bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ionic Liquids for Controlled Synthesis of Functional Materials for Energy-Related Applications
Authors: Dai Sheng 
Published: February 2020

The conventional synthesis of functional materials relies heavily on water and organic solvents. Alternatively, the synthesis of functional materials using or in the presence of ionic liquids represents a burgeoning direction in materials chemistry.1-4 Ionic liquids are a family of non-conventional molten salts that can act as both templates and precursors to functional materials, as well as solvents. They offer many advantages, such as negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility of both organic and inorganic molecules, and much synthesis flexibility. The unique solvation environment of these ionic liquids provides new reaction media for controlling formation of porous materials, creating functional groups in biphasic media, and tailoring morphologies of advanced materials. Challenges and opportunities in using ionic liquids for synthesizing functional materials in energy-related applications will be discussed.

Acknowledgment: This work was conducted at the Oak Ridge National Laboratory and supported by the Office of Basic Energy Sciences, U.S. Department of Energy, under contract No. DE-AC05-00OR22725 with UT-Battelle, LLC.

References

(1) Ma, Z.; Yu, J. H.; Dai, S. Preparation of Inorganic Materials Using Ionic Liquids. Adv. Mater.
2010, 22, 261-285.
(2) Sun, X. Q.; Luo, H. M.; Dai, S. Ionic Liquids-Based Extraction: A Promising Strategy for the Advanced Nuclear Fuel Cycle. Chem. Rev.
2012, 112, 2100–2128.
(3) Huang, K.; Chen, F. F.; Tao, D. J.; Dai, S. Ionic liquid-formulated hybrid solvents for CO2 capture. Curr. Opin. Green Sustain. Chem.
2017, 5, 67-73.
(4) Yang, Q. W.; Zhang, Z. Q.; Sun, X. G.; Hu, Y. S.; Xing, H. B.; Sheng Dai, S. Ionic liquids and derived materials for lithium and sodium batteries. Chem. Soc. Rev.
2018, 47, 2020-2064.
Electrochemical Formation of Dy-Fe and Nd-Fe Alloys in Molten CaCl2-LiCl Systems
Authors: Konishi Hirokazu , Hua Hang , Ono Hideki , Koizumi Yuichiro , Oishi Tetsuo , Nohira Toshiyuki 
Published: February 2020

We proposed a new separation and recovery process for rare earth (RE) metals from scraps using molten salt and an alloy diaphragm. RE containing scrap is used as the anode. A RE-transition metal (TM) alloy is used as the diaphragm, which functions as a bipolar electrode. During electrolysis, all the RE metals in the anode are dissolved in the molten salt as RE ions. One or several specific RE ions are selectively reduced to form RE-TM alloys on the alloy diaphragm according to their formation potentials and/or alloying rates. Subsequently, the RE atoms chemically diffuse through the alloy diaphragm and are dissolved into the molten salt as RE ions in the cathode room. The permeated RE ions are finally deposited on the Mo or Fe cathode as RE metals. The RE ions remaining in the anode room can be collected by electrolysis using another cathode in the anode room. Almost all impurities remain in the anode room as residue or anode slime.
The present study focused on Fe alloys as alloy diaphragms. The electrochemical formation of Dy-Fe and Nd-Fe alloys in molten CaCl2-LiCl systems at 873-973 K. To confirm the formation of Dy-Fe alloys, potentiostatic electrolysis was conducted at 0.30 V(vs. Li+/Li) and 0.50 V for 1 h using Fe plate cathodes at 873 K in CaCl2-LiCl-DyCl3 (0.50 mol% added). The two samples were analyzed by XRD. The alloy phases were identified as DyFe2 or DyFe3. On the other hand, potentiostatic electrolysis was conducted at 0.30 V and 0.50 V for 1 h using Fe plate cathodes at 873 K in CaCl2-LiCl-NdCl3 (0.50 mol% added). From the result of XRD analysis, it was found that several Nd-Fe phases were formed.
Effects of Introducing Metal Adatoms on the Electrochemical CO2 Reduction Behavior of Copper
Authors: Nishimura Yusaku F , Chan Karen , Hahn Christopher , Jaramillo Thomas F 
Published: February 2020

The electrochemical CO2 reduction reaction (CO2RR) is considered as a promising candidate for a carbon negative technology to realize ecological and economical sustainable development. At present, copper is the only metal that can produce fuels (hydrocarbons and oxygenates) through CO2RR, but has many key scientific challenges remaining for implementation as an electrocatalyst (especially, selectivity and activity). One of the common strategies to tune electrocatalytic properties is tailoring active sites in an electrocatalyst by introducing another metal to one metal surface. In this work, we investigated the effect of introducing another metal M onto Cu(100) on the CO2RR.
Physical vapor deposition was performed to obtain a 100-nm Cu(100) film epitaxially grown onto Si(100) substrate, followed by introducing 1-Å-equivalent another metal M (M: Ag, Au, In, Mo, Ni, Pd, and Sn) atoms onto the Cu(100) surface in vacuum. Atomic force microscopy and X-ray photoelectron spectroscopy guaranteed that M certainly existed on Cu and the M/Cu electrocatalyst had a smooth surface whose roughness was ±2 nm. The M/Cu electrocatalyst was supplied to a series of 15-min electrolysis in 0.1 mol dm−3 KHCO3 aqueous solution at potentials ranging from −0.6 to −1.1 V with respect to reversible hydrogen electrode at pH 6.8. Gaseous and liquid products were quantified with gas chromatography and nuclear magnetic resonance, respectively.
A series of electrocatalytic evaluation pointed out the following general trends concerning the electrocatalytic properties of the M/Cu bimetallic thin films for CO2RR. For selectivity, the M atoms introduced to Cu(100) surface vary the Faradaic efficiency for each product to decrease average number of electrons transferred to a CO2 molecule. For activity, the introduction of M atoms onto Cu(100) surface suppresses the production rates for both C1 and C2+ products although it increases or decreases the total current density as seen in cyclic voltammetry, depending on M. The aforementioned experimental facts suggest the role of M that the M atoms introduce onto Cu(100) surface seem to cause some bimetallic effects on the CO2RR selectivity of Cu as well as an inhibition effect on the CO2RR activity of Cu. Electron-transfer reaction kinetics are further studied via a combined experiment and theory approach to discuss the nature of active sites in M/Cu bimetallic systems and the role of M in determining product distribution, which will be explained in the conference.
Investigation of Graphene Supported Au-Cu Nanoparticles As Electrocatalyst for CO2 Electro-Reduction
Authors: Balčiūnaitė Aldona , Rutkauskas Andrius , Tamašauskaitė-Tamašiūnaitė Loreta , Norkus Eugenijus 
Published: February 2020

Carbon dioxide (CO2) is the most common greenhouse gas in our planet. Reduction of CO2 production and conversion of CO2 into useful materials at the same time is necessary. CO2 conversion using electro-catalysis can be controlled by electrode potentials and the reaction temperature. Also the electrochemical reaction systems are compact, modular and easy for scale-up applications. Cu-based composites with different compositions can seriously influence its electrocatalytic performance toward CO2 reduction reaction.
In the present study, a rapid microwave heating method was used to prepare the graphene or carbon supported Au-Cu nanoparticles as electrocatalysts for the electrochemical reduction of CO2. The morphology and composition of the fabricated catalysts were examined using Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). The activity of the fabricated catalysts for CO2 electro-reduction was examined using cyclic voltammetry and linear sweep voltammetry in acidic (pH=1.7), neutral (pH=6.3) and alkaline (pH=10.3) media.
It was found that the graphene or carbon supported Au-Cu catalysts show a similar electrocatalytic activity for the electro-reduction of CO2 in the acidic media, whereas the graphene supported Au-Cu catalyst shows a higher activity in the neutral and alkaline media as compared with that of carbon supported Au-Cu catalyst.
Development of an Electrochemical Sensor for the Detection of Dopamine Based on PEDOT and Silver Nanoparticles
Authors: Lucero Gisella Liliana , Gruia Violeta-Tincuta , Ispas Adriana , Bund Andreas 
Published: February 2020

Dopamine is an organic compound that plays a crucial role in many brain processes. Several neurological and neuropsychiatric disorders are associated to the deficiency of dopamine and for that reason the detection of this compound is a major concern. Poly(3,4-ethylenedioxythiophene) (PEDOT) is a conducting polymer whose properties depend on the method used for its deposition and of the counterions included in its structure during the deposition process. This polymer has been used with different dopants for the detection of many organic and inorganic compounds. Furthermore, nanostructures such as carbon nanotubes, metal oxides, reduced graphene oxide and metal particles have been used for the detection of dopamine [1,2].
In this work electrodeposition of PEDOT was carried out by scanning the working electrode (glassy carbon) potential between -0.3 and 1.1 V vs Ag/AgCl 3.5 M at 50 mV/s. After the electrodeposition, the films were reduced at -0.3 V for 10 minutes and then silver nanoparticles were deposited on the films at open circuit potential for 30 minutes. The morphology of the PEDOT/ClO4 films with and without SDS modified with silver particles was analyzed by SEM. The nanoparticles are seen as bright spots in the SEM images. In both films there are isolated and conglomerated nanoparticles. In the PEDOT/ClO4 films the nanoparticles are distributed mainly in the globules while in the PEDOT/ClO4/SDS films silver nanoparticles are also placed a greater depth in the porous structure. The size of the nanoparticles in the PEDOT/ClO4/SDS films is between 6 and 100 nm. The elemental composition of the modified electrodes was determined by EDX. The spectrums of PEDOT/ClO4 films with and without SDS modified with silver nanoparticles confirmed the presence of carbon, sulfur and oxygen, the constituents of PEDOT in the films. In addition, the spectrums also showed the peak for silver which proves that silver nanoparticles were incorporated into the PEDOT films.
The prepared structures differ from films prepared in previous reports and exhibit a different electrochemical behavior [3,4]. The analytical performance of PEDOT/ClO4/SDS modified with the nanoparticles for the detection of dopamine was evaluated by differential pulse voltammetry. The sensitivity of the sensor was 0.03 +/-0.01 µA µM-1.
[1] K. Liu, H. Pang, J. Zhang, H. Huang, Qing L. and Y. Chua. RSC Adv.4 (2014) 8415.
[2] C. L. Weaver H. Li, X. Luod and X. T. Cui. J. Mater. Chem. B. 2 (2014) 5209.
[3] V. Karabozhikova and V. Tsakova. Chem. Pap. 71 (2017) 339.
[4] E. Tolstopyatova, N. Pogulyaichenko, and V. Kondratiev. Russ J. Electrochem. 50 (2014) 510

Figure 1
Sensitive Determination of Mefenamic Acid in Biological Fluids and Pharmaceutical Formulations on Carbon Nanotubes Fabricated Sensor
Authors: Tarlekar Pravin , Chatterjee Sanghamitra 
Published: February 2020

Mefenamic acid (MFA) is a member of fenamate group of non- steroidal anti-inflammatory drug used in the therapy of pain phenomena and blockade of inflammatory areas; for the stimulation of the immune system in patients with arthritis and arthrosis. The degree of menstrual blood loss is reduced with the treatment of MFA and it is also used to treat autoimmune haemolytic anaemia. Measurement of plasma levels of MFA may provide valuable information for MFA treatment in premature infants with symptomatic patent ductus arteriosus and for preventing possible toxic effects. However, the excessive intake of MFA leads to diarrhoea, vomiting, lactic acidosis, hepatic necrosis, liver injury, morbidity and mortality in humans. Consequently, the development of an inexpensive, sensitive and accurate analytical method for determination of MFA is of considerable importance.
Non-steroidal anti-inflammatory drugs (NSAIDs) are among the most commonly prescribed agents worldwide due to their anti-inflammatory, antipyretic and analgesic properties and are usually used in the treatment of inflammatory and degenerative diseases of the articulations. In addition, epidemiological studies have shown that long-term use of NSAIDs reduces the risk of developing Alzheimer disease and delays its onset. This category of drugs alleviate pain by counteracting the cyclooxygenase (COX) enzyme. On its own, COX enzyme synthesizes prostaglandins, creating inflammation. In whole, the NSAIDs prevent the prostaglandins from ever being synthesized, which otherwise lead to an increase of vascular permeability, edema, hyperalgesia, pyrexia, and inflammation. These drugs have also shown to induce various forms of adverse drug reactions, including adverse gastrointestinal effects, renal dysfunction and nephrotoxicity, liver damage, adverse neurological effects, and rhabdomyolysis.
Herein, we report the selective and sensitive determination of mefenamic acid on single walled carbon nanotubes modified glassy carbon electrode (GCE) employing square wave voltammetry. The developed sensor exhibited amelioration in the peak current response with a negative shift in the peak potential in comparison to multi walled carbon nanotubes modified GCE and bare GCE. Voltammetric studies indicated the oxidation of MFA at the electrode surface through a one electron and one proton irreversible step and fundamentally controlled by adsorption. A good linear relationship has been found between the anodic peak current and mefenamic acid concentration in the range of 0.1 – 35 µM with limits of quantification and detection as 44.7 and 13.4 nM, respectively. The interfering effect of physiologically common interferents on the current response of mefenamic acid has been reported. Furthermore, the proposed method was successfully applied to the determination of mefenamic acid in pharmaceutical formulations and human plasma samples.
Early Diagnosis of Diabetes Using Stochastic Sensors
Authors: Stefan-van Staden Raluca-Ioana 
Published: February 2020

Diabetes is one of the most frequent diseases, affecting 1 in 12 persons worldwide according to International Diabetes Federation, therefore improved methods of monitoring and screening are needed.
Stochastic sensors represent a promising candidate in early diagnosis due to their capacity to perform qualitative and quantitative analysis of multiple biomarkers.
For the determination of C-peptide, insulin, proinsulin, leptin, adiponectin and CRP the immunoassay techniques are routinely used in clinical practice, requiring diferite detection kits, therefore one of the main advantage in using this method consists in determining in one run all the analytes.
In this paper, stochastic microsensors based on new carbon materials were proposed for the assay of diabetes related biomarkers like: proinsulin, insulin, C-peptide, leptin, adiponectin, Zn, pyruvic and lactic acids and CRP in biological fluids like urine and serum samples.
Visualization of Potential Distribution inside Crevice of Type 430 and 304 Stainless Steels
Authors: Takaya Natsumi , Muto Izumi , Sugawara Yu 
Published: February 2020

Stainless steels are widely used in industries because of their high anti-corrosive performance due to their passivation ability. However, crevice corrosion sometimes occurs in chloride environments. It is known that crevice corrosion is initiated when electrode potential inside crevice changes from the passive to active state. Therefore, the potential is the important factor to understand the mechanism of crevice corrosion. In this research, visualization of the potential inside the crevice for type 430 and 304 stainless steels was performed in 0.01 M NaCl at pH 3.0.
An indium-tin oxide (ITO) glass with a sensing layer was applied for visualizing the potential. In the sensing layer, a redox indicator was entrapped. Figure 1 shows the schematic illustration of apparatus for the calibration procedure for color change of the plate. The ITO glass with the sensing layer (sensing plate) was used as a working electrode. In an electrolyte, a mirror polished Pt plate was put below the sensing plate to reflect the image of the sensing plate, and the optical microscope images were taken through the sensing plate by a CCD camera system. Electrode potential of the sensing plate was changed from -0.52 to 1.08 V in 0.01 M NaCl (pH 3.0 adjusted with HCl). All potentials reported in this work refer to Ag/AgCl (3.33 M KCl).
Figure 2 shows the optical micrographs of the sensing plate placed above the Pt. It is clear that the color was changed from light green to dark blue with increasing electrode potential. The sensing plate was applied to crevice corrosion tests in 0.01 M NaCl (pH 3.0 adjusted with HCl). In the crevice corrosion tests, the sensing plate was used as a crevice former. The distributions of electrode potentials inside the crevice of the stainless steels were monitored from the color of the sensing plate.

Figure 1
New Electrolyte Composition for High-Voltage Lithium-Ion Cathodes – Enhancing the Cycling Stability in Half- and Full-Cells
Authors: Kazzazi Arefeh , Bresser Dominic , Kuenzel Matthias , Kim Guk-Tae , Passerini Stefano 
Published: February 2020

The steadily rising utilization of lithium-ion batteries for large-scale applications, in particular, electric vehicles requires the development of cell chemistries that offer increased energy and power densities.1,2 Essentially, there are two options to enhance the energy density: Increasing the capacity of the employed active materials and/or elevating the full-cell voltage by switching to high-voltage cathode materials. The latter, however, face the great challenge to identify a suitable electrolyte composition, as commonly used organic carbonate-based electrolyte are not sufficiently stable towards oxidation. To avoid the resulting detrimental side reactions, the use of electrolyte additives is easily implementable into common cell manufacturing technologies and, thus, very cost-efficient.3,4 For such reason, a plethora of electrolyte additives has been reported in recent years, but frequently these additives have been proven only to enhance the performance for selected cathode materials, while particularly the evaluation with graphite-based anodes has been commonly overlooked.
Herein, we report on a new electrolyte composition, incorporating functional electrolyte additives for high-voltage cathode materials like LiNi0.5Mn1.5O4 or 5V-olivines, which moreover reveal a beneficial impact also for graphite-based anodes and, consequently, also in lithium-ion full-cells. As a result, lithium-ion half- and full-cells with a cell voltage of >4.5 V show a greatly enhanced cycling stability, increased capacities, and improved efficiencies.

References

B. Scrosati, J. Hassoun, and Y.-K. Sun, Energy Environ. Sci., 4, 3287 (2011).

D. Bresser et al., J. Power Sources, accepted manuscript (2018).

S. S. Zhang, J. Power Sources, 162, 1379–1394 (2006).

J. Kalhoff, G. G. Eshetu, D. Bresser, and S. Passerini, ChemSusChem, 8, 2154–2175 (2015).
A Study on Cathode Interface of Li-La-Zr-O Solid-State Electrolyte Fabricated Via Rapid Sintering Process
Authors: Yang Hwichul , Lee HoJae , Kim Sunmin , Christy Maria , Kim Young-Beom 
Published: February 2020

For recent lithium-ion batteries (LIBs), there have been lots of researches about convert liquid-phase electrolyte to solid-state electrolyte (i. e. all-solid-state battery) to improve safety and stability. Solid-state electrolyte materials have to satisfy some criteria including high ionic conductivity at room-temperature, chemical stability against reducing environment, and mechanical strength. Many solid-materials for electrolyte have been researched, including perovskite, garnet, and sulfide-type of materials. Among them, garnet-type based lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12) has been received attention due to its high ionic conductivity (~10-4 S/cm at room temperature) and wide electrochemical stability window (~6 V versus Li/Li+). The main issue of LLZO is the high interfacial resistance with anode and cathode materials such as Li metal and LiCoO2. Many researchers have tried to understand the cause of this interfacial resistance for LLZO. K. Park et al. researched about the cathode/electrolyte (LLZO) interface and revealed co-diffusion and second-phase formation of LLZO at high-temperature [1]. M. Zarabian et al. reported that spin-coated LLZO on the LiCoO2 pellet fabricated at low-temperature (~400oC) and co-diffusion of La and Co at the interface by using X-ray photoelectron spectroscopy (XPS) [2]. They commonly suggested that elevated temperature make chemical interaction and this make high interfacial resistance.
In this study, we adopted novel sintering method, flash light annealing (FLA) process, to fabricate LLZO solid-electrolyte. This method is also called rapid, cool sintering because of its unique characteristics compared to conventional sintering methods [3]. FLA uses instantaneous high current to generate intensive pulsed light (IPL), and irradiate IPL toward the specimen to sinter the materials. Unlike the conventional sintering methods, this novel method has lots of advantages including availability of treatment at STP and fast sintering time (~ a few ms). Rapid sintering process gives no time for the diffusion at the interface, thus the interfacial resistance between cathode and LLZO solid-electrolyte must be reduced. We fabricated LLZO solid-electrolyte on the commercial LiCoO2 pellet by using solution-based spin-coating method and sintered the film by using FLA method. XPS and energy-dispersive X-ray spectroscopy (EDX) analysis were conducted to observe interface and diffusion of La and Co elements. Also, X-ray diffraction (XRD) method was used to investigate sintering ability of FLA through crystallinity development. The interfacial resistance between LiCoO2 and LLZO solid-electrolyte was analyzed by electrochemical impedance spectroscopy (EIS) through cross-plane set-up.
(Invited) Present Status and Future R&D Needs for Batteries for Vehicle and Grid Applications
Authors: Srinivasan Venkat 
Published: February 2020

Electrochemical energy storage (i.e., batteries) is an enabling technology that holds the key to transitioning from fossil fuels for our vehicle needs and managing the intermittency of renewables on the grid. Over the last 5 years, numerous electric vehicles have entered the market and storage technologies are being deployed on various grid applications. These changes are mainly driven by innovations in lithium-ion batteries, both in materials and in manufacturing, that have resulted in the cost of the technology decreasing at a steady pace. This cost reduction is expected to accelerate in the near future, by leveraging economies of scale (e.g., Tesla’s recently announced Gigafactory) and vertical integration. However, despite these exciting changes, more is needed to ensure widespread deployment of electrified vehicles and stationary storage for grid-connected applications. Further decreases in cost, increase in cycle/calendar life and energy density, and significant improvement in safety will remain challenges. Advances in battery technology, ranging from incremental improvements to Li-ion technologies, “beyond” Li-ion concepts, and lower-cost technologies for grid storage, including flow batteries, are needed to enable an electrified future.
This talk will summarize the present status of battery technology for vehicle and grid applications and provide a gap analysis between the present status and the requirements. The talk will also describe the efforts now underway to bridge the gap, both in development of new technologies and in manufacturing of these systems with an eye on reduction in cost. Using techno-economic modeling efforts at ANL and elsewhere, we will summarize the prospects of Li-ion, Li-metal (including Li-air and Li-S), Mg-ion based systems, and flow batteries compared to the requirements.