bluuebunny/crossref_metadata_2025_split huggingface dataset:
Real-Time Collection, Visualization, and Processing of Electrochemical-Acoustic Data from Battery Cycling Experiments
Authors: Van Tassell Barry , Hsieh Andrew , Davies Greg , Steingart Daniel A 
Published: February 2020

In all batteries, the distributions of density and elastic modulus change as the cells are charged and discharged. As speed of sound in a material is a strong function of both its density and modulus, the behavior of an acoustic wave passing through a battery will therefore change during the cycle. In an earlier publication, electrochemical-acoustic analysis was demonstrated both experimentally and computationally as a simple-yet-powerful technique utilizing this phenomenon, providing unique in operando characterization of the physical dynamics within an operating battery in real-time.
To date, testing of a wide range of battery chemistries and form factors has shown that the instantaneous acoustic fingerprint of a cell is strongly and consistently correlated to its state of charge (SOC), and the time-resolved acoustic behavior of a cell during cycling is unique to both its chemistry and form factor. This technique quickly generates large data sets (particularly with multiplex testing) that are rich with information and require proper strategies and algorithms for analysis, not only to determine useful SOC correlations but also to perform the inverse analysis and deconvolute the dynamic acoustic waveforms to extract layer-by-layer physical information. Additionally, spectral analysis and signal processing can be applied to these data sets in order to identify time-evolving physical phenomena, which would enable the use of this method for determining the state of health (SOH) of the cell. The development of such strategies and algorithms will allow the simultaneous analysis of a large number of cells, for example in an advanced battery management system, and will be the focus of this talk.
The Electrodeposition of Germanene
Authors: Stickney John Lewellen , Ledina Maria , Jung Jin , Bui Nhi 
Published: February 2020

Germanene is the Ge analogue Silicene or Graphene. A number of ab-initio calculations in the literature suggest that Germanene sheets should exist. Those reports suggest that the material would have a buckled structure, where half the atoms are about 0.7 nm higher than the other half. Micro Raman, electrochemistry and in-situ scanning tunneling microscopy (EC-STM) have been used to better understand the electrochemical growth of Ge from aqueous solutions, from the first atomic layers on Au(111). Our initial studies of the electrodeposition of Ge resulted in some interesting, though not clearly understood results, such as why only about 2 ML of Ge could be formed by direct electrodeposition on Au, depending on the pH. Some reports in the literature indicate that thicker deposits of Ge can be formed by electrodeposition on electrode surfaces other than Au. It is not yet clear why Au would be different. In-situ STM studies of the first atomic layers of Ge have shown a number of processes which indicate that nanoscopic atomically flat layers are forming on the surface. The authors believe that Germanene is being formed. In addition, there is clear evidence of the formation of a surface alloy with the Au substrate, though the phase diagram suggests no significant alloying at room temperature, used in these studies. Further, though Au(111) displays the expected reconstructed (√3X23) “herringbone” structure expected, incorporation of Ge into the this structure occurs very slowly by reduction at negative potentials, starting at defects and step edges. Previous work by this group, lead to development of an electrochemical ALD cycle for the growth of thicker Ge films. That cycle is being further investigated, as some spots in early deposits displayed a Raman spectrum indicative of the presence of germanene. Presently it appears that at sufficiently negative potentials, germanene is being formed. That is, a honeycomb structure is observed, but the domain size is on the order of one or two nm, at which point, defects result in a twist in the structure.

References

Liang, et al., Langmuir, 26(4) (2010) 2877-2884
Xuehai Liang and John L. Stickney, Chemistry of Materials, 23(7)(2011)1742-1752
Xuehai Liang, et al., J. Am. Chem. Soc., 133(2011)8199-8204
M. A. Ledina, et al., ECS Transactions, 66 (6) 129-140 (2015)
Theoretical Investigation of Atomic-Scale Structure and Energetics of the Metal-Electrolyte Interface
Authors: Letchworth-Weaver Kendra , Umbright Christine K. , Chan Maria K. Y. , Arias T. A. 
Published: February 2020

Understanding the complex and inherently multi-scale interface between a charged electrode surface and a fluid electrolyte would inform design of more efficient and less costly electrochemical energy storage and conversion devices. Joint density-functional theory (JDFT) [1] bridges the relevant length-scales by joining a fully ab initio description of the electrode with a highly efficient, yet atomically detailed classical DFT description [2] of the liquid electrolyte structure, avoiding the costly statistical sampling of the liquid required by molecular dynamics calculations. Leveraging JDFT within our framework to treat charged systems in periodic boundary conditions [3], we then predict the voltage-dependent structure and energetics at the interface between a liquid electrolyte and single-crystalline metallic electrodes. We compare the JDFT-predicted interfacial water structure next to a metallic electrode with results obtained from classical and ab initio molecular dynamics simulations. We go on to elucidate the physical origin of the experimentally measured voltage-dependent differential capacitance of an Ag(111) electrode in aqueous electrolytes, examining the crucial role of ion desolvation and plating onto the electrolyte. Finally, we conclude with an exploration of how the choice of cation and anion in the electrolyte affects the atomically-detailed structure of the metal-liquid interface, yielding fundamental insight into processes in electrodeposition and corrosion.

Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

[1] S.A. Petrosyan et al, Phys. Rev. B 75, 205105 (2007)
[2] R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, J. Chem. Phys. 140, 144504 (2014)
[3] K. Letchworth-Weaver and T. A. Arias, Phys. Rev. B. 86, 075140 (2012)
(Invited) Pt Monolayers and Submonolayers on Nobel Metal Nanoparticles: Substrate- and Coverage-Depdendent Atomic Structures and Electrocataltyic Activities
Authors: Peng Lingyi , Du Hongda , Gan Lin 
Published: February 2020

Galvanic replacement of underpotentially deposited Cu monolayers (UPD) on noble metal substrates by Pt has been shown a robust strategy to synthesis Pt monolayer catalysts with ideally a 100% Pt utilization efficiency for energy conversion reactions, such as methanol oxidation reaction (MOR) in direct methanol fuel cells. The true atomic structures of the ‘Pt monolayers’ on different noble metal substrates, particularly on nanoscale metal nanoparticles, however, have still remained elusive.
By using high resolution (scanning) transmission electron microscopy combined with highly efficient energy-dispersive X-ray spectra mapping, we report here the atomic structures of Pt (sub)monolayers deposited on different noble metal nanoparticles (e.g. Au, Pd, Pt, and Ir, etc.) and at different coverage using the UPD and subsequent galvanic replacement method. Our results reveal that the Pt-substrate interaction has a pronounced influence on the growth mode and atomic structures of the Pt ‘monolayer’, which follows either Volmer-Webber island growth mode or Franck- van der Merwe layered growth mode, leading to different Pt utilization efficiencies and thus different electrocatalytic MOR activities. The nominal coverage of the Pt (sub)monolayers on the noble metal nanoparticles plays an additional role in fine-tuning the atomic structures, Pt utilization efficiency and electrocatalytic MOR activities. Our results provide important atomistic insights into a rational design of Pt (sub)monolayer catalysts with high Pt utilization efficiency and high catalytic activities.
(Invited) Electrodeposition of PbTe Thick Films for Micro Thermoelectric Devices
Authors: Wu Tingjun , Myung Nosang Vincent 
Published: February 2020

Heat is the natural by-product of energy conversion processes. Of the 4.25 × 1020 J of energy the United States consumes every year, more than 60% is wasted in the form of heat. Therefore, waste heat recovery is a crucial step to improve the energy generation and utilization efficiency. Thermoelectric (TE) materials, which can directly convert rejected or waste heat into usable electric power, has been extensively developed for this issue. Thick-film-based devices have advantages over conventional TE module because of its compact size. By shrinking the size of thermoelectric devices, it not only allows the device to operate under smaller temperature gradients, but by so doing it expands its capability to handle a wider range of thermal and power management microelectronic systems. The combination of electrochemical deposition of compound semiconductors (metal tellurides) with standard integrated circuit technique makes fabrication of thermoelectric microdevices possible.
In our work, we demonstrated a rapid deposition process (180 µm/h) in alkaline solution to synthesize dense thick PbTe film (>50 µm) for thermoelectric applications. Compared to the commonly used acidic baths with deposition rate about 4 µm/h, our electrodeposition process enhanced the film growth rate 48 folds higher. The electrodeposition mechanism of PbTe was examined. The thermoelectric property of thick PbTe films were optimized by introducing energy barriers from crystal grain boundary and tellurium nanoinclusion, which was achieved by tailoring composition and crystal structures of the thick PbTe films. Additionally, control over the composition and crystal structures was realized by tuning the electrodeposition conditions, such as the ratio of [TeO3
2-], [Pb2+], [EDTA4-]/[Pb2+], solution pH, and applied potential, as well as post-annealing process.
Facile Fabrication of Large-Area and Free-Standing Ni Inverse Opals
Authors: Hung Pei-Sung , Liao Chen-Hong , Huang Bo-Han , Chiang Wei-Shen , Hsieh Tsung-Lin , Wu Pu-Wei 
Published: February 2020

In this work, we demonstrate a simple scheme combining electrophoresis and electrodeposition to fabricate large-area unsupported Ni inverse opals. A variety of experimental variables are explored and the optimized parameters allows for the packing of 495 nm polystyrene microspheres on an ITO substrate to form a defectless colloidal crystal. Subsequently, a Ni plating is adopted to produce inverse opals, followed by the removal of the colloidal template and ITO substrate via chemical and physical routes. The large-area and free-standing Ni inverse opals (2×2 cm2) reveal hexagonally-arranged pores with interconnected pore channels. Materials characterization including SEM, XRD, AFM, Hall effect, 4-point probe, and porometer measurements are performed and their results are discussed.
Electrodeposition of Nickel from Aqueous Chloride Electrolytes
Authors: Jensen Mats , Haarberg Geir Martin , Seland Frode , Sunde Svein , Ratvik Arne Petter , Åkre Torjus 
Published: February 2020

Nickel may be produced by electrolysis in acidic chloride based electrolytes. Nickel is initially deposited on stainless steel or titanium starting sheets while chlorine gas is evolved on DSA anodes. Stress in the nickel deposit may cause bending of the cathode sheet. Also irregular growth such as dendrite formation may occur. In extreme cases short circuiting of electrodes will happen. Fundamental electrochemical studies of the initial stages of the electrodeposition process may give valuable information for obtaining smooth nickel deposits.
Initial experiments were carried out by using cyclic voltammetry on cathodes of titanium. Ongoing studies are performed by potential step chronoamperometry to study the nucleation and growth of nickel on titanium cathode substrates. Experiments to study the effect of electrolyte composition, pH and temperature on the nickel deposition process are under way. Electrolysis to deposit macroscopic amounts of nickel will be carried out to characterize the deposits by optical methods.
Electrochemical Reactor Design and Operation for the Simons Fluorination of Methyl Sulfonyl Fluoride
Authors: WANG Dawei , WANG Yaqiong , Xu Wenlin 
Published: February 2020

The key problems in the process for the industrialization of the Simons electrochemical fluorination of methyl sulfonyl fluoride (CH3SO2F) to trifluorometan-sulfonyl fluoride (CF3SO2F), such as reactor design and optimization of the process are discussed. Based on recent developments, the nickel fluorinating agent mediated mechanism in the Simons electrochemical fluorination of CH3SO2F to CF3SO2F is proposed. It is shown that the yield and current efficiency of the product mainly depend on the operating current density and the mass tranport rate. Thus useful rules to optimize the process of electrochemical fluorination in anhydrous hydrogen fluoride (HF) for reactor design and operation for the Simons fluorination of CH3SO2F are formulated for the solid-liquid heterogeneous reaction system.
In order to improve the yield and current efficiency as well as reduce the produce rate of the free fluorine (F2), an effective method is proposed to improve the mass transfer and reduce current density. A three-dimensional electrode electrochemical reactors is designed with a large specific surface area, which can significantly reduce the operating intrinsic current density, and effectively improve mass transfer with a large specific surface area, increase the concentrations of CH3SO2F on the reaction surface of the anode. The three-dimensional electrode electrochemical reactors fundamentally reduce the likelihood of fluoride chemical reaction, and raise the production efficiency of electrochemical reactor.
The experimental result shows that the product molar yield is more than 85% and current efficiency is more than 90% using 20 mesh metal nickel net as anode materials at 15-25% CH3SO2F in HF, operation temperature 0 to 15 °C and apparent operating current density between 1000-1600 A/m2.

Key words: Simons electrochemical fluorination, electrochemical reactor design, methyl sulfonyl fluoride, trifluorometansulfonyl fluoride.
Approximability of Impedance Spectra By RC Elements and Implications for Impedance Analysis
Authors: Schoenleber Michael , Ivers-Tiffée Ellen 
Published: February 2020

A commonly used class of impedance spectra validity tests is based on fitting serially connected parallel coupled pairs of resistor and capacitor (RC elements) to a measured impedance spectrum [1-4]. If the model approximates the spectrum well, the measurement is considered valid. It is considered invalid if approximation is poor. Despite being widely used, for a long time a precise theoretical justification for these techniques was missing. It was not clear, which class of electrochemical processes could be approximated by such a model and hence, for which processes a poor approximation of the spectrum truly indicates a false measurement, instead of merely a lack of generality of the model. The scope of our talk is to derive from a system theory point of view, which class of systems can be approximated by serially connected RC elements and from that to conclude for which electrochemical systems the mentioned class of validity tests is applicable [5].
References:
[1] P. Agarwal, M.E. Orazem, L.H. Garcia-Rubio, “Measurement models for electrochemical impedance spectroscopy”, J. Electrochem. Soc. 139 (1992) 1917
[2] B.A. Boukamp, “A linear Kronig–Kramers transform test for immittance data validation”, J. Electrochem. Soc. 142 (1995) 1885
[3] M. Schönleber, D. Klotz, E. Ivers-Tiffée, “A method for improving the robustness of linear Kramers–Kronig validity tests”, Electrochim. Acta 131 (2014) 20–27
[4] https://www.iam.kit.edu/wet/english/Lin-KK.php (Impedance Testing Software)
[5] M. Schönleber and E. Ivers-Tiffée, "Approximability of impedance spectra by RC elements and implications for impedance analysis", Electrochemistry Communications 58 (2015) 15-19
(Invited) Linear and Nonlinear Electrochemical Impedance Spectroscopy: A Data Science Perspective
Authors: Murbach Matthew D , Schwartz Daniel T. 
Published: February 2020

Electrochemical impedance spectroscopy (EIS) is widely used in the study of lithium ion batteries to determine important kinetic and transport parameters1 as well as to estimate internal state metrics and health prognostics.2,3 Typical analysis of the frequency dependent response involves fitting an equivalent circuit model to extract a few characteristic values for further study. This simple process is easy to implement and computationally efficient, but can artificially limit the information content of these techniques. Several rigorous physics-based models have laid the groundwork for a more sophisticated analysis of linear impedance for lithium ion batteries.4,5 These physics-based approaches offer improved confidence in parameter estimates, better phenomenological insight, and easier adaptation to changing chemistries. Previous work has been limited to analysis of the linear impedance response and variations in single physicochemical parameters.
Nonlinear electrochemical impedance spectroscopy (NLEIS) provides greater information content than linear impedance.6 Here we extend the previous physics-based models to compute the linear impedance, Z1,1(ω), as well as the nonlinear impedance from the 2nd harmonic, Z2,2(ω), and 3rd harmonic, Z3,3(ω), response of an LiCO2|C battery subject to moderate amplitude sinusoidal current modulations. To show the sensitivity to particular parameters (and interactions between parameters) variance-based sensitivity analysis is presented. The results enable the partitioning of the response into measures of sensitivity that are used to generate insight into the techniques and inform design of experiments to optimally extract specific information related to electrochemical processes or internal states. The increased informational content in nonlinear impedance measurements are also evaluated viz-a-viz standard linear impedance.

References:

1. Dokko, K. et al. Kinetic Characterization of Single Particles of LiCoO2 by AC Impedance and Potential Step Methods. J. Electrochem. Soc.
148, A422 (2001).
2. Tröltzsch, U., Kanoun, O. & Tränkler, H.-R. Characterizing aging effects of lithium ion batteries by impedance spectroscopy. Electrochimica Acta
51, 1664–1672 (2006).
3. Saha, B., Goebel, K., Poll, S. & Christophersen, J. Prognostics Methods for Battery Health Monitoring Using a Bayesian Framework. IEEE Trans. Instrum. Meas.
58, 291–296 (2009).
4. Doyle, M., Meyers, J. P. & Newman, J. Computer simulations of the impedance response of lithium rechargeable batteries. J. Electrochem. Soc.
147, 99–110 (2000).
5. Sikha, G. & White, R. E. Analytical Expression for the Impedance Response for a Lithium-Ion Cell. J. Electrochem. Soc.
155, A893 (2008).
6. Wilson, J. R., Schwartz, D. T. & Adler, S. B. Nonlinear electrochemical impedance spectroscopy for solid oxide fuel cell cathode materials. Electrochimica Acta
51, 1389–1402 (2006).

Figure 1
(Invited) Impedance Analysis of the Aluminum Oxide Formation
Authors: Sancy Mamié , Pineda Fabiola 
Published: February 2020

In the present work, electrochemical impedance spectroscopy measurements of the aluminum alloy 2024-T3 (AA2024) were performed as a function of the immersion time in different corrosive media to quantify the oxide film thickness. The impedance diagrams were obtained under potentiostatic conditions at the corrosion potential. The experimental electrochemical impedance spectroscopy data revealed a CPE behavior of the oxide film formation for all media and exposure times studied. The representations of the complex capacitance at high-frequency range and thickness of the oxide films were obtained from EIS analysis, which were in good agreement with the values obtained from surface analysis techniques.
Acknowledgements: The authors are grateful to Fondecyt Grants 1121085 and 1160604
On Interpretation of Constant-Phase Elements
Authors: Orazem Mark E. , Tribollet Bernard , Vivier Vincent , Musiani Marco , Pebere Nadine 
Published: February 2020

Electrical circuits invoking constant-phase elements (CPE) are often used to fit impedance data arising from a broad range of experimental systems. The CPE is often used simply as a way to improve the fit of a model to impedance data, justified by a vague assertion that a distribution of time constants is present in the system under investigation. The development in the present work shows that the CPE parameters have a physical meaning. The CPE may be seen as a special case of time-constant dispersion in which the time constants follow a particular distribution. The interpretation of CPE parameters in terms of physically meaningful properties such as capacitance requires an understanding of the nature of the time-constant distribution.
This presentation provides a review of recent work on the interpretation of constant-phase elements. A power-law distribution of resistivity in the direction normal to the electrode surface is shown to yield CPE behavior.[1-5] A formula developed by Brug et al. yields physical parameters for time–constant distributions along the surface of an electrode.[6] Work is underway to explore the physical origin of surface distributions that may give rise to a CPE.[7-9]
It should be noted that not all time-constant distributions can be described by a constant-phase element. For example, the impedance of the passive layer for a stainless steel electrode presented by Frateur et al.[10] shows CPE behavior; whereas, the time-constant distribution associated with a niobium oxide covered niobium electrode [11] is not a CPE.
References

B. Hirschorn, M. E. Orazem, B. Tribollet, V. Vivier, I. Frateur, and M. Musiani, Journal of the Electrochemical Society, 157 (2010) C452–C457.

B. Hirschorn, M. E. Orazem, B. Tribollet, V. Vivier, I. Frateur, and M. Musiani, Journal of the Electrochemical Society, 157 (2010) C458–C463.

M. E. Orazem, B. Tribollet, V. Vivier, S. Marcelin, N. Pébère, A. L. Bunge, E. A. White, D. P. Riemer, I. Frateur, and M. Musiani, Journal of the Electrochemical Society, 160 (2013) C215–C225.

S. Amand, M. Musiani, M. E. Orazem, N. Pébère, B. Tribollet, and V. Vivier, Electrochimica Acta, 87 (2013), 693-700.

M. Musiani, M. E. Orazem, N. Pébère, B. Tribollet, and V. Vivier, Progress in Organic Coatings, 77 (2014) 2076–2083.

G. J. Brug, A. L. G. van den Eeden, M. Sluyters-Rehbach, and J. H. Sluyters, Journal of Electroanalytical Chemistry, 176 (1984) 275–295.

C. L. Alexander, B. Tribollet, and M. E. Orazem, Electrochimica Acta, 173 (2015) 416–424.

C. L. Alexander, B. Tribollet, and M. E. Orazem, Electrochimica Acta, 188 (2016) 566–573.

C. L. Alexander, B. Tribollet, and M. E. Orazem, Electrochimica Acta, (2016) in press.

I. Frateur, L. Lartundo-Rojas, C. M´ethivier, A. Galtayries, and P. Marcus, Electrochimica Acta, 51 (2006) 1550–1557.

S. Cattarin, M. Musiani, and B. Tribollet, Journal of the Electrochemical Society, 149 (2002) B457–B464.