bluuebunny/crossref_metadata_2025_split huggingface dataset:
In Situ X-Ray Absorption Spectroscopy Investigation of Silver-Copper Nanoparticles for the Oxygen Reduction Reaction
Authors: Gibbons Brenna M. , Higgins Drew Christopher , Wette Melissa , Mehta Apurva , Davis Ryan C. , Clemens Bruce M. , Jaramillo Thomas F 
Published: February 2020

The electrochemical conversion between oxygen and water is a key process gating the wider deployment of a variety of renewable energy technologies. In particular, the slow kinetics and limited selection of suitable catalysts for the oxygen reduction reaction (ORR) are main impediments to the expansion of critical clean-energy technologies such as hydrogen fuel-cell vehicles or grid-scale energy storage. While Pt-based catalysts are the conventional choice for acidic electrolytes, favorable oxygen reduction kinetics and stability considerations that occur in alkaline electrolytes provide possibility for using non-platinum group metal catalysts, including silver. In particular, bimetallic or alloyed systems of silver and copper have been predicted by theory to be active for the ORR [1]. While these two metals have a large miscibility gap in the bulk, it has been shown that small nanoparticles can support intermixing of the silver and copper in a stable or metastable phase [2]. In addition, we have shown that co-sputtering silver and copper as both thin films and nanoparticles results in ORR catalytic activity that surpasses that of either metal on its own. In this work we investigate these bimetallic catalysts using in situ x-ray absorption spectroscopy (XAS) in order to help understand the activity enhancements seen when combining copper and silver for the ORR.
[1] K. Shin, D.H. Kim, and H.M. Lee. ChemSusChem (2013), 6: 1044-1049.
[2] P. Grammatikopoulos, J. Kioseoglou, A. Galea, J. Vernieres, M. Benelmekki, R.E. Diaz, and M. Sowwan. Nanoscale (2016), 8: 9780-9790.
(Invited) Investigating the Water-Stimulated Mg2+ Insertion Mechanism in an Electrodeposited MnO2 Cathode
Authors: Sahadeo Emily , Song Jaehee , Gaskell Karen J. , Rubloff Gary W , Lee Sang Bok 
Published: February 2020

Magnesium batteries are an important energy storage technology being investigated to improve upon, and move beyond, current lithium-ion (Li-ion) battery systems. Some advantages of magnesium-based batteries include magnesium’s abundance, increased volumetric capacity, and lower reactivity compared to Li. However, Mg batteries have many challenging problems hindering their implementation. One major issue is the slow intercalation kinetics of the Mg2+ ion in many metal oxide cathodes conventionally used in Li-ion batteries. A potential solution that has been demonstrated is adding water molecules into organic electrolyte; this method has shown increased Mg insertion and performance of cathode materials such as vanadium oxide (V2O5) and manganese oxide (MnO2). MnO2 is the cathode of interest for this work, and an in-depth investigation is necessary to fully understand the role of the water molecules in the Mg intercalation into this material.
In this work, the Mg insertion mechanism is being investigated in a system of water-in-organic electrolyte, with electrolytes containing an H2O to Mg ratio of 6:1. The cathode is an amorphous, electrodeposited MnO2 thin film. Thin film MnO2 electrodes were prepared so that they could be electrochemically cycled in magnesium perchlorate/propylene carbonate electrolyte, and subsequently examined via ex-situ XPS at different stages of charge and discharge to monitor the surface chemical speciation and any changes. Herein, we will elucidate upon the XPS results to help explain the mechanism of Mg insertion in this mixed electrolyte. Results demonstrate that an Mg(OH)2 layer forms upon discharge, and this hydroxide layer is reversibly formed and removed during charge and discharge. Additionally, after first cycling electrodes in wet electrolyte and transferring them to dry organic electrolyte and cycling further, the Mg(OH)2 layer is still observed although in a diminished capacity.
We propose that in the mixed water-in-electrolyte system, there is a combined insertion/conversion reaction mechanism whereby an Mg(OH)2 layer is formed on the surface. We therefore believe water inserted into the MnO2 structure upon cycling in wet electrolyte may be responsible for the Mg(OH)2 formation in dry electrolyte and continual increased Mg-ion capacity. A more complete understanding of the mechanism for this phenomenon may help in further developing strategies to improve metal oxide cathode performance. For instance, one possibility may be trying to reproduce the positive effect of water with another additive that does not react with the Mg anode as water does.
Preparation and Characterization of Electrochemical Tyrosinase Biosensor
Authors: Polatoglu Ilker 
Published: February 2020

Tyrosinase enzyme is a binuclear copper cluster containing monooxygenase contains a dicopper core in the active site [1]. This enzyme catalyzes the o-hydroxylation of monophenols and subsequent oxidation of the formed o-diphenols into the o-quinones. Depending on the electrochemical reduction of o-quinone, amperometric detection of phenol which is a high toxic compound can be achieved. For this aim spectrophotometric and chromatographic methods have been commonly used. Due to their lots of disadvantages, electrochemical enzyme sensors become promising alternative [2]. The performance of enzyme sensors strongly depends on the immobilization of the enzyme to the appropriate support. Many significant biological and chemical properties of chitosan attract attention as a potential support for enzyme immobilization [3]
In current study, tyrosinase enzyme was immobilized on chitosan support enhanced by magnetite nanoparticles. Electrochemical biosensor was constructed by coating this bionanocomposite film on 5mm diameter of working electrode. All electrochemical measurements were performed with a model PGSTAT 128N (AUTOLAB Instruments) having three electrode system (working electrode: tyrosinase–magnetite-chitosan modified glassy carbon, reference electrode: Ag/AgCl, auxiliary electrode: platinum wire). The interaction between the sensor component and their structure were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. Electrochemical characterizations were also performed by cyclic voltammetry (CV) and impedance spectroscopy (EIS). The performance of electrochemical tyrosinase biosensor was tested by amperometric method in magnetically stirred PBS, followed by the addition of catechol solution as a phenolic compound.
The binding of tyrosinase enzyme to the bionanocomposite support was confirmed by FTIR and SEM analysis. According to the CV measurements, the reduction peak was observed attributed to the direct reduction of quinone on the electrode surface. EIS results showed decrease in mass transfer resistance indicate conducting properties of magnetite nanoparticles. Electrochemical sensing characteristics and analytical performance of developed sensor was also evaluated by amperometric detection of catechol. The designed sensor depicted wide linear range of catechol concentration with high correlation coefficient, high sensitivity, low detection limit and Kmvalue.
Acknowledgements
This study was supported financially by the Scientific and Technological Research Council of Turkey (TUBITAK Grant Number 114Z417).

References
[1] Abdullah J, Ahmad M, Karuppiah N, Henga LY, Sidek H, Sensors and Actuators B, 114 (2006) 604-609.
[2] Li GY, Jiang Y, Huang K, Ding P, Chen J, Journal of Alloys and Compounds, 466 (2008) 451–456
[3] Krajewska B, Enzyme and Microbial Technology, 35 (2004) 126–139
Magnesium-Ion Batteries Based on Tin-Based Anode Material
Authors: Nguyen Dan Thien , Song Seung-Wan 
Published: February 2020

Rechargeable magnesium batteries have received a considerable attention as one of the beyond-lithium batteries for next-generation energy storage systems. Magnesium is earth abundant and low cost compared to lithium, and has higher theoretical volumetric capacity (3833 mAhcm-3) than lithium. The use of magnesium metal anode is often limited due to the irreversible formation of surface blocking layer in conventional electrolytes and the limited choice of counterpart cathode material in Grignard reagent-based electrolytes. Recently, insertion-type materials such as Bi, Sn, Sb, etc., which is based on the alloy reaction with magnesium, have been proposed as a new class of alternative anode materials to magnesium metal. Obtaining a good charge-discharge cycling performance of those new materials is however a challenge. We have been pursuing the development and application of tin-based anode materials, which enables magnesium-ion batteries. Herein, we report our recent research results of the electrochemical performance and interfacial phenomena of tin-based anode materials.
This work was supported by National Research Foundation of Korea (2015062107).
On the Stability of Interphases in Na Batteries
Authors: Ponrouch Alexandre , Dugas Romain , Iermakova Daria , Palacin M Rosa 
Published: February 2020

Lithium metal anodes are widely used as counter (or also reference) electrodes in the so termed half cell tests, used mostly at laboratory scale within the battery research community. These are intended to assess the electrochemical performance of a given compound as either positive or negative electrode material for Lithium ion batteries in a simple way, avoiding the assembly of full cells in which electrode balancing can severely affect performance.
The reliability of extrapolating such half cell testing results to potential performance in full cells is linked to the stability of the Solid Electrolyte Interphase (SEI) typically formed on the surface of lithium metal anodes as a result of electrolyte degradation reactions. Reliability and representativity of analogous half test cells in Sodium ion battery research has been generally taken for granted.
In this context, the aim of our work was to perform a comparative study of the composition, morphology and stability of the SEI formed on lithium and sodium with state-of-the art electrolytes. The impact of the use of Li or Na counterelectrodes in half cell configuration when testing hard carbon electrodes was also investigated. Our results clearly point at the existence of significant differences which cast some doubts on the representativity of half-cell tests and call to exercise care in the extrapolation of their results.1,2

Figure 1. Charge/discharge curves of symmetric Li/Li (red curve) and Na/Na (blue curve) cells cycled at 0.05 mA/cm2 (25˚C) and using 1 M LiPF6 or NaPF6 in EC0.5DMC0.5. Poorer cyclability was observed for Na cells when compared with Li cells.
References:
1. D. Iermakova, R. Dugas, M.R. Palacín, A. Ponrouch, J. Electrochem. Soc., 162 (2015) A7060.
2. R. Dugas, A. Ponrouch, G. Gachot, R. David, M.R. Palacín, J.M. Tarascon, J. Electrochem. Soc., 163 (2016) A1.

Figure 1
Computational and Spectroscopic Analysis of Ion Interactions in Sodium and Lithium Ion Battery Electrolytes
Authors: Cresce Arthur v. , Borodin Oleg , Greenbaum Steven , Peng Jing , Gobet Mallory , Rogers Reginald , Xu Kang 
Published: February 2020

Rising interests in sodium ion batteries as low-cost alternatives to lithium ion batteries necessitates a closer look at the interactions between the sodium ion and its anion in electrolyte solution. As demonstrated in lithium ion batteries, solvent and anion species involved in solvation of the lithium ion contribute to the nucleation and growth of the solid electrolyte interphase of the anode. The same is true of sodium ion batteries, which parallel lithium ion batteries in their use of carbonate-based organic solvents and the hexafluorophosphate (PF6
-) anion. Infrared spectroscopy (FTIR) was used to probe the interaction between PF6
- and sodium in various carbonate-based solvent, and these measurements were interpreted using predictions made by density functional theory (DFT) calculations on the model LiPF6 and NaPF6-based solvates. In addition, molecular dynamics (MD) simulations were performed on the EC:DMC/LiPF6 and EC:DMC/NaPF6 electrolytes. A revised many-body polarizable APPLE&P force field was used in MD simulations. Solvate structures extracted from MD simulations were found in good agreement with interpretations of FTIR spectra. Specifically, initial MD results supported our previous finding indicating that the Li+ and Na+ solvation numbers from Raman measurements are found are similar in linear carbonates. Moreover, MD simulations predicted that the PF6
- anion coordination to Li+ and Na+ are quite different. Mono-dentate LiPF6 binding prevailing in LiPF6-DMC, and a combination of bi- and tri-dentate binding dominating in NaPF6-DMC in agreement with the free energies of solvates estimated from DFT cluster – continuum calculations. MD simulations also predicted solvent, anion, Li and Na self-diffusion coefficients in excellent agreement with pfg-NMR measurements.
Predicting Lithium Polysulfide Solubility and Reaction Pathway Using a Unique Donicity Scale for Li-S Electrolytes
Authors: Watkins Tylan S , Zavadil Kevin R 
Published: February 2020

Sparingly Solvating Electrolytes for Li-S Cells:

Use of electrolytes with low lithium polysulfide (Li2Sn) solubility limits has attracted considerable interest in recent literature.1 This “sparingly solvating” strategy has been adopted by some as a means for significantly reducing redox shuttling of Li2Sn between the cathode and anode. Interestingly, some sparingly solvating electrolyte compositions, employing significantly high concentrations of LiTFSI, have not only shown promising cycling performance, but have also shown a unique discharge voltage profile—lacking the typically observed two plateau response produced by sequential soluble long chain Li2Sn and short chain Li2Sn formation. This unique voltage profile is thought to be the result of significantly suppressed concentrations of longer chain Li2Sn (n > 4) leading to initial sulfur reduction through a solid state pathway followed by Li2Snreduction mediated by a low solubility intermediate.

Predicting Li2Sn Solubility and Reaction Pathway:

What remains to be elucidated is a more quantitative assessment for the solubility regimes in which the alternative sulfur reduction pathway occurs. Furthermore, a deeper understanding of the electrolyte characteristics that dictate Li2Sn solubility is lacking. In this talk, a unique 23Na NMR-derived donor number (DN) scale is presented, similar to that described by Schmeisser et al.2 Evaluation of donicity in this manner allows for a direct comparison between electrolytes utilizing different solvating species; see Figure 1 for THF and acetonitrile (AcN)-based electrolytes. It will be demonstrated that the 23Na-DN assignments are predictive indicators for solubility of Li2Sn (Figure 2). Finally, it will be shown that solubility can be used to predict the thermodynamic redox potentials for Li-S cells as a function of discharge capacity. Figure 3 shows representative galvanostatic intermittent titration technique (GITT) experiments performed on two different AcNxLiTFSI electrolytes, with drastically different Li2Sn solubility limits; the black traces follow the open circuit potentials at given capacities. Clearly, AcN6LiTFSI shows a classic two plateau response, in which the second plateau (later discharge) is at a lower potential than the early discharge plateau—consistent with higher Li2Sn solubility. Alternatively, AcN2LiTFSI shows a mid-discharge plateau higher than that of the potential at early discharge—consistent with a mechanism driven by a lack of solution phase Li2Sn (n > 4) species. Further details describing how these voltage profiles change as a function of Li2Snsolubility will be provided.

References:

Cheng, L.; Curtiss, L. A.; Zavadil, K. R.; Gewirth, A. A.; Shao, Y.; Gallagher, K. G. ACS Energy Lett. 2016, 1, 503−509.

Schmeisser, M.; Illner, P.; Puchta, R.; Zahl, A.; Eldik, R. Chem. Eur. J. 2012, 18, 10969–10982.­­

Figure 1
A Sodium Hybrid Capacitor with High Energy Retention and Ultra-High Stability
Authors: Thangavel Ranjith , Kim So Young , Gong Ming Kyung , Park Joo Yeon , Ramasamy Hari Vignesh , Lee Yun Sung 
Published: February 2020

Sodium ion batteries have been recently proved to be a cost-effective and promising alternative to lithium-ion batteries for next generation high-energy applications. However, the sluggish intercalation kinetics in batteries greatly forbid the efficient high power operation.[1] Recently, sodium hybrid capacitors (NHCs) emerged as a promising energy storage system to retain high specific energy at high power conditions. Benefiting from the simultaneous sodium intercalation/deintercalation in battery type electrode and anionic adsorption/desorption in capacitor type electrode, a fast kinetics in NHCs have been achieved.
However, the poor sodium ion storage in battery electrode along with limited anionic adsorption in commercial electrode diminish the output performance of NHCs. The research on NHCs is still in a nascent stage and requires deep investigation to improve energy retention and cycle stability at high power. The kinetics in both battery and capacitor type electrodes must be synergistically improved to achieve a high energy.[2] In this work, we developed a high performing NHC with metal oxide nanoparticles embedded in graphene network as a battery electrode along with a highly mesoporous carbon derived from bio-mass precursor as a capacitor electrode. The highly favorable architecture in both the electrodes showed an enhanced capability towards ion storage (Shown in Ragone plot). A high energy retention at high power condition along with ultra-high stability have been achieved. The detailed results will be presented and discussed in detail.

References

[1] J. R. Miller, P. Simon, Science
2008, 321, 651.
[2] R. Thangavel, B. Moorthy, D. K. Kim, Y.-S. Lee, Adv. Energy Mater.
2017, 1602654.

Figure 1
Synthesis and Characterization of V2-X
Mo
x
O5 Cathode Materials for Calcium Ion Batteries
Authors: Sakurai Yoji , Minami Ryoji , Murata Yoshiaki , Takada Syoki , Tojo Tomohiro , Inada Ryoji 
Published: February 2020

Recently, a great deal of attention has been paid to multivalent ion batteries as post lithium ion batteries (LIBs) [1]. Among them, calcium ion batteries (CIBs) could exhibit a high cell voltage and energy density due to the low standard electrode potential of Ca/Ca2+, -2.87 V vs. NHE, which is comparable to that of Li/Li+ (-3.05V vs. NHE). In addition, CIBs have attractive advantages such as the higher safety and lower cost compared with LIBs. However, there are only a few reports in which electrodes for CIBs show a reversible calcium ion insertion/extraction. Almost a decade ago, we found that some vanadium oxides, e.g. crystalline V2O5 with layer structure, undergo reversible reaction with Ca2+[2,3].
However, a V2O5 cathode exhibits the large overvoltage as well as the poor rate performances due to its low electronic conductivity. In this study, we studied the effect of substituting Mo6+ for a part of V5+ in V2O5 in order to improve the electronic conductivity of V2O5. The carrier electrons are expected to be generated by the substitution of Mo in terms of the so-called valence control expressed as V5+/V4+. We synthesized a series of Mo-substituted V2O5, i.e. V2-x
Mo
x
O5 (x=0.02, 0.06, 0.1), by solid state reaction, and evaluated their electrochemical properties in comparison with a parent V2O5.
XRD patterns of the synthesized V2-x
Mo
x
O5 (x=0.02, 0.06, 0.1) powder all exhibited main diffraction peaks similar to those of V2O5 without impurity phases, indicating the solid solution formation. In addition, XPS measurements of V2p and Mo3d orbital showed main peaks attributed to V4+ and Mo6+ by Mo substitution in V2O5. Therefore, the V sites in V2O5 were suggested to be partially substituted to Mo. Galvanostatic cycling in LIBs revealed that a V1.94Mo0.06O5 electrode showed the lowest overvoltage than that of other compositions. Therefore, we focused on V1.94Mo0.06O5 in order to evaluate electrochemical characteristics for CIBs. The V1.94Mo0.06O5 cathode evaluated in CIBs showed reversible discharge and charge profiles with less overvoltage as well as the improvement in cycle performance compared to V2O5. XRD and EDX analyses also supported the reversible insertion/extraction reaction of V1.94Mo0.06O5 with Ca2+ ions. Therefore, it is suggested that V1.94Mo0.06O5is feasible as one of cathode materials for CIBs.
References
[1] J. Muldoon, C.B. Bucur and T. Gregory, Chem. Rev., 114 (2014) 11683.
[2] M. Hayashi, H. Arai, H. Ohtsuka and Y. Sakurai, J. Power Sources, 119-121 (2003) 617.
[3] M. Hayashi, H. Arai, H. Ohtsuka and Y. Sakurai, Electrochem. Solid-State Lett., 7 (2004) A119.
Electrochemical and Chemical Stability of Solid Electrolyte–Electrode Interfaces: A First Principles Computation Study
Authors: Zhu Yizhou , He Xingfeng , Mo Yifei 
Published: February 2020

All-solid-state Li-ion battery based on solid electrolyte materials is a promising next-generation energy storage technology. It can provide intrinsic safety, enable high-voltage electrode materials, and boost the achievable energy density. Currently, the key performance limiting factor of all-solid-state Li-ion battery is the high interfacial resistance and interfacial degradation at the solid electrolyte-electrode interfaces.
In this presentation, I will show how we use first principles computation to provide unique insights and fundamental mechanisms at these buried interfaces, which are difficult to access in experiments. We systematically investigated and compared the electrochemical stability and chemical stability of the solid electrolyte-electrode interfaces, and studied how these interfaces affect the battery performance, including interfacial resistance, long-term stability and cyclability.
Our computation results suggest the critical role of decomposition interphase layers at electrolyte-electrode interface and the significant effects of these interphase layers on the electrochemical performance of the all-solid-state Li-ion batteries. Different types of interfaces between solid electrolyte and electrode materials may have different problems at the interfaces, which require different interfacial engineering strategies to resolve. The mechanisms of artificial layers to improve the interfacial properties are also revealed by our computation. This computational study provides novel insights and general guidance for interfacial engineering in all-solid-state Li-ion batteries.
(Invited) Technology’s Role in Sustainable Energy
Authors: Williams Ellen D. 
Published: February 2020

Extracting useful heat and work from energy sources is essential to human civilization, and the energy infrastructure that has developed to meet the world’s needs is immense, complex and weighted with legacy technology. Today issues of energy equity, environment, climate change and climate adaptation are transforming the context in which the energy system is evolving. Linkages to world-wide water, land and mineral use must be included in developing world’s future energy systems
Fortunately, the U.S. infrastructure of research and development has created a wealth of tools and approaches that allow new progress in providing energy efficiently, cleanly and sustainably.
The connectivity of energy with other resources will be reviewed, and examples of high-potential energy innovation will be presented, including highlights from the goal-oriented programs of the Advanced Research Projects Agency – Energy.