bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) From Solid State Chemistry to Battery Materials Electrochemistry: A Tool for Solid State Chemistry
Authors: Delmas Claude
Published: February 2020

Researches on battery materials has considerably increased during the last 30 years due to the huge development of lithium-ion batteries for portable devices (laptops, cellular phones, …) and more recently with the need to store energy in order to optimize its consumption. The next goal is the development of batteries for electric vehicles and their use into the grid. Nevertheless, the aqueous batteries (Ni-Cd, Ni-MH and Lead Acid) are always used in numerous applications thanks to their low price. In most of the batteries, the intercalation (deintercalation) of monovalent cations (H+, Li+, Na+) and electrons is the basic electrochemical reaction. The cell voltage is equal to the difference in Fermi level between the two electrodes. If one electrode exhibits a constant voltage it can act as reference and therefore, the cell voltage reflects all structure modifications which occurs on the material upon intercalation. The change is cell voltage depends on: (i) the electronic band filling, (ii) the change in the band structure due to change in composition, (iii) the modification of the Magdelung energy. In some cases the monotonous decreases of the voltage during the intercalation reaction indicates that the reaction occurs through a monophasic domain. In numerous cases, the reaction mechanism is more complicated and involves biphasic domains and/or formation of materials with a specific composition. The voltage vs composition curve is much more complicated and gives directly the phase diagram of the studied system.

 For the solid state chemist, the studies of the electrochemical reaction using a battery opens new possibilities to determine phase diagram at RT, but also to synthesize new metastable phases from a precursor made by classical solid state chemistry. The in situ or in operando experiments allow to follow directly the structural modifications occurring during the electrochemical reaction. Using synchrotron experiments it is possible to make experiments at high rate and therefore evidence intermediate states and understand the reactions mechanism. In the recent years, XRD diffraction and XAS analysis were intensively used.

On the opposite way, very sophisticated Solid State Chemistry techniques like solid state MAS NMR, Mossbauer spectroscopy and high resolution electron microscopy in aberration corrected microscope allowed to characterize battery materials at the atomic level.

In this presentation, some typical results obtained in Bordeaux concerning lithium and sodium layered oxides will be presented to emphasize the dual approach:

batteries to solid state chemistry and solid state chemistry to batteries.
Energy Dispersive X-Ray Diffraction (EDXRD): An Effective in-Situ Approach for Spatial Resolution of Electrode Reactions
Authors: Takeuchi Esther S , Marschilok Amy C , Takeuchi Kenneth J
Published: February 2020

Energy dispersive x-ray diffraction (EDXRD) presents a special opportunity to achieve spatial resolution of an electrochemical process within the electrode inside a functioning electrochemical cell, providing the opportunity for tomographic-like data analysis. White beam radiation coupled with a synchrotron “wiggler” insertion device emits high energy radiation which can penetrate bulk engineering materials such as steel, enabling in-situ measurement of conventionally designed prototype and production level batteries. Unlike other in-situ methods, EDXRD does not require the use of a modified or special cell design. Rather, the method enables a direct probe of electrode reactions in cells fully encased in their steel housings. These studies used a family of AgxVOy(PO4)z materials as model systems to provide insights into the electrochemical reduction process for inherently poorly conducting phosphate and diphosphate based cathode materials. The systems proved to be particularly well suited for EDXRD in-situ studies as the Ag0metal product formed on reduction could be detected in small amounts.

In-situ EDXRD was measured at several x-direction locations in several stainless steel coin cells with AgxVOy(PO4)z cathodes discharged to different depths of discharge under several rates. At each location spectra were collected in increments through the thickness of the electrode. The presence of Ag0 as a reduction product in silver vanadium phosphate cathodes had been verified ex situ using x-ray diffraction and scanning electron microscopy experiments. However, in situ measurements of the Ag0 provided the opportunity for further insight into the electrochemical reduction mechanism, regarding the location and distribution of the reduction products.
Charge Transfer Parameters (rCT, j0 and k) Determined By Combining Tomography Analysis with Impedance Modelling
Authors: Costard Janina , Joos Jochen , Weiss Michael , Ivers-Tiffée Ellen
Published: February 2020

Lithium-ion batteries allow for a broad range of power to energy ratio, i.e., originating from their flexibility in terms of (positive) electrode material, blend ratio, and microstructure design. Electrode models, which consider the required functionality in an appropriate way, are mandatory for optimization. Among them, electrochemical models are based on fundamental equations describing migration, diffusion and intercalation kinetics.

A crucial and challenging part of the model development is its parameterization. Material parameters, especially for (positive) intercalation electrodes, are hardly available from literature and/or the variance of the available values is (too) large, as discussed in [1].

The present work investigates the charge transfer process taking place at the interface between a (positive) electrode material and the liquid electrolyte. The model parameters (i) area specific charge transfer resistance rCT (ii) exchange current density j0 and (iii) rate exchange coefficient k are determined using a combination of focused ion beam milling (FIB) and electrochemical impedance spectroscopy (EIS). The microstructure parameters tortuosity, porosity and active surface area are determined from a 3-dimensional reconstruction of the electrode and the measured impedance spectra are fitted with an appropriate transmission line model (TLM). These methods have already been applied by our group for the investigation of battery electrodes [2, 3] but a combination of both methods has not been performed so far. By correlating the microstructure parameters (obtained by FIB) with the loss processes (obtained by EIS), the required material parameters for modelling the charge transfer process became accessible.

For validating the reliability of the presented approach, 4 cathodes of the (NixMnyCo1-x-y) solid solution system with varying microstructure are examined and compared yielding very low variance compared to values from literature.

 

References

[1] M. Ecker, T.K.D. Tran, P. Dechent, S. Käbitz, A. Warnecke and D.U Sauer, J. Electrochem.
Soc.
162, A1836-A1848 (2015)

[2] M. Ender, J. Joos, T. Carraro and E. Ivers-Tiffée, J. Electrochem. Soc.
159, A972-A980 (2012)

[3] J. Illig, M. Ender, A. Weber, E. Ivers-Tiffée, J. of Power Sources
282, 335-347 (2015)

Figure 1
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.
Redox Deposition of Hydrous Ruthenium Dioxide Onto Porous Vanadium Oxide Nanowires Prepared By Electroless Deposition
Authors: Li Jing-Mei , Hu Chi-Chang , Hsu Yung Jung
Published: February 2020

Hydrous ruthenium dioxide/vanadium oxide (RuO2×nH2O/VOx×mH2O) shell-core composites have been simply fabricated by means of a simple redox deposition method, i.e., immersing hydrous vanadium oxide thin film into a ruthenium (III) chloride solution for 1 hour. Because VOx×mH2O nanowires contain tetravalent and pentavalent states of vanadium species, quartz crystal microbalance (QCM) analyses is utilized to clarify that the tetravalent vanadium species dominates the deposition rate of RuO2×nH2O. Changes in the open-circuit potential (EOCP) and pH are recorded to understand the deposition mechanism. Rotating ring-disc electrode (RRDE) voltammetry is used to further ascertain the mechanism. X-ray photoelectron spectroscopic (XPS) analysis is used to identify the composition of RuO2×nH2O/VOx×mH2O shell-core composites. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) are used to examine the nanocoral morphology, the core-shell microstructure, and the homogenous dispersion of 2-nm RuO2×nH2O nanoparticles on VOx×mH2O nanowires.

Figure 1
(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.
Synthesis of Novel Graphene Composite Adsorbent for Water Treatment By Adsorption and Electrochemical Regeneration
Authors: Sharif Farbod , Roberts E.P.L.
Published: February 2020

One of the efficient and cost effective ways to remove organic contaminants from water is adsorption coupled with electrochemical oxidation. Graphite intercalated compounds (GIC) and activated carbons (AC) are among the common adsorbents for the adsorption - electrochemical regeneration process; nevertheless, they have significant shortcomings, i.e. GIC has low adsorptive capacity, whereas AC requires long regeneration time and high energy consumption associated with low current efficiency and high cell voltages. Owing to their huge surface area and high electrical conductivity, graphene-based materials are promising candidates as adsorbents suitable for electrochemical regeneration. This results in higher adsorptive capacity and current efficiency compared to AC and GIC. In this study, we prepared different types of graphene-based materials, namely graphene foam and magnetite reduced graphene oxide (rGO). The synthesized materials were characterized and tested for adsorption and electrochemical regeneration. Our findings revealed that, in addition to high current efficiency (greater than 80 %), these materials had a good adsorptive capacity compared to GIC. However, during the regeneration, graphene was oxidized and corroded after only a few cycles, contaminating the treated water. In the case of graphene foam, the integrity of the foam was lost after electrochemical regeneration. In order to overcome this corrosion problem and increase the current efficiency, a new composite was developed that is resistant to oxidation. The composite was characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy. Methylene blue was employed as a model adsorbate in synthetic wastewater samples. Regeneration was carried out in an electrolytic cell operated at a constant current. In spite of the slight reduction in adsorptive capacity compared to the pure graphene, the composite facilitated the oxidation of the organics to an extent in which a current efficiency of around 100 % was achieved. TEM images indicated that the composite was not significantly corroded during the electrochemical treatment. Even after ten cycles of adsorption and regeneration, no reduction in the adsorptive capacity and no contamination of the treated water was observed. In brief, the results of the current study introduce graphene composites as efficient materials for the adsorption - electrochemical regeneration 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.
(Invited) Theory of Impedance Response of Porous Electrodes: Simplifications, Inhomogeneities, Non-Stationarities and Applications
Authors: Huang Jun , Zhang Jianbo
Published: February 2020

Impedance is a standard and elegant tool in characterizing porous electrodes in electrochemical systems. The full potential of impedance characterization can be achieved only when a physically meaningful impedance model is used. Building a theoretically consistent framework, this study aims to develop a series of impedance models for porous electrodes with different properties. The framework starts with a full problem formulated by the concentrated solution theory and then simplifies it to four limited cases under different assumptions and approximations. In-plane, through-plane, multi-dimensional inhomogeneities are incorporated. In addition, based on the analytical Fourier transform, the impedance response during dynamic processes is numerically calculated. The theory is then applied to three typical cases: blocking, with Faradaic reactions, and with intercalation particles, which find their practical counterparts in electrochemical capacitors, proton exchange membrane fuel cells, and lithium-ion batteries. In each case, the structure, asymptotic behaviors, and characteristic frequencies of and inhomogeneous effects on the impedance spectrum are analyzed. Special attention is paid to the assumptions and applicability of each model. Experimental strategies to justify the use of an electric circuit model are discussed. The use of Warburg impedance to fit the diffusion coefficient in the solid active particles is scrutinized.

Figure 1
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.
(Invited) New Benzoxazine Resins Coated on Anodized Aluminium Alloys: Electrochemical Behaviour of Efficient Corrosion Protection Systems
Authors: Olivier Marjorie , Renaud Alexis , Dumas Ludovic , Delangre Adrien , Paint Yoann , Bonnaud Leila , Poorteman Marc , Dubois Philippe
Published: February 2020

Aluminum alloys are widely used in aircraft applications, especially series 2xxx (Cu) and 7xxx (Ti). Those alloys offer improved mechanical properties compared to pure aluminum, but are strongly sensitive to corrosion. Chromic anodizing combined with chromate containing epoxy primer was used as an efficient system to prevent corrosion. Nevertheless, due to health and environmental issues, this treatment is going to be forbidden. Alternative solutions have to be developed to reach aircraft standards considering health and environmental concerns. This work aims at proposing an alternative protective system, consisting in an oxide layer obtained from sulfotartaric anodizing (TSA) and coated with benzoxazine organic layers. Benzoxazine resins offer high chemical resistance and low shrinkage and so are very good candidates for coating applications. Investigated layers have been prepared on both bare and clad Al-2024 T3 substrates. The morphology and the thickness of coating systems were determined using Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Electrochemical Impedance Spectroscopy (EIS) was used to characterize the electrochemical behaviour of obtained systems and separated layers in order to emphasize synergetic effects. The AC/DC/AC electrochemical tests were carried out to evaluate the cathodic disbonding sensitivity of these new coating systems. The results were fitted by Equivalent electrical circuits to model the electrochemical properties of different layers and the evolution of their properties over immersion time in an aggressive saline solution and during AC/DC/AC cycles.

The results confirmed the strong potential of such systems for future corrosion protection applications.
(Invited) Effect of Position of Reference Electrode on Electrochemical Impedance in Laminated Lithium-Ion Rechargeable Batteries
Authors: Hoshi Yoshinao , Narita Yuki , Shitanda Isao , Itagaki Masayuki
Published: February 2020

Electrochemical impedance spectroscopy (EIS) is a powerful method to investigate the performance of lithium-ion rechargeable batteries (LIRBs). The three-electrode cell was used for the electrochemial impedance measurement of LIRBs to examine the electrochemical properties of the positive and negative electrodes in LIRBs 1-4). It is important to determine the position of the reference electrode in the LIRBs cell because the measured impedance spectra are affected by the current distribution between positive and negative electrodes. Our group 5) determined the suitable position of the reference electrode for impedance measurements in LIRBs with a three-electrode cell by finite element method (FEM). On the basis of FEM analysis, the effect of the position of the reference electrode on the impedance spectrum was investigated by the measurement of the impedance spectrum of the laminated LIRBs. The condition of reference electrode before and after the impedance mesurement of the laminated LIRBs was discussed with the measured impedance spectrum in the present study.

 

References:

1.  D.P. Abraham, S.D. Poppen, A.N. Jansen, J. Liu, D.W. Dees, Electrochim. Acta, 49 (2004) 4763-4775.

2. J. Zhou, P.H.L. Notten, J. Electrochem. Soc., 151 (2004) A2173-A2179.

3. C.H. Huang, S.X. Zhuang, F.Y. Tu, J. Electrochem. Soc., 160 (2013) A376-A382.

4. O.S. Mendoza-Hernandez, H. Ishikawa, Y. Nishikawa, Y. Maruyama, Y. Sone, M. Umeda, Electrochim. Acta, 131 (2014) 168-173

5. Y. Hoshi, Y. Narita, K. Honda, T. Ohtaki, I. Shitanda, M. Itagaki, J. Power Sources, 288 (2015) 168-175.
(Invited) Analysis of Li-Ion Battery By EIS Response By Equivalent Circuit and Verification of Estimated Parameters
Authors: Momma Toshiyuki , Mukoyama Daikichi , Nara Hiroki , Yokoshima Tokihiko , Osaka Tetsuya
Published: February 2020

Analyzing technique of Li-ion batteries (LIB) is strongly demanded both in the field of developments of LIB with improved properties such as safety, long life, and high capacity with high power, and in the field of checking the condition of the installed LIB in the power unit. Electrochemical impedance spectroscopy (EIS) is one of the most effective methods of investigation of LIB without disassembling of the cell. We have proposed an equivalent circuit for analysis of electrochemical reactions, diffusion parameters, and resistivity of solid electrolyte interphase (SEI), and demonstrated analysis of impedance spectra with using the proposed circuit.[1-3]

Since the impedance responses of the LIB are the results of impedance of each anode and cathode connected in series, it is hard to distinguish them into elemental steps for each electrode. In this paper, our strategy for the analysis of LIB impedance with resolving the response classified by time constant into elemental steps of each electrode is demonstrated.

The impedance of whole LIB cell was analyzed based on the equivalent circuit with the values of time constant of impedance response for elemental steps of each electrode. The impedance response of elemental step for each electrode was confirmed with two symmetric cells which have a set of two LIB anodes or two LIB cathodes. In order to confirm the correspondence between the each elemental step and the estimated parameters, impedance analyses of symmetric cells to obtain each value of time constant for response of each elemental step.

Furthermore, parameter analysis with shifting profile of time constant of impedance responses by sequence change in temperature of the LIB also helps to verify the reliability of the estimated values. Figure 1 shows the estimated values of each resistance in the equivalent circuit with the analysis of ac response of LIB under various temperatures. The values are aligned straightly against the LIB temperature, while the values obtained at 20 degree C locates out of the lines. These values at 20 degree C could be considered to be difficult to estimate adequately since the time constant of the response were over-lapping.

At the presentation, detailed explanation of these analyses will be introduced and discussed their potential for reliable analysis of impedance spectra.

This work was partly supported by “Research & Development Initiative for Scientific Innovation of New Generation Batteries” from NEDO, Japan.

[1] T. Osaka, et al., J. Power Sources, 119 (2003) 929-933.

[2] T. Osaka, et al., J. Power Sources, 205 (2012) 483-486.

[3] D. Mukoyama, et al., Chem. Lett., 41 (2012) 444-446.

[4] T. Momma, et al., J. Power Sources, 216 (2012) 304-307.

Figure 1
(Invited) Corrosion Inhibitor (Decanethiol) for Carbon Steels Exposed to Aqueous CO2
Authors: Belarbi Zineb , Farelas Fernando , Singer Marc , Young David , Nesic Srdjan
Published: February 2020

CO2 corrosion mitigation is a challenge in the oil and gas industry. In order to decrease the severity of CO2 corrosion of carbon steel pipelines and equipment, different mitigation practices are recommended. One such strategy is the application of surface active chemical inhibitors. The objective of this study was to evaluate the inhibition effectiveness of decanethiol in a CO2-saturated aqueous electrolyte (1 wt.% NaCl). The inhibition properties of decanethiol were evaluated by electrochemical measurements (linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS)) and the steel surface characterized by scanning electron microscopy (SEM). The obtained data show that decanethiol successfully prevents corrosion of carbon steels in a CO2 environment. An inhibition mechanism was also proposed based on adsorption characteristics and film formation.

Keywords
:
CO2 corrosion, decanethiol, carbon steel, EIS, surface film
Detection Method of Corrosion Site of Reinforcing Steel in Concrete By Two Electrode System
Authors: Koike Taisuke , Tokieda Hiroyuki , Hoshi Yoshinao , Shitanda Isao , Itagaki Masayuki
Published: February 2020

A reinforced concrete has been used for the building structures and bridge in the world. However, the degradation of reinforced concrete related to the corrosion of the reinforcing steel in concrete is now serious problem. It is important to establish the method to evaluate the durability of reinforced steel in concrete. Dawson et al. [1] applied the electrochemical impedance spectroscopy to investigation of the corrosion resistance of reinforced steel in concrete. Koleva et al. [2] investigated the durability of the steel rebar casted mortal cylinder by the rest potential, polarization curve and electrochemical impedance measurements.

The present study developed the method to determine the corroded reinforcing steel in concreate by two electrode system. Figure 1 shows the schematic of developed system in the present study. Two copper electrodes are placed on the surface of the concrete in which the steel bar was embedded. The cover thickness of concrete was 10 mm. The half side of the steel bar corroded to simulate the degradation of the steel bar.

Schematic of the impedance spectrum of reinforcing steel in concrete measured by two electrode system is shown in Fig. 2. Two loops were observed in the impedance spectrum when the copper electrodes are placed on the concrete in which corroded steel was embedded. It indicated that the current flowing though the copper electrodes was flowed into the corroded region of the steel bar. The loop in the high frequency range was related to concrete and the loop in the low frequency range was related to interface of concrete between steel rebar.

Reference:

[1] J. L. Dawson, L. M. Callow, K. Hladky and J. A. Richardson, Corrossion/78, 125 (1978).

[2] D. A. Koleva, K. van Breugel, J. H. W. de Wit, E. van Westing, N. Boshkov and A. L. A. Fraaij, J. Electrochem. Soc., 154, E45 (2007).

Figure 1
(Invited) Using Industry to Inspire Academic Research
Authors: Takeuchi Esther S , Marschilok Amy C , Takeuchi Kenneth J
Published: February 2020

Market driven applications may benefit from improved or next generation products. However, the scope of the product modification for the new application may be substantial, require significant investment and be high risk. Thus, the new product introduction may be beyond the risk tolerance of a company even though the application and product are aligned with company objectives. This scenario provides an opportunity for academically based research. Academic research can pursue higher risk alternatives in parallel with the investigation of the basic science phenomena associated with the new concept.

Several case studies will be described. For example, one case focuses on the investigation of a new class of active cathode materials for an implantable medical battery. A known life limiting phenomena, cathode solubility, was explored at a fundamental level for the benchmark commercialized system and compared with the new class of materials under development. It was demonstrated that the life limiting mechanism of the battery could be significantly reduced. The second case study describes improvement in pulse power for a lithium/carbon monofluoride (CFx) battery. While the Li/CFx system provides high energy density, it has been limited by its power capability. Electrode design approaches were utilized to address the limitation to broader market adoption.