC) electrolysis can be applied to the surface treatment of large-sized and long aluminum products such as building materials. However, conventional anodization is unsuitable for the simultaneous surface treatment of a large number of small components including fine particles because direct conduction between the aluminum anode and the cathode is essential for completing the electrical circuit.

Recently, we proposed new surface treatment method, i.e., indirect oxidation and investigated the influences of electrolysis conditions such as voltage, frequency, reaction time, concentration of electrolyte, and temperature on the growth of porous oxide film [1]. In our previous study, high-purity (99.99 %) aluminum sheets with a working area of 10 cm2 and aluminum particles (99.5 %) of 3 mm diameter were used as processing objects. In the case of AC electrolysis in 8 mmol dm−3 oxalic acid at 20 °C, 60 VM, and 150 Hz, which were the base condition in this study, the current density was approximately 100 A m−2. When AC electrolysis was conducted at higher temperatures and voltages using a high concentration of oxalic acid compared with that in the base condition, a high current density in the 120–200 A m−2range was observed. Frequency had relatively small effect on current density. Even in the indirect oxidation, we observed that the relationship between the film thickness and the AC electrolysis time was approximately linear. We also used aluminum particles as a processed material to demonstrate the versatility of the indirect-oxidation-based surface treatment [1]. After indirect oxidation for 240 min under the base condition, the treated aluminum particles were immersed in dye solution. The dye was absorbed in porous alumina films over the entire surface of the aluminum particles. This result indicates that the porous films were uniformly and simultaneously formed on aluminum particles, i.e., the present technique can accommodate a wide variety of particle shapes and sizes with high throughput and low costs.

In this study, we carry out a preliminary study to investigate the effect of frequency on the structure of porous alumina formed by indirect oxidation. We mainly focus on the difference between the proposed method and conventional AC anodization. The correlation between the cell dimensions and applied voltage will be also discussed.

[1] H. Asoh, M. Ishino, H. Hashimoto, RSC Adv., 6, 90318 (2016).
Anisotropic Etching Characteristics of the Copper Electrodeposits with a Preferred Orientation on Si Substrates
Authors: Kim Sang-Hyuck , Park Chae-Min , Mun Seongjae , Lee Hyo-Jong
Published: February 2020

Copper is one of highly elastically anisotropic materials, it is possible to acquire the films with (111) preferred orientation by sputtering and electroplating processes on Si substrate. The Cu films on Si substrate has very flat surface, and we investigated etching rates for various oriented surfaces by coupled techniques of AFM and FIB. The faceting surface appeared after etching in 10 vol% nitric acid and the etched surfaces with three kind orientations of (111), (110) and (100) had triangular flake, ridge and rectangular pyramidal shapes, respectively. The etching rates were measured quantitatively, it was found that etching rates for nanosized as-plated initial region, (111), (110) and (100) oriented regions were 383, 270, 276, and 317 ㎚/min, respectively. These faceting surfaces seemed to be built up based on the thermodynamic equilibrium state of etching reaction because most of them had (111) front surface. The difference of etching rates was owing to the planar density of kink or ledge for each recrystallized orientation grains. In other words, the etching happened by step flow mechanism maintaining the thermodynamic equilibrium state. By using this technique, we expect to robustly perform fundamental studies of etching solutions with various organic and inorganic additives, effects of stress and impurity in the Cu thin films.
Using Redox-Induced Proton Transfer to Convert a Weak 3-H-Bond Dimer to a Strong 3-H-Bond Dimer
Authors: Choi Hyejeong , Smith Diane K.
Published: February 2020

An important goal in supramolecular chemistry is the development of stimuli-responsive systems in which the strength of the intermolecular interactions can be altered by external signals such as changes in light, temperature, pH or voltage of an electrode. Our group is exploring the latter possibility, primarily by trying to develop systems in which electron transfer perturbs the strength of H-bonding interactions between molecules. The underlying principle is straightforward: an oxidation that decreases the negative charge on a H-acceptor (A) or a reduction that decreases the positive charge on a H-donor (D) will weaken a H-bond. Alternatively, reduction that increases the negative charge on a H-acceptor or oxidation that increases the positive charge on a H-donor will increase the strength of a H-bond. However, in the latter case, it is possible that oxidation or reduction could also lead to full proton transfer. If this occurs across the H-bond, the primary H-bonds will remain, but the secondary H-bonds will change. This can lead to an increase in unfavorable secondary interactions, which would counteract the effect of the initial proton transfer. However, with proper design, proton transfer could lead to an increase in favorable secondary interactions, which would enhance the effect of initial transfer. The goal of this project is to do the latter. In particular, 3-H-bond DAD-ADA arrays will be studied in which the DAD component contains a N-alkyl-4,4'-bipyridinium or “monoquat” redox couple (see figure). DAD-ADA arrays have relatively weak association constants (102 in non-competitive solvents such as CHCl3) due to the three favorable primary H-bonds (shown as solid double-headed arrows in the figure) being counterbalanced by four unfavorable secondary interactions (cross interactions shown as dashed double-headed arrows). As shown in the figure, reduction of the monoquat by one electron should lead to proton transfer, creating not only a strong ionic primary H-bond, but converting all the secondary H-bonds to favorable ones. Examples of similar ionic DDD-AAA complexes have been reported in the literature with association constants greater than 109, suggesting it may be possible see a binding enhancement on the order of 107 upon reduction in this system. Initial voltammetric studies with just monoquat itself (x = nothing) and the diimide ADA guest will be reported in this presentation, along with our synthetic progress in making the complete DAD array, which will have X = NC(=O)R to make the H-donor a strongly donating amide NH.

Figure 1