bluuebunny/crossref_metadata_2025_split huggingface dataset:
Suitable Position of Reference Electrode in Three-Electrode Cell for Impedance Measurements in Lithium-Ion Rechargeable Battery Investigated By Finite Element Method
Authors: Hoshi Yoshinao , Narita Yuki , Honda Keiichiro , Ohtaki Tomomi , Shitanda Isao , Itagaki Masayuki 
Published: February 2020

Our group [1] determined the suitable position of the reference electrode for impedance measurements in lithiumion rechargeable batteries (LIRBs) with a three-electrode cell by finite element method (FEM). Electrochemical impedance spectroscopy (EIS) is a powerful method to investigate the performance of batteries [2-7]. It is important to obtain the electrochemical paramters of the positive and negative electrodes in LIRBs. In order to measure the impedance spectra of both electrodes in LIRBs cell, a three-electrode cell is used for the impedace measurement. Although the electrochemical properties of the positive and negative electrodes in LIRBs cell were investigated using the three-electrode cell by EIS [8-11], the position of the reference electrode was yet to be established for the impedance measurement. As the measured impedance spectra are affected by the current distribution between electrodes, it is important to determine the suitable position of the reference electrode in the LIRBs cell.
In the present study, we proposed the best position of the reference electrode for measurement of the impedance spectra of the positive and negative electrodes in the LIRB cell by using a three-electrode cell. A symmetrical model for the LIRB cell is used for the FEM simulation. The simulations of the current and potential distributions for both electrodes are performed by FEM. The impedance spectra of both electrodes were also calculated by FEM to discuss the effect of the position of the reference electrode on the current distribution between both electrodes.
References:
[1] Y. Hoshi, Y. Narita, K. Honda, T. Ohtaki, I. Shitanda, M. Itagaki, Journal of Power Sources, 288 (2015) 168-175.
[2] N. Takami, A. Satoh, M. Hara, I. Ohsaki, Journal of the Electrochemical Society, 142 (1995) 371-379.
[3] K. Chung, M.W. Chung, W.S. Kim, S.K. Kim, Y.E. Sung, Y.K. Choi, Bulletin of the Korean Chemical Society, 22 (2001) 189-193.
[4] C.S. Wang, A.J. Appleby, F.E. Little, Electrochimica Acta, 46 (2001) 1793-1813.
[5] S.S. Zhang, M.S. Ding, K. Xu, J. Allen, T.R. Jow, Electrochemical and Solid State Letters, 4 (2001) A206-A208.
[6] M. Itagaki, N. Kobari, S. Yotsuda, K. Watanabe, S. Kinoshita, M. Ue, Journal of Power Sources, 135 (2004) 255-261.
[7] M. Itagaki, N. Kobari, S. Yotsuda, K. Watanabe, S. Kinoshita, M. Ue, Journal of Power Sources, 148 (2005) 78-84.
[8] D.P. Abraham, S.D. Poppen, A.N. Jansen, J. Liu, D.W. Dees, Electrochimica Acta, 49 (2004) 4763-4775.
[9] J. Zhou, P.H.L. Notten, Journal of the Electrochemical Society, 151 (2004) A2173-A2179.
[10] C.H. Huang, S.X. Zhuang, F.Y. Tu, Journal of the Electrochemical Society, 160 (2013) A376-A382.
[11] O.S. Mendoza-Hernandez, H. Ishikawa, Y. Nishikawa, Y. Maruyama, Y. Sone, M. Umeda, Electrochimica Acta, 131 (2014) 168-173.
Time Domain Analysis on Current Response of Equivalent Circuit Involving Constant Phase Element
Authors: Itagaki Masayuki , Suzuki Suguru , Hoshi Yoshinao , Shitanda Isao 
Published: February 2020

Electrochemical impedance spectroscopy (EIS) is powerful method to investigate electrolyte/electrode interface of various energy devices and electrochemical phenomena. The electrolyte/electrode interface is simply represented by a parallel circuit of charge transfer resistance (R
ct) and double-layer capacitance (C
dl), and its impedance spectrum describes a true semicircle on the Nyquist plane theoretically. However, the depressed semicircle is often observed in the experimental result of the impedance spectrum. The depressed semicircle has been explained by distribution of various relaxations at electrolyte/electrode interface [1, 2]. Burg and co-workers [3] reported the relation between constant phase element (CPE) and distribution of time constants and proposed the calculation method of a capacitance from CPE parameters on the basis of ladder equivalent circuit. In the present paper, a time domain data of current response by parallel circuit of CPE and resistance were calculated by the following algorithm in order to attempt the separation of time constants in the current response in the time domain.
(1) The pulse voltage V (t) in the time domain including the data of the 2N unit is converted into the voltage V (ω) in the frequency domain by a fast Fourier transform (FFT).
(2) The impedance Z (ω) is calculated as a complex number at each frequency from the equivalent circuit involving CPE.
(3) The current I (ω) in the frequency domain is calculated by dividing Z (ω) by V (ω) in the frequency domain.
(4) I (ω) is converted into the time domain current I (t) by an inverse fast Fourier transform (IFFT)
(5) The number and value of the time constant of I (t) are determined by curve fitting of the ladder equivalent circuit.
(6) The impedance spectrum calculated by (5) is compared with that by the equivalent circuit involving CPE.
The calculated results indicate that the current response by the equivalent circuit involving CPE is a sum of those with plural time constants. It was found that the distribution of time constants is concerned with the CPE index (p) remarkably. In addition, the relation between the CPE constant (T
CPE) and C
dl was discussed.
References
[1] Z. Kener, T. Pajkossy, J. Electroanal. Chem.
448 (1998) 139.
[2] C. A. Schiller, W. Strunz, Electrochim. Acta
46 (2001) 3619.
[3] G. J. Burg, V. D. Eeden, M. Sluyters-Rehbach, J. H. Sluyters, J. Electroanal Chem., 176 (1984) 275.
In-Situ TEM Observation of Solid Electrolyte Interface Evolution during Li-Ion Battery Opeeration
Authors: Kushima Akihiro , Kuriyama Nariaki , Maebashi Takanori , Fujiwara Yoshiya , Li Ju 
Published: February 2020

Solid electrolyte interface (SEI) plays a critical role in the Li-ion battery. The formation of the SEI passivates the electrode surface and prevents excessive decomposition of the electrolyte. On the other hand, it can degrade the electrolyte and cause a battery to fail if the electrolyte continues to decompose due to insufficient passivation of the electrode. This can be severe for the high capacity anode with large volume changes during charge/discharge cycles. With the expansion and the contraction of the electrode, SEI formed on the surface can crack or delaminate exposing a fresh surface to the electrolyte and cause poor cyclability of the battery. Understanding how does the SEI response to the volume change of the electrode is important to design the electrode structure to improve the cycle performance. The thickness of the SEI is in the nano-meter scale. Therefore, high-resolution imaging using electron microscopy is essential for observing the reaction process.
In this work we present the in-situ transmission electro microscopy observation of the structural evolution of the SEI formed on a Si anode during lithium ion battery operations. Here, we developed a liquid confining cell to prevent electrolyte from evaporating into the high vacuum inside the TEM. We observed the formation of a SEI layer on the Si film during charge along with the volume expansion of the film. Upon discharge, the contraction of the film was observed. The shrinking of the film was not uniform across the film and the strain gradient caused a tension on the SEI layer resulting in the crack formation. New SEI will form on the freshly exposed Si surface on the following charge. This can cause continuous decomposition of the electrolyte and eventual failure due to the electrolyte consumption. The in-situ TEM experiment in this work shows the breaking of the SEI can take place during the discharge after it was formed on charging. Various combinations of the electrolyte, electrode, and the applied potential or current density are necessary to obtain the optimum battery design for producing adequate SEI layer or prevent them from forming. However, out observation provides important information toward designing a battery structure with improved performance.

Figure caption: Sequential TEM image of the SEI cracking on Si anode discharged at 0.0 V vs. LiCoO2.

Figure 1
Measuring Dynamic Changes in Si SEI Chemistry
Authors: Veith Gabriel M , Browning James F , Sacci Robert L , Fears Tyler , Doucet Matthieu 
Published: February 2020

In this presentation we will present experimental in situ measurements of the thickness and chemistry of the SEI layer that forms over amorphous silicon electrodes as a function of state-of-charge and cycle. These measurements were performed using neutron reflectometry which was supported by XPS, IR and electrochemical measurements. We will show the thickness of the Si SEI layer changes as a function of state-of-charge becoming thicker with lower states of lithiation and thinner with greater lithiation. Furthermore, the chemistry changes with cycle from more LiF rich at higher states-of-charge to more polymeric when delithiated. The thickness and the chemistry of the SEI layer changes with the addition of electrolyte additives, like fluorinated ethylene carbonate. Together these results help develop an understanding of additive chemistry and will direct the development of new additives.
This research was supported by the Materials Sciences and Engineering Division, Office of Basic Energy Sciences, U.S. Department of Energy under contract with UT-Battelle, LLC (GMV, TF, RLS – XPS, NR data collection, electrochemistry). Neutron reflectometry measurements were carried out on the Liquids Reflectometer at the Spallation Neutron Source which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy (JFB, MD – Data collection and analysis).
Chemical, Electrochemical and Physical Properties of the Solid Electrolyte Interphase on HOPG Surface: Mechanisms of Formation and Transition Metal Deposition
Authors: Antonopoulos Byron Konstantinos , Kirdar Cansu , Maglia Filippo , Schmidt-Stein Felix , Hoster Harry Ernst 
Published: February 2020

Both the reaction pathways that lead to the formation of the solid electrolyte interphase (SEI) on the negative electrode of a lithium ion battery and the chemical, electrochemical and physical properties of the SEI are not well understood. Consequently, a full control of the SEI composition and properties through the selection of appropriate formation conditions is far from being achieved. In this contribution we present the influence of the formation potential on the chemical and electrochemical properties of SEIs formed on model carbon electrodes. Our results show that, on HOPG, SEI is formed via a two-step process, where the step occurs at respectively ~700 and ~400 mV vs. Li/Li+. The SEIs that are formed at potentials corresponding to the first or the second potential step exhibit drastically different characteristics in terms of chemical composition, thickness and transport properties. Our results are consistent with electrochemical investigations that are performed on commercial composite carbon electrodes. The SEI formed at higher potentials appears to be disadvantageous for Li+ ion intercalation. A further reduction of the SEI at lower potential is required to improve the intercalation.
The still debated mechanism of transition metal deposition on the anode of Li-ion batteries was also investigated on model HOPG electrode surfaces exposed to contaminated electrolyte after completion of the SEI formation. Our results indicate, that the deposition of transition metals is strongly affected by the nature of the SEI, in particular by its thickness. By introducing transition metal cations in our model system we demonstrate, that the respective deposition takes place at the SEI compact layer surface via an electron tunneling mechanism.

Figure 1
Study of the Interface Layer Between Lithium Metal and a Single Ion Conductor Ceramic, Based on Block Copolymer, for Lithium Air Batteries
Authors: Frenck Louise , Bouchet Renaud , Stevens Philippe , Balsara Nitash P. 
Published: February 2020

The electrification of transport is a formidable challenge, however the energy storage possible in Li ion batteries is not sufficient to this purpose. A potential option is Lithium-air battery, first because of their very high energy densities and second because of their low costs. Two different approaches to the development of these batteries are possible: the anhydrous system which uses an organic electrolyte, and the aqueous system which uses an aqueous electrolyte [1]. An advantage of the aqueous system is its safety since toxic or inflammable solvents are not used. In order to protect the negative lithium electrode from the aqueous electrolyte, a thin ceramic water and gas tight membrane is used. The interface between the lithium metal and the ceramic membrane plays an important role in the cycling performance of the aqueous lithium air cell. Nonetheless, the poor or non-chemical stability of most ceramic electrolytes in contact with lithium metal limits the performance. A possible strategy to improve the interface between ceramic electrolyte and lithium metal might be by the use of polymer membranes [2].
This study reports the effect of a polymer membrane between a ceramic electrolyte and lithium metal. Block copolymer electrolytes, such as polystyrene-block-poly (ethylene oxide) copolymer electrolyte (SEO) mixed with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, were used. The single ion conductor ceramic electrolyte was a Lithium Ion Conducting Glass Ceramic (LICGC) purchased from Ohara Corporation (1 inch X 1 inch 150µm thick). Impedance spectroscopy has been used, so as to study the lithium ion - lithium metal transfer from a lithium ion conducting polymer interface. Furthermore, in order to know if the sandwich polymer-ceramic cell showed an additional interfacial resistance, ionic conductivity experiments using electrochemical impedance spectroscopy were performed. Besides, polarization loss quantification at a lithium ion conducting polymer/single ion conductor interface was studied by DC current measurement by the Srinivasan et al method [3]. Finally, in order to confirm the intimacy of the ceramic and the polymer, the interface between the ceramic and the polymer was studied by synchrotron hard X-Ray micro tomography experiments on symmetric lithium-sandwich polymer-ceramic cells.

P.G. Bruce, S. A. Freunberger, L. J. Hardwick, J-M. Tarascon, Nature Materials, 11, 19-29 (2012)

G.M. Stone, S.A. Mullin, A.A. Teran, D.T. Hallinan, A.M. Minor, A. Hexemer, N.P. Balsara, Journal of the Electrochemical Society 159(3) A222-A227 (2012)

Mehrotra, P. N. Ross, V. Srinivasan, Journal of the Electrochemical Society, 161 (10) A1681-A1690 (2014)
Speciation of Haloaluminate Electrolytes in Mg-Ion Batteries: A Combined Study of ab Initio Molecular Dynamics and Simulated X-Ray Absorption Spectroscopy
Authors: Wan Liwen , Prendergast David 
Published: February 2020

Since the development of prototype Mg-ion battery system [Aurbach et al., Nature 407, 724 (2000)] that employs organohaloaluminate (Mg(AlCl2BuEt)2) in tetrahydrofuran (THF) as the electrolyte, the exact solvation structure of Mg2+ in solution is still under debate. For further development of divalent Mg-ion batteries, a molecular-scale understanding of how Mg ion is solvated in such complex solution is vital to understand and improve ion transport properties in the electrolyte and dissolution/deposition processes at the electrolyte/electrode interfaces.
In this work, we aim to resolve the controversy of the exact solvation structure of Mg2+ by performing ab initio molecular dynamics (AIMD) simulations. To validate our AIMD predicated Mg solvation structures, we also simulate the corresponding Mg and Cl K-edge X-ray absorption spectra and compare with existing literature. We conclude that in the dilute limit of salt concentration, Mg ion is always tetracoordinated. This corrects a long-standing bias that Mg ions should be hexacoordinated in THF solution. By comparing with various experimental measurements, our results also imply that the solvation structure of Mg ion in haloaluminate solution is very sensitive to local salt concentration, relative Mg/Al ratio and bias-dependent electric filed during cycles.
This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.
Nucleation and Growth Behavior of Electrodeposited Lithium in Ionic Liquid
Authors: Sano Hikaru , Sakaebe Hikari , Senoh Hiroshi , Matsumoto Hajime 
Published: February 2020

Metallic lithium is a promising anode candidate for rechargeable battery; however, the dendrite formation during charging should be suppressed to improve safety and cycleability. Many researches have been reported from the viewpoint of the control of the surface film on lithium metal1. Ionic liquids nowadays attract much attention from electrochemists, some of which have excellent stability at highly cathodic states (such as Li/Li+). Our group has focused on their unique features and utilized these ionic liquids as electrolyte with lithium metal anodes. In the present study, in order to determine the condition for the non-dendritic lithium deposition, we investigated the electrodeposition behavior during nucleation and growth state in ionic liquids based on overpotential and Li-ion diffusion.
10 wt.% of Li[Tf2N] was added to [C3mpip][Tf2N], [C4mpyr][Tf2N], and [N6,1,1,1][Tf2N] as the electrolytes. Lithium metal was electrodeposited on nickel substrates at current densities ranging from 5 to 200 μA cm-2 for total charge amount of 0.1 and 3 C cm-2. The morphology of electrodeposited lithium was observed by SEM.
For the nucleation state, we focused on the case with charge amount of 0.1 C cm-2. The deposits were better distributed when the current density was increased (Figure 1). Additionally, the deposits were better distributed when the electrolyte viscosity was increased. In these conditions, an increased overpotential was confirmed. This is believed to lead to a wide distribution of nucleation sites due to decreased critical radii of the nuclei2. On the contrary, for the growth state, we focused on the case with the charge amount of 3 C cm-2. More deposits were more dendritic when the current density was increased (Figure 2) and also when the electrolyte viscosity was increased. This result can be rationalized by considering that the lithium ion concentration extremely decreased at the electrode surface, since Li-ion diffusion is slower than the decrement in the concentration of Li-ion at the electrode surface3. These tendency is common for noble-metal electrodeposition. The reason why these tendency is also observed for less noble metals such as lithium is considered to be that the ionic liquid used in this study is very stable at the highly cathodic state and therefore less effect of native film formation on the deposition.
1. D. Aurbach, E. Zinigrad, Y. Cohen, H. Teller , Solid State Ionics, 148, 405 (2002).
2. H. Sano, H. Sakaebe, H. Senoh, H. Matsumoto, J. Electrochem. Soc., Submitted.
3. H. Sano, H. Sakaebe, H. Senoh, H. Matsumoto, J. Electrochem. Soc., 161, A1236 (2014).

Figure 1
Overcoming Key Challenges for a Viable Lithium-Sulfur Transportation Battery
Authors: Zavadil Kevin R 
Published: February 2020

The lithium-sulfur electrochemistry is viewed as an attractive electrical energy storage system for transportation applications because of projections of system level energy density and specific energy in excess of state-of-the-art lithium ion technology. The current lack of a low cost ($100/kWh), high performance (400 Wh/L, 1000 cycle) Li-S battery technology is the consequence of limits imposed by several key materials science challenges that must be overcome to move this technology forward. A recent material-to-system analysis demonstrates that the most direct path to increased energy density and low cost is through the reduction of the electrolyte volume fraction (with respect to sulfur) and a reduction in excess metallic lithium [1]. Reduced electrolyte volume fraction requires developing knowledge of how sulfur redox chemistry is altered under lean or starved electrolyte conditions; including electrochemical limits to capacity, the spatial distribution and properties of solid discharge products, and occlusion of sulfur. Reduced Li metal excess requires science informed strategies for protecting the anode against parasitic reaction and maintaining dimensional control during Li electrodeposition and dissolution. The Joint Center for Energy Storage Research (JCESR) has assembled a multidisciplinary team to conduct the necessary science, translate this knowledge to test platforms, develop data fed performance models, and demonstrate progress through cell prototypes [2]. The goal of this presentation is to communicate JCESR’s current progress on these challenges and to provide perspective on where achievable performance will likely be pinned by select fundamental limits.
This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Sandia is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. DOE’s NNSA under contract DE-AC04-94AL85000.

D. Eroglu, K.R. Zavadil, K.G. Gallagher, “Critical Link between Materials Chemistry and Cell-Level Design for High Energy Density and Low Cost Lithium-Sulfur Transportation Battery,” J. Electrochem. Soc., 2015, 162 (6), A982-A990.

G. Crabtree, “The Joint Center for Energy Storage Research: A New Paradigm for Battery Research and Development”, AIP Conf. Proc., 2015, 1652, 112-128.
Advancing Operando Tools to Probe Multiscale Complexity in Chemical Energy Storage
Authors: Chapman Karena W , Grey Clare P , Chupas Peter J , Batson Philip , Cosandey Frederic , Cabana Jordi , Meng Shirley , Zhou Guangwen 
Published: February 2020

Electrochemical energy storage is a rapidly expanding area of study, driven by critical applications in alternative energy technologies (e.g. for grid storage coupled to intermittent solar/wind energy sources) and improved efficiency (e.g. in vehicle technology). Batteries, by their nature, do not operate under equilibrium conditions. Accordingly, there is a growing need for operando characterization tools to understand the dynamic mechanisms and kinetics of the electrochemical reactions which govern energy storage. Within the NorthEast Center for Chemical Energy Storage (NECCES) EFRC, we are developing and applying a series of complementary operando tools to probe and decouple the structural, chemical, and electronic changes in operating batteries at the atomic-, particle- and electrode-levels. This will allow us to develop a comprehensive understanding of the fundamental processes that underlie performance limitations and failure. Methodologies span hard and soft X-ray scattering, spectroscopy and imaging, electron microscopies, and NMR-based spectroscopy and imaging.