bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Impedance Analyzer: An Open-Source, Web-Based Tool for Sophisticated Interrogation of Experimental EIS Spectra
Authors: Murbach Matthew D. , Hu Victor Waiman , Schwartz Daniel T. 
Published: February 2020

Electrochemical impedance spectroscopy (EIS) is a powerful technique for partitioning a system’s performance into contributions from individual physicochemical processes via their characteristic frequencies.1 Typically, analysis of experimental EIS spectra aims to extract meaningful information by fitting an equivalent circuit analog composed of ideal circuit elements representing different physicochemical phenomena within the cell. While fitting an equivalent circuit to experimental data is easily accomplished using nonlinear least squares regression, the lumped nature and lack of direct physical interpretation of the resulting parameters can limit the information content of the analysis.2

An alternative approach for extracting meaningful parameters from the data is to directly fit physics-based mathematical models of the electrochemical systems. In fact, many decades of electrochemical modeling research have laid the groundwork for the physics-based modeling of impedance in a wide variety of fields including corrosion,3 hydrodynamic systems,4
fuel cells,5
and lithium ion batteries.6However, despite the important role and wide acceptance of these physics-based models, their impact in experimental impedance analysis has been limited by their complexity – these models often contain many coupled partial differential equations representing the different physicochemical processes.
Here we present an open-source, web-based tool for the in-depth analysis of experimental EIS spectra. We show that building a large database of simulated spectra across a wide range of parameters enables deeper insight into the electrochemical system under study. As a demonstration, we present an analysis of experimental lithium ion battery data using the widely utilized pseudo 2-dimensional (P2D) battery model.

References:

1. M. E. Orazem and B. Tribollet, Electrochemical impedance spectroscopy, p. 523, Wiley, Hoboken, N.J, (2008).
2. S. Fletcher, J. Electrochem. Soc., 141, 1823–1826 (1994).
3. D. D. Macdonald, S. Real, S. I. Smedley, and M. Urquidi‐Macdonald, J. Electrochem. Soc., 135, 2410–2414 (1988).
4. D. T. Schwartz, P. Stroeve, and B. G. Higgins, J. Electrochem. Soc., 136, 1755–1764 (1989).
5. J. R. Wilson, D. T. Schwartz, and S. B. Adler, Electrochimica Acta, 51, 1389–1402 (2006).
6. M. Doyle, J. P. Meyers, and J. Newman, J. Electrochem. Soc., 147, 99–110 (2000).

Figure 1
Use of Kissa Software for Accurate Simulation of Electrochemical Problems of Any Compexity
Authors: Svir Irina , Klymenko Oleksiy , Oleinick Alexander , Amatore Christian Andre 
Published: February 2020

KISSA-software (for 1D and 2D electrode geometry) developed in our group, provides a general framework to treat electrochemical problems (by providing mechanism, rate constant, diffusion coefficients etc.) of any complexity in a user-friendly environment and returns the simulations results without any intervention into numerical part from the user side [1]. The accuracy of the numerical solution is guaranteed in KISSA by employment of a non-uniform and adaptive grid. The latter is constructed on the basis of a kinetic criterion (rather than on a gradient-based one as in other programs) and provides a high dynamic resolution at the acute reaction fronts which are automatically detected and followed by the program [2-5]. The efficiency of this strategy was proved by addressing such sophisticated problems as i) simulation of reaction mechanisms leading to the emission of electrochemiluminescence (ECL) and ii) including the reactive dynamic adsorption.
In this context considered ECL systems [6,7] are representative example of systems possessing extremely sharp reaction fronts since some reaction constants are close to the diffusion limit (either cation/anion radicals annihilation reactions or luminophor/co-reactant reaction). More precisely, for the ECL co-reactant system, such as alkyl amines / transition metal(II) complexes, it was shown via simulations with KISSA that changes in ECL intensities emitted by these systems are much more dependent on the relative diffusivities of the two co-reactants than on the range of thermodynamic and kinetic rate constants that are possible to explore and vary.
Second example is the competitive reactive adsorption is also involved as an important class of problems covered by KISSA [8-10].
A couple examples of real data imported to KISSA for comparison to simulations for elucidation of mechanism and determination of the parameters are presented. References:

KISSA-group: http://kissagroup.com/

C. Amatore, O. Klymenko, I. Svir, Electrochem. Commun., 12, 1170-1173 (2010).

C. Amatore, O. Klymenko, I. Svir, Electrochem. Commun., 12, 1165-1169 (2010).

O. V. Klymenko, I. Svir, A. I. Oleinick, C. Amatore, ChemPhysChem, 13, 845-859 (2012).

C. Amatore, O. Klymenko, I. Svir, Anal. Chem., 84, 2792-2798 (2012).

O.V. Klymenko, I. Svir, C. Amatore, ChemPhysChem, 14, 2237-2250 (2013).

I. Svir, A. Oleinick, O.V. Klymenko, C. Amatore, ChemElectroChem, 2, 811-818 (2015).

O. V. Klymenko, I. Svir, C. Amatore, J. Electroanal. Chem., 688, 320-327 (2013).

O.V. Klymenko, O. Buriez, E. Labbé, D. Zhan, S. Rondinini, Z. Tian, I. Svir, C. Amatore, ChemElectroChem, 1, 227-240 (2014).

O. Klymenko, I. Svir, C. Amatore, Mol. Phys., 112, 1273-1283 (2014).
(Invited) Visualizing Electrochemical Reactions at the Nanoscale By in-Situ TEM
Authors: Xin Huolin L. , Ge Mingyuan , Chu Yong S 
Published: February 2020

Over the past five years, we have witnessed a rapid growth in liquid and gas flow holders for TEM and X-ray microscopes. These holders have enabled direct imaging of material transformations in liquid and gaseous environments with submicron-scale to atomic-scale spatial resolution. In particular, research regarding electrode materials in lithium ion batteries and nanocatalysts in heterogeneous catalysis has greatly benefited from the emergence of these capabilities. Despite their initial success in in-situ battery studies, similar class of problems in electrocatalysis has been rarely addressed using existing liquid electrochemical holders. In this talk, I will showcase the capability of direct nanoscale visualization of electrochemical formation and degradation of electrocatalysts utilizing an operando TEM liquid holder and I will also discuss existing challenges that the in-situ EM field need to address.
Acknowledgement
The research used resources of the National Synchrotron Light Source II and the Center for Functional Nanomaterials, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. The electron microscopy experiment was performed at the Center for Functional Nanomaterials. This research is also partially supported by Laboratory Directed Research and Development (LDRD15-037) program at the Brookhaven National Laboratory.
Nanoscale Electrochemistry Via Lithium Focused Ion Beam
Authors: McGehee William R. , Strelcov Evgheni , Gardner Jamie , Takeuchi Saya , Kirillov Oleg A. , Oleshko Vladimir P. , Gundlach David J. , Soles Christopher L. , Zhitenev Nikolai , McClelland Jabez J. 
Published: February 2020

The increasing demand for smaller, lighter, cheaper, and more stable power sources for portable electronics, vehicles and aircrafts spurs intensive research of the lithium ion batteries. Rational battery engineering, including design of smart electrode materials, is impossible without in-depth understanding of the chemical and physical processes in galvanic cells at the microscopic, nanoscopic, and eventually, molecular levels. Reaction mechanisms, cathode expansion, formation of cracks and SEI layer, electrolyte decomposition etc., are being extensively studied with a variety of ex and in situ microscopic, spectroscopic and electrochemical techniques. However, a significant drawback of the existing methodologies is their inability to deliver Li+ ions and control their concentration at the nanoscale level. In addition, the classic electrochemical techniques imply existence of liquid-solid interfaces and inevitable formation of SEI layer. This is a significant impediment for studying lithium diffusion and associated morphological changes in cathode materials.
We report progress in developing Li+ focused ion beams (FIB) as a novel probe for exploring nanoscale electrochemistry in battery-relevant materials. This work focuses on implantation of lithium ions in crystalline silicon to benchmark this technique and builds on recent, qualitative studies of FIB implantation in Sn microspheres [Takeuchi et al. JES 163 (6), A1010-A1012]. FIB implantation opens the possibility of precise spatial control of nanoscale lithium concentration though variation of the beam positioning and current. Experiments are performed in vacuo without the presence of electrolytes or associated solid-electrolyte interface. The Li+ ion beam operates with energies ranging from 0.5 to 5 keV, currents up to 15 pA, and minimum spot size of 27 nm using a magneto-optical trap ion source (MOTIS).
WRM acknowledges support from the National Research Council Research Associateship Program. ES and JG acknowledge support under the Cooperative Research Agreement between the University of Maryland and the National Institute of Standards and Technology Center for Nanoscale Science and Technology, Award 70NANB14H209, through the University of Maryland.
An Au-[Fe-S]-NAD-Glucose Dehydrogenase Bioanode for Glucose Detection
Authors: Mahadevan Aishwarya , Fernando Sandun 
Published: February 2020

Immobilization of NAD-dependent redox enzymes on electrode surfaces has been widely reported for the construction of enzymatic biosensors for detection of various biomolecules in different industries. Molecular wiring of such redox enzymes facilitate an efficient electron transfer by connecting redox center of the enzyme with the electrode surface. Iron-sulfur complexes are known for being the firstlink between protein and the mediating molecules in the mitochondrial electron transport chain to abstract electrons from NAD+. The application of iron-sulfur molecules as molecular wires to mediate electron transport between NAD-dependent glucose dehydrogenase (NAD-GDH) and gold electrode surface (i.e. a glucose bioanode) was studied. Methodology for fabrication and characterization of iron-sulfur based glucose biosensor at different construction stages were described. The biosensor performance characteritics of the novel Fe-S based glucose biosensor was investigated using amperometric analyses in the presence of glucose.
Stress Detection Using Polymer Optical Fiber with FRET Pair Dyes
Authors: Furukawa Rei , Kamimura So 
Published: February 2020

Noble fiber-optic strain sensor using dye-doped polymer optical fiber (POF) was proposed, and its ability to sense stress (strain) by simple viewing of the large-core cross section was proposed. Conventional well-known fiber-optic strain sensors such as BOTDR or FBG types require spectral analysis to determine the strain value. Our sensor does not require expensive equipments such as spectral analyzer or well-tuned light source that are required in conventional fiber-optic strain sensors.
A pair of luminescent organic dyes, Coumarin 540A and Rhodamine 6G, that functions as donor and acceptor of excitation energy were doped in core and cladding of the fiber, respectively. By taking this structure, stress applied to the fiber could be detected as an increase in cladding intensity. This happens because emission of core dye leaks to the cladding due to the deformation, and it excites the cladding dye.
Using the fabricated POF, change in near field pattern upon different fiber bending diameter was detected. Lasers with three different wavelengths were used; namely, 406 nm, 532 nm, and 635 nm. 406 nm is the optimum wavelength for exciting the Coumarin 540A of the core efficiently. 532 nm excites Rhodamin 6G well, but does not excite Coumarin 540A well. 635 nm excites neither dyes. Pigtail end was coupled to the test fiber with direct contact to the core center of the test fiber in which no cladding excitation was expected. Fibers were stressed in various magnitudes by bending them in different loop diameters, namely, 1.5 cm, 3 cm, and 6 cm. Single loop was created in the middle point of the whole length. Relaxed condition, which the fiber was naturally straightened with no loop, was also investigated. Output beam from the test fiber was analyzed using Near Field Pattern measuring system (Hamamatsu C9664-01G02).
In addition, dye-doped POF with lower numerical aperture had shown enhancement in sensitivity. Therefore, it was suggested that sensitivity of the sensor is controllable by further optimization of the waveguide parameters. Therefore, the proposed results suggests a potential for an enhanced fiber-optic stress detection with simpler and inexpensive accessory components.
A Comparison of Thiospinel Mg Battery Cathode Materials: MgxTi2S4 and MgxZr2S4
Authors: Bonnick Patrick , Sun Xiaoqi , Blanc Lauren , Nazar Linda F 
Published: February 2020

The search for batteries with higher volumetric energy densities than conventional Li-ion batteries has led to the pursuit of several new technologies including rechargeable Mg batteries. Mg metal is attractive as a negative electrode material because it has a higher volumetric capacity density (3833 mAh/mL) than Li metal (2062 mAh/mL), is the 8th most abundant element in the earth’s crust, is safe to handle in ambient atmosphere, and can be electrodeposited (charged) without the formation of dendrites.1 The seminal work by Aurbach et al. in 20002 established an electrolyte and a positive electrode material, the Chevrel phase (Mo6S8), that was paired with Mg metal to form the first rechargeable Mg battery.
Mg2+ intercalation in host materials is more difficult than that of Li+ or Na+, displaying lower ion mobility in solid oxide hosts,3 a tendency toward conversion reactions,4 and a possibly higher desolvation energy penalty.5 In fact, the second material to reversibly intercalate Mg2+, without debilitating decomposition over more than 100 cycles, was only demonstrated last year: the thiospinel Ti2S4.6 Unfortunately, our attempts to insert (or remove) Mg2+ into other 1st row transition metal thiospinels were unsuccessful; however, Mg2+ can be reversibly intercalated from thiospinel Zr2S4, a 2nd row transition metal.
Figure 1 shows the 1st discharge and charge of two coin cells using Mg foil anodes, Mg(CB11H12)2 in tetraglyme electrolyte and either a MgxTi2S4 or MgxZr2S4 electrode. We will present a comparison of the Mg intercalation into the Zr2S4 and Ti2S4 thiospinels, including Mg site occupancy, cell parameter variation, and Mg diffusion coefficients. In doing so, we will explore the crucial parameters that allow facile Mg2+ diffusion for consideration when designing new Mg2+ intercalation materials.
References

J. Muldoon, C. B. Bucur, and T. Gregory. Chem. Rev.
114, 11683-11720 (2014).

D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, R. Turgeman, Y. Cohen, M. Moshkovich and E. Levi. Nature
407, 724-727 (2000).

E. Levi, Y. Gofer, and D. Aurbach. Chem. Mater.
22, 860-868 (2010).

P. Canepa, G. Sai Gautam, D.C. Hannah, R. Malik, M. Liu, K.G. Gallagher, K.A. Persson and G. Ceder. Chem. Rev.
117, 4287-4341 (2017).

L. F. Wan, B. R. Perdue, C. A. Apblett and D. Prendergast. Chem. Mater.
27, 5932-5940 (2015).

X. Sun, P. Bonnick, V. Duffort, M. Liu, Z. Rong, K.A. Persson, G. Ceder and L. F. Nazar. Energy Environ. Sci.
1, 297-301 (2016).

Figure 1
Designing New Magnesium-Based Cathode Materials
Authors: Vaughey John T. , Key Baris , Proffit Danielle L. , Sa Niya , Ingram Brian J. , Lipson Albert L. , Poeppelmeier Kenneth , Incorvati Jared T 
Published: February 2020

Lithium-ion batteries have been a mainstay of the consumer electronics industries for nearly 25 years. Unlike many older energy storage systems, lithium-ion does not describe a specific chemistry but a family of chemistries and a mechanism of operation. As a result numerous types of materials are under the umbrella of lithium-ion batteries that can be modified and developed to meet a variety of end-user goals. Looking beyond-lithium ion, the landscape is less understood and explored. One of our research efforts is to look at non-lithium cation based energy storage chemistries, including the MgxV2O5 and MgxV2O5*H2O systems. This talk will focus on recent developments from our lab in Mg-ion and Ca-ion chemistries with highlighting new types of cathodes, electrolytes, and anode materials1-5

References
(1) Lipson, A.L; Han, S.-D; Kim, S. Pan, BF; Sa, N.; Liao; C, Fister, TT; Burrell, AK; Vaughey, JT; Ingram, BJ J. Power Sources
325 646-652 (2016).
(2) Sa, N; Wang, H; Proffit, DL; Lipson, AL; Key, B; Liu, M; Feng, ZX; Fister, TT; Ren, Y; Sun, CJ; Vaughey, JT; Fenter, PA; Persson, KA; Burrell, AK J. Power Sources
323 44-50 (2016).
(3) Sa, N; Kinnibrugh, TL; Wang, H; Gautam, GS; Chapman, KW; Vaughey, JT; Key, B; Fister, TT; Freeland, JW; Proffit, DL; Chupas, PJ; Ceder, G; Bareno, JG; Bloom, ID; Burrell, AK Chemistry of Materials, 28(9) 2962-2969 (2016).
(4) Lipson, AL; Han, SD; Pan, B; See, KA; Gewirth, AA; Liao; Vaughey, J; Ingram, BJ J. Electrochem. Soc.,
163(10) A2253-A2257 (2016).
(5) Mukherjee, A.; Sa, N.; Phillips, P.; Burrell, AK; Vaughey, JT; Klie, R. Chemistry of Materials, 29, 2218−2226 (2017).

Figure 1
Ultrasonically Dispersed Sodium Powders As Electrode Additives for Improved Cycling of Sodium Ion Batteries
Authors: Tang Jialiang , Kye Daniel Kyungbin , Pol Vilas G. 
Published: February 2020

Solid electrolyte interphase (SEI) growth on the anode surface remains a major challenge to sodium ion batteries. Excessive SEI buildup in the formation cycles or later cycles would consume electrolyte, deplete available alkaline ions, and increase cell polarization. These issues with SEI growth become more prominent in full cells in which cathodes store limited amount of alkaline ions that are available for electrochemistry. The reduction in the amount of available alkaline ions upon cycling often results in low capacity and poor capacity retention in full cells. To compensate the Na loss from SEI formation, we developed a sodium powder based presodiation technique that could potentially be applied to both anode and cathode materials with minimal modification to conventional battery making process. The synthesis of sodium powders is accomplished via ultrasonic dispersion of molten sodium in mineral oil. When suspended in hexane, the sodium powders can be easily applied onto electrodes as presodiation additives. Reduction in the 1st cycle loss and enhancement in reversible capacity have been observed in this study.
Charging Lithium-Oxygen Battery Via Protic Solvent-Enhanced Redox Shuttle Mechanism
Authors: Shen Yue , Zhang Wang , Huang Yunhui 
Published: February 2020

Lithium-oxygen battery has the highest theoretic energy density among all rechargeable batteries. But its discharge product Li2O2 is difficult to be oxidized back in the charge process, which causes high charge overpotential, serious electrolyte decomposition and poor cyclability. An effective way to solve this problem is adding redox mediator (RM) in the electrolyte to catalyze the charge reaction via a solution phase process. However, the reaction kinetics between the oxidized RM and Li2O2 is seldom investigated. Here, taking iodine species as the model RM, we find that the efficiency of the solution phase catalysis is limited by the reaction rate between the oxidized RM and Li2O2, which is largely dependent on the electrolyte solvent. Protic solvents, such as water and alcohols lead to high reaction rate because of the hydrogen bond induced solvation of Li2O2. However, too high proton activity may also bring unwanted peroxide disproportionation. Among a series of alcohols, n-butanol is found to show proper proton activity and significantly improves the solution phase catalytic efficiency.
Some issues on objectively evaluating the cathode performance of lithium-oxygen battery will also be discussed in this talk. Because of the complexity of the multi-phase electrochemical reaction, conventional half-cell testing methods and parameters to evaluate the performance of lithium-ion cathodes are not suitable for lithium-oxygen cathodes. It is common to use unlimited lithium and unlimited oxygen in half-cell tests. But such tests are just testing the “reusability of the catalyst” instead of the “reversibility of the electrochemical reaction”. The result cannot objectively reflect the parasitic reactions. To objectively evaluate the electrochemical reversibility, we propose a Li2O2-graphite cell with limited amount of lithium-ion. Such configuration can eliminate the “fake reversible capacity” caused by parasitic cathodic reactions, and thus is more reliable. We found that the real reversible ratio of the cathode reaction is much improved with the presence of redox mediator and butanol, but still far from satisfactory.
ref:
1. Shen, Y.; Zhang, W.; Chou, S.-L.; Dou, S.-X. Science
2016, 352, 667.
2. Sun, D.; Shen, Y.; Zhang, W.; Yu, L.; Yi, Z.; Yin, W.; Wang, D.; Huang, Y.; Wang, J.; Wang, D.; Goodenough, J. B. J. Am. Chem. Soc.
2014, 136, 8941.
3. Zhang, W.; Shen, Y.; Sun, D.; Huang, Z.; Zhou, J.; Yan, H.; Huang, Y. Nano Energy
2016, 30, 43.
4. Zhang, W; Shen, Y. ; Sun, D.;Huang, Z.; Huang, Y. Adv. Energy Mater.
2017, DOI:aenm201602938.
Large-Scaled Li-Air Batteries
Authors: Kang Jin-Hyuk , Sun Yang-Kook 
Published: February 2020

Actual cell capacities of Li-air batteries are very low and, since only small-scale electrodes are currently tested, it is hard to predict the properties of large-size electrodes and cells, thus evaluating and judging real practical challenges related to this battery technology.1-3

In this report, we report on fabrication, operation and evaluation of pouch-type Li-air cells using 3×5 cm2 sized electrodes, in which we intend deal with higher capacity (mAh) of the electrodes, compared to most previous studies in the field. With the relatively large-sized cells, operating at high current density and capacity, we could recognize some remarkable problems that may not be significant in small cells.
In relatively large cells as those explored in this work issues related to non-uniform current distribution, mechanical and electronic integrity of electrodes are much more influencing compared to small cells. Hence, problems such as lithium dendrites formation and non-uniform deposition of oxygen reduction product become severe.
This study can help to determine which parameters are the most important for developing practical Li-air batteries.

References

1. K. M. Abraham, Z. Jiang, J. Electrochem. Soc.
1996, 143, 1.
2. H. G. Jung, J. Hassoun, J. B. Park, Y. K. Sun, B. Scrosati, Nature Chemistry
2012, 4, 579. 3.
3 M. M. O. Thotiyl, S. A. Freunberger, Z. Peng, Y. Chen, Z. Liu, P. G. Bruce, Nature Materials
2013, 12, 1050.