bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrodeposition of Void-Free Nanostructured Aluminum from AlCl3–Diglyme Electrolyte
Authors: Zhang Zelei , Kitada Atsushi , Fukami Kazuhiro , Murase Kuniaki 
Published: December 2020

Since Al has a lower redox potential (–1.68 V vs. SHE), the use of aqueous baths fails to electrodeposit less noble Al. The development of AlCl3–based nonaqueous electrolytes attracts intense interest in the field of Al and its alloys electrodeposition. In our previous studies on AlCl3–glyme electrolytes, AlCl3–G2 has been successfully used for Al and Al–CNTs electrodeposition.
The nature properties of AlCl3–G2 electrolyte will be influenced by amount of AlCl3. AlCl3–G2 electrolyte has been investigated via NMR, Raman, ionic conductivity, dynamic viscosity and cyclic voltammetry. AlCl3–G2 electrolyte contains ionic complex ([AlCl2(G2)2]+ and AlCl4
–) and neutral molecule (AlCl3·G2 and G2). Increasing the molar ratio (x) of AlCl3 from 0.1 to 0.2 and 0.4, the dynamic equilibrium towards the direction of forming ionic species. The AlCl3–G2 electrolyte with x = 0.4 has a lower conductivity (2.6 mS cm–1) than that of molar ratio x = 0.2 at 25oC, due to an increased viscosity (15.2 mPa s). However, it exhibits the best ionicity and can be used to electrodeposit void-free Al deposit with smooth appearance. As shown in Figure 1(a) and (b), the Al deposit from x = 0.4 electrolytes is accumulated by fine particles, giving rise to a compact and smooth surface with metallic luster. In contract, x = 0.2 electrolyte gives a flake-like Al deposit (Figure 1(e) and (f)), resulting in a rough surface with black appearance. In addition, adjacent Al flakes grow at a certain angle indicated by the yellow arrows shown in Figure 1(h), thus, the voids pointed by green circle are remained in the deposits during the continuous electrodeposition.
The corrosion behaviour of Al deposits have been compared using EIS and cyclic polarization techniques. The corrosion behaviour shows a strong dependence on the crystalline size, orientation and compactness. Al deposit obtained from x = 0.4 electrolyte has a trait of nanosized crystalline (about 30 nm), <200> preferential crystal face and a compact microstructure. It accounts for an improved resistance to free corrosion and pitting corrosion in 3.5 wt% NaCl aqueous solution. By contrast, the preferential crystal faces are <111> and <220> for Al deposits obtained from x = 0.1 and 0.2, respectively. Besides, Al deposits from x = 0.1 and 0.2 have a much loose structure compared to that from x = 0.4, thereby leading to a more negative E
corr and E
pit.

Figure 1
Comparison of Ni-Rich Li[Ni1
−x−YCoxAly]O2(NCA) Cathodes for Lithium-Ion Batteries Depending on Extent of Microcracks
Authors: Park Nam-Yung , Nam Gyeong Won , Sun Yang-Kook 
Published: December 2020

Ni-rich layered cathode materials Li[Ni1
−
x
−
yCoxMy]O2 (M = Al and Mn are denoted as NCA and NCM, respectively) are typical cathodes for the batteries of electric vehicles (EVs). In particular, Tesla, one of the most promising EVs producers, uses the Panasonic NCA cathode in its Model S. For the wide adoption of EVs, driving range need to be raised by the increase in energy density of lithium ion batteries (LIBs). However, developing LIBs which have high energy density with stable cycle life is mainly hampered by the cathode materials.
The general strategy for increasing the reversible capacity of NCM and NCA cathodes is to increase the relative Ni fraction in their composition. However, it is well acknowledged that increasing the Ni composition in NCM cathodes leads to the deterioration in both cycling performance and thermal stability.1 The fast capacity fading of Ni-rich NCM cathode is mostly attributed to the H2–H3 phase transition at the charged state, inducing an anisotropic lattice volume change generating internal microcracks in the particles.2 The extent of microcrack, which is a crucial factor dictating a performance of cathode material, increases as Ni fraction increases. Similar to NCM cathodes, Ni-rich NCA cathodes are also supposed to suffer from capacity fading and thermal instability problems owing to microcracks. To apply Ni-rich NCA cathodes in high-energy batteries for EVs, it is important to establish the capacity-cycling stability-thermal stability relationship depending on the extent of microcracks.
Based on the results in NCM cathodes, we investigated the comparative study of NCA cathodes whose Ni fraction are 80%, 88%, and 95% to assess their cycling stability and to determine the capacity limit that can be attained by Ni-rich NCA cathodes without substantial sacrifice of the cycling stability. In addition, The extent of microcracks during charging and discharging was focused to identify the capacity-fading mechanism of these Ni-rich NCA cathodes. The results can provide the technical and scientific basis for further material development of these cathodes.

Reference
s

1. H.-J. Noh, S. Youn, C. S. Yoon and Y.-K. Sun, J. Power Sources, 2013, 233, 121.
2. H.-H. Ryu, K.-J. Park, C. S. Yoon and Y.-K. Sun, Chem. Mater. 2018, 30, 1155.
Understanding Non-Uniformities in 3D Lithium-Ion Battery Electrode Architectures
Authors: Hung Chih-Hsuan , Allu Srikanth , Cobb Corie Lynn 
Published: December 2020

Conventional Lithium-ion intercalation batteries that are composed of planar cathode, separator, and anode layers have an intrinsic trade-off between energy density and power density. While thick electrodes allow for more active material loading and higher energy densities, thick electrodes lengthen ion transport pathways and limit power performance. Conversely, thin electrodes have fast ion transport at the cost of reduced material loading which leads to lower energy densities. Three-dimensional (3D) batteries can potentially mitigate this power and energy trade-off through electrode architecture. Unlike planar electrodes, 3D batteries have unique and integrated electrode architectures that can modify ion transport pathways in three-dimensions on a micron to millimeter scale. These architectures may be locally imbalanced in material loading, leading to nonuniform current density and local depletion of the electrode or electrolyte material. These nonuniformities can terminate a discharge or charge cycle prematurely. Although many 3D battery architectures have been proposed to date, few comparative modeling studies have been conducted for these architectures to understand their relative performance gains.
In this presentation, we will investigate the impact of 3D electrode architecture on current density uniformity and material lithiation at different discharge rates in several 3D batteries. Our batteries are simulated using the software CAEBAT: AMPERES
1
, which provides a 3D electrochemical model on the continuum level using volume-averaging techniques. 3D batteries with different parameterizations and geometries of interdigitated anode and cathode electrodes are studied. In addition, the effects of current collector placement, material loading, and electrode feature shapes are also presented.
1. Allu, S., Kalnaus, S., Simunovic, S., Nanda, J., Turner, J. A., and Pannala, S., J. Power Sources, 325, 42 (2016)
Electrodeposition of Cadmium Selenide on Silicon to Integrate the Semiconductors Properties
Authors: Giurlani Walter , Vizza Martina , Fabbri Lorenzo , Marcantelli Patrick , Martinuzzi Stefano , Lo Faro Maria Josè , Irrera Alessia , Innocenti Massimo 
Published: December 2020

Monocrystalline silicon has been considered for years among the materials at the base of the macro and micro-electronics industry. At the bulk state silicon is an intrinsic semiconductor whose conductive properties can be easily modulated by using doping agents. This feature combined with high availability and accessible production costs makes it particularly suitable for many applications based on semiconductor technology. With the development of vacuum deposition techniques, it has been possible to create systems that integrate monocrystalline silicon with other materials of technological interest, thus allowing the realization of highly performing devices. However, the use of these techniques is limited by special working conditions and very expensive instruments. An alternative to these techniques is the electrodeposition from aqueous solution. Studies on the deposition of materials of technological interest on gold and silver have been known for several years now. In this work we use the electrodeposition technique, with all the advantages it brings both in terms of costs and deposition quality, on monocrystalline 100 n-type silicon. The study dealt with the co-deposition and alternate deposition of the semiconductor cadmium selenide (CdSe) [1]. First of all, we carried out the electrochemical characterization of the precursors on the substrate to find the optimal conditions (pH and concentrations) for the deposition, then the deposition was performed using two different approaches: co-deposition (both the precursors present in the same solution) and charge controlled alternate deposition of the two components. Finally, deposits were characterized spectroscopically and microscopically: we found that, with the electrochemical method, we obtained to the formation of micro-clusters of CdSe on n-Si. The present study funded by the PRIN Project (“Progetti di Ricerca di Rilevante Interesse Nazionale”), “Novel Multilayered and Micro-Machined Electrode Nano-Architectures for Electrocatalytic Applications (Fuel Cells and Electrolyzers)”, grant number 2017YH9MRK.
References:
[1] Giurlani, W. et al. Electrodeposition of Nanoparticles and Continuous Film of CdSe on n-Si (100). Nanomaterials 9, 1504 (2019). 10.3390/nano9101504.
Smoothed Boundary Method Simulations of Complex Electrode Microstructures Using Adaptive Mesh
Authors: Malik Affan , Yu Hui-Chia 
Published: December 2020

Rechargeable battery electrodes comprise of highly complex microstructures and convoluted electrolyte courses. These configurations dictate the macrohomogeneous properties and electrochemical performances of the electrodes. In addition to the geometric complexity, multiple concurrent physical mechanisms take place in the electrochemical processes of charge-discharge cycles. Understanding these detailed processes occurring in the complex electrode microstructure is the key to improve the design of electrodes. In this work, we present a framework to implement detailed electrochemical simulations in complex electrode microstructures. The framework employs the Smoothed Boundary Method(SBM)[1] which allows simple and fast mesh generation for complex geometries. In SBM, a continuous domain parameter is utilized to distinguish the phases of electrode particles and electrolyte, wherein the particle-electrolyte interface is defined by the region where the domain parameter transitions from zero to one in a continuous manner. With the electrochemical governing equations reformulated using the domain parameter, conformal mesh to the complex geometries is circumvented in the simulations. The SBM is implemented with Octree-based adaptive mesh refinement (AMR)[2], in which fine cubic meshes are generated near the particle-electrolyte interfaces while coarse cubic meshes are used in the bulk regions of particles and electrolyte. As a result, the diffuse interface in the SBM is effectively decreased and the accuracy of the electrochemical simulations is comparable to those of conventional sharp-interface methods. Intercalation electrode materials, namely NMC for the cathode and graphite for the anode, are used in the simulations to reveal the detailed electrochemical processes in the complex electrode microstructures and as a demonstration of the presented simulation framework. Material parameters in the simulations are directly obtained from experimental data to study the electrochemical phenomena occurring in the microstructures. The results can be used to extract macrohomogeneous electrode properties in the Porous Electrode Modeling for device-level simulations. Thus, it is shown that the presented simulation framework can serve as a useful tool for examining the effects of electrode microstructures and intrinsic material properties on the electrodes’ performance and as well as for electrode design.
References:
[1] Hui-Chia Yu, Hsun-Yi Chen, and K Thornton. Extended smoothed boundary method for solving partial differential equations with general boundary conditions on complex boundaries. 2012.
[2] Chohong Min, Fr ́ed ́eric Gibou, and Hector D Ceniceros. “A supra-convergent finite difference scheme for the variable coefficient Poisson equation on non-graded grids”. In: J. Comput. Phys.218.1 (Oct. 2006), pp. 123–140.
Characterisation of Redox Species in Pure IL and Its Mixtures with a Molecular Solvent By Electrochemical Impedance Spectroscopy
Authors: Chaabene Nesrine , Ngo Kieu , Turmine Mireille , Vivier Vincent 
Published: December 2020

Ionic liquid (IL) are molten salt at room temperature. They are of ever increasing interest due to their outstanding properties and appear to be candidates for many electrochemical applications. Thus, there are more and more works concerning their use as electrolyte for storage or conversion energy1. For this application, the addition of redox species is needed. In such case, the electrochemical properties of these compounds in IL must be determined and especially the determination of their diffusion coefficient (D) and heterogeneous electron-transfer rate constant (k°). One of the drawbacks of IL is their important viscosity. To reduce it, a molecular solvent can be added2.
In this work, we studied the electrochemical properties of some redox compounds (Alizarine, Tempo, Quinone, iron chloride) in an aprotic IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, C2mimTFSI, and its mixtures with γ-butyrolactone (GBL) as molecular solvent. The addition of this solvent decreases drastically the viscosity of the medium, at 298K, from 30 mPa.s to 10 mPa.s for a molar fraction of IL about xIL = 0.5. The diffusion coefficient and heterogeneous electron-transfer rate constant of the four redox compounds in IL-GBL mixtures of different composition were determined by cyclic voltammetry and electrochemical impedance spectroscopy. For all these species the diffusion coefficients were about 10-7 to 10-8 cm2 s-1 and their value decreases when the IL content increases as expected, due to the viscosity of the medium. The same trend is observed for the heterogeneous electron-transfer rate constant values.

Martins, V. L.; Torresi, R. M., Ionic liquids in electrochemical energy storage. Curr. Opin. Electrochem.
2018,
9, 26-32.

Papović, S.; Bešter-Rogač, M.; Vraneš, M.; Gadžurić, S., The effect of the alkyl chain length on physicochemical features of (ionic liquids+γ-butyrolactone) binary mixtures. The Journal of Chemical Thermodynamics
2016,
99, 1-10.
Electrochemical Impedance Spectroscopy Study with a Blocking Symmetric Cell: Qualitative Analysis for Interface of Electrode-Electrolyte
Authors: Kim Wonhee , Kim Hyeong-Jin 
Published: December 2020

Li-ion transport which is the fundamental driving force affects to lithium-ion batteries performance thermodynamically and kinetically. A facile and accurate tool is needed to analyze Li-ion transport affected by the electrode structure and electrolyte. Electrochemical impedance spectroscopy (EIS) is a well-known tool to evaluate a battery system. The actual interface of electrode-electrolyte and Li-ion transport can be confirmed quantitatively by analyzing low frequency region of EIS.
Herein, symmetric cells with SOC 0 state electrodes are analyzed with complex capacitance. In low frequency, Li-ion is accumulated along the electrode surface in the symmetric cell assembled with SOC 0 state electrodes (SC-SOC 0). Therefore, the interface of electrode-electrolyte can be investigated using this cell configuration. The accumulated amount of Li-ion is expressed as a real capacitance (C') (Figure 1a). In addition, the time constant (τ) is the value representing double-layer formation time related with the transport of Li-ion (Figure 1b). This approach can be used as a fundamental tool to understand Li-ion batteries performance by studying the interface of electrode-electrolyte (Figure 1c).

Figure 1
Development of an Accurate Life-Time Prediction Model for Lithium-Ion Batteries
Authors: Atalay Selcuk , Sheikh Muhammad , Widanage Widanalage Dhammika 
Published: December 2020

The growing demand of lithium-ion batteries (LIBs) on electric vehicles requires a lifespan of 8-10 years on average for electric vehicles to satisfy the needs of successful market introduction. The life-time of LIBS is, however, typically the bottleneck, hence the fundamental understanding and development of a more accurate life-time predictive model is crucial to estimate the battery life-time without running experimental test for years. In this work, we present a physics-based LIB aging model able to predict aging behaviours associated with a multi-layered SEI, lithium-plating and porosity change. Our model demonstrates that it can predict the life-time of the battery accurately with the 98% goodness-of-fit-error for applied constant-currents and dynamic power duty cycles. It is an important modelling tool for vehicle designers and for the implementation of business models. A key contribution of this work is the parameterization of the aging model by experimental data, while aging simulation in the literature usually lacks the capture of the transition point from linear to nonlinear aging.
*This work has been supported by WMG’s High Value Manufacturing Catapult and APC6 Project H1PERBAT.

Figure 1
Electrochemical Control and Understanding of the Electronic and Optical Properties of ZnO Formed in Rechargeable Zn-Alkaline Batteries
Authors: Hawkins Brendan , Turney Damon E. , Jadhav Ankur , Yadav Gautam Ganapati , Kiss Andrew M. , Lambert Timothy N. , Banerjee Sanjoy , Messinger Robert J. 
Published: December 2020

Rechargeable alkaline batteries using zinc metal (Zn) electrodes are of significant interest for next-generation energy storage because of their high energy density, low cost, environmental friendliness, and inherent safety. Rechargeable Zn-alkaline batteries, however, have not been widely commercialized in part due to the low cyclability of Zn electrodes. At high depths of discharge, zinc oxide (ZnO) discharge product accumulates in the electrode, passivating the zinc-electrolyte interface and ultimately leading to cell failure. While the ZnO discharge product has been studied for decades, there is no general consensus on its local structure, composition, and electrochemical properties, nor on how these properties are affected by the electrode potential or cycling conditions.
In this work, we used in operando analytical techniques including X-Ray diffraction (XRD), confocal Raman spectroscopy, electrochemical impedance spectroscopy (EIS), and ultraviolet-visible (UV-vis) spectroscopy to demonstrate that the discharge product is proton-doped ZnO with oxygen vacancies, and that the electrical conductivity, band gap, and color vary systematically as a function of electrode potential. To investigate local hydrogen and zinc environments within the ZnO discharge product, we performed ex situ solid-state 1H, 2H, and 67Zn magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. Solid-state 1H and 2H NMR measurements establish that hydrogen environments change as a function of potential, while solid-state 67Zn NMR spectra indicate that the local zinc environments are distorted compared to ZnO generated via conventional routes. We also performed 2D 1H-1H exchange (EXSY) NMR measurements to investigate proton mobility between defect environments and acquired 1D 1H-1H dipolar-mediated double quantum-filtered MAS NMR spectra to establish through-space molecular-level proximities between proton sites. This work provides insights into the dynamics of zinc electrodes in alkaline environments, as well as how to electrochemically control the defect structures and electronic and optical properties of ZnO in alkaline media, which are expected to aid the development of next-generation Zn alkaline batteries and electronic devices utilizing ZnO.
Non-Destructive Analysis of Crystal Structure Changes of Component Materials in Cylindrical Lithium-Ion Batteries at Elevated Temperature By Synchrotron Radiation x-Ray Diffraction Measurement
Authors: Saito Yoshiyasu , Okada Ken , Kuratani Kentaro , Shikano Masahiro , Kobayashi Hironori , Hirooka Motoyuki , Unemoto Atsushi , Abe Makoto , Kawaji Jun , Okumura Takefumi 
Published: December 2020

Temperature is one of the important factors for lithium-ion battery (LIB) which accelerates degradation of the performance. In many cases, degradation mechanism is studied by post-mortem analysis with destruction of degraded LIBs to obtain their component materials. However, these studies has a risk that any chemical and structural changes may have occurred in the samples during preparation process after destruction. Hence, development of in-situ and non-destructive analytical methods are strongly required. In this study, we report x-ray diffraction (XRD) measurement system using synchrotron radiation facility by which cylindrical LIB itself can be used as the sample without destruction and XRD patterns of cathode and anode layers are obtained separately. In addition, temperature of the sample can be controlled between RT and 250 °C.
18650 type cylindrical LIBs were used as the sample of which capacity were ca. 1.2 Ah. The cathode active material was Li(Ni1/3Mn1/3Co1/3)O2 and the anode active material was graphite.
XRD measurement was performed at BL46XU in SPring-8 with Huber multi-axis diffractometer. The incident beam was high-energy (72 keV) x-ray. A LaBr3 scintillation counter was used as the detector. The temperature of the sample batteries was controlled by specially designed system. Figure 1 shows XRD patterns of the anode layer of a sample LIB located at 1.65 mm inner from surface of the case. While only stage-1 structure (LiC6) was observed at RT, a new peak of stage-2 (LiC12) appeared and increased after the temperature beyond 90 °C which suggested that self-discharge would be accelerated at 90 °C and above.

Figure 1