bluuebunny/crossref_metadata_2025_split huggingface dataset:
Parametrization of a Doyle-Fuller-Newman (DFN) Model for a Commercial 37Ah Li-Ion Battery and Validation with Incremental Capacity Analysis
Authors: Haber Marc , Genies Sylvie , Azaïs Philippe , Martin Alexis , Chandesris Marion , Raccurt Olivier 
Published: July 2022

Physico-chemical modeling is considered as a very interesting way of simulating the behavior of a Li-ion battery cell by linking its internal state to its performance and aging. However, an accurate parametrization of such models is necessary for a truly representative outcome. In the case of commercial batteries, the parametrization procedure is hardly ever entirely undergone, leaving room for parameters tweaking and inaccurate simulation results. In the framework of this work, over 70% of the parameters were measured for a Samsung SDI 37Ah Li-ion prismatic battery (NMC111/Graphite) for PHEV (Plug-in Hybrid Electric Vehicle) applications. A Doyle-Fuller-Newman (DFN) Pseudo 2D model is chosen based on the work of Dufour et al.1. The major electrochemical characterization technics and measurement results for every component in the cell will be presented. The cells were opened in the ante-mortem procedure2, materials were identified, geometrical parameters were measured and samples were taken for coin-cell experiments. A small portion of the electrolyte was recovered and studied to conclude that it was made of EC-DMC-EMC at 1:1:2 portions. A similar solution was synthetized in order to conduct ionic conductivity measurements at temperatures ranging from -30 to 60°C. Samples from the separator were taken for both effective ionic conductivity and porosity measurements. The tortuosity of the electrodes was calculated via an EIS (Electrochemical Impedance Spectroscopy) with a blocking-electrodes configuration, and finally the diffusion factor in the active particles was estimated via GITT (Galvanostatic Intermittent Titration Technique) experiments. A very slow current regime was used to lithiate and de-lithiate the active materials in a half-cell experiment for electrode balancing purposes. The model was compiled using COMSOL Multiphysics 5.5, and results were compared to validation experiments conducted on the full-setup prismatic cell. The charge curve was validated under different current and power regimes at 25°C, and the Incremental Capacity (IC) curve showed a reasonable accuracy. With this in hand, the following step would be to couple this performance model to an aging model and to compare the evolution of the IC peaks with the experimental aging.
References:

N. Dufour, M. Chandesris, S. Geniès, M. Cugnet, and Y. Bultel, Electrochimica Acta, 272, 97–107 (2018) http://www.sciencedirect.com/science/article/pii/S0013468618307229.

T. Waldmann et al., Journal of The Electrochemical Society, 163, A2149–A2164 (2016) https://doi.org/10.1149/2.1211609jes.

Figure 1
(Digital Presentation) Pulsed-Waveform Electrodeposition of Fe-W Brazing Interlayers for Fusion Applications
Authors: Garich Holly , Lee Katherine , Snyder Stephen , Skinn Brian 
Published: July 2022

Numerous government and commercial entities are currently engaged in research toward net-energy-positive nuclear fusion electricity generation technology, which if successfully developed would revolutionize the energy economy and have a significant beneficial impact on carbon emissions and anthropogenic climate change. One fusion subsystem with significant remaining engineering challenges comprises the multitude of divertor modules installed on the plasma-facing surface of modern nuclear fusion reactors. These divertors must absorb/conduct steady-state heat fluxes on the order of 10–20 MW/m2 in an extremely harsh environment, including high-energy neutron bombardment. One common material choice for the plasma-facing portion of these components is tungsten, which provides a high melting point, high sputtering resistance, low tritium retention, and other benefits. As the thermal conductivity of tungsten is somewhat low, however, these tungsten components are often paired with a heat sink made from a more thermally-conductive material, such as copper-chromium-zirconium alloy, CuCrZr. While these materials can be joined by a number of methods, such as diffusion bonding and brazing, the dramatic mismatch in coefficient of thermal expansion (CTE; ~4 μm/m/K and ~17 μm/m/K for tungsten and CuCrZr, respectively) has a significant detrimental effect on the joint strength under these high-temperature, high-heat flux conditions. Development of a means for mitigating this CTE mismatch is imperative for the use of these materials to be feasible in a practical fusion device.
This talk will present results to date on development of an electrodeposited functionally-graded iron-tungsten (Fe-W) interlayer system for mitigation of the CTE mismatch between tungsten and CuCrZr in brazed joints. In theory, an interlayer with a CTE functionally graded between “tungsten-like” and “copper-like” values should significantly mitigate the thermally-induced stresses at the tungsten/CuCrZr joint. A key objective of the work is to demonstrate sufficient control over the local interlayer composition, residual stress, and other properties by adjusting primarily the pulse/pulse-reverse electrical waveform parameters, so as to allow interlayer preparation from a single electrodeposition bath. Results from electrodeposition trials and mechanical testing of brazed joints under ambient conditions as an initial screen for interlayer performance will be discussed, in anticipation of high-heat flux testing of joint performance under fusion-relevant conditions, where the ultimate goal is demonstration of increased tungsten/CuCrZr joint lifetime under thermal load via inclusion of graded interlayers, as compared to similar joints without interlayers.

Figure Caption

(Left) Tungsten substrate with electrodeposited Fe/W interlayer. (Right) Brazed tungsten/CuCrZr sample with Fe/W interlayer.

Figure 1
Electrohydrodynamic Redox 3D Printing: Confined Electroplating of Alloys for Additive Manufacturing at the Submicron Scale
Authors: Nydegger Mirco , Porenta Nikolaus , Menétrey Maxence , Hammadi Souzan , Reiser Alain , Spolenak Ralph 
Published: July 2022

Combining the unprecedented design freedom in microscale additive manufacturing (AM) with the ability to control the chemical nature of each printed voxel could unlock unique possibilities for tailoring mechanical, chemical, electrical, optical and magnetic properties of metal microstructures. A variety of techniques for micro- and nanoscale AM has been proposed for the fabrication of device-grade metals and alloys [1]. Electrochemical approaches to small-scale AM generally lead to superior microstructures (in terms of porosity and contamination) compared with techniques that transfer pre-synthesized materials [2]. The deposition of alloys with controlled composition, however, remains a challenge with electrochemical small scale AM techniques.
In this talk, we will present our work on additive manufacturing of alloyed structures using electrohydrodynamic redox (EHD-RP) 3D printing [3]. EHD-RP is based on the deposition of solvent droplets containing metal ions onto a conductive substrate, where the solvent evaporates and the ions are reduced. In general, this technique allows the direct deposition of polycrystalline 3D metal structures with a resolution of approx. 250 nm and a feature size down to 100 nm. We will present our work in expanding the materials range of EHD-RP from the limited range reported previously to a wide range of metals and subsequently discuss in detail the direct deposition of alloys. As it will be shown, the approach of spatially confining electrodeposition enables the fabrication of multi-metal and alloyed structures with a chemical voxel size <400 nm, hence making a step towards chemically architected materials. We will show how we can control the composition of the deposited material and the challenges involved in its characterization.
In summary, we present a novel approach to the bottom-up manufacturing of locally alloyed microstructures, adding an additional parameter in the design of novel nano- and microstructured inorganic materials.
[1] L. Hirt, A. Reiser, R. Spolenak & T. Zambelli. Additive Manufacturing of Metal Structures at the Micrometer Scale. Adv. Mater., 29(17), 2017.
[2] A. Reiser, R. Spolenak et al. Metals by Micro-scale Additive Manufacturing: Comparison of Microstructure and Mechanical Properties. Adv. Funct. Mater., 30, 1910491, 2020
[3] A. Reiser, M. Lindén, P. Rohner, A. Marchand, H. Galinski, A. S. Sologubenko, J. M. Wheeler, R. Zenobi, D. Poulikakos & R. Spolenak. Multi-metal electrohydrodynamic redox 3D printing at the submicron scale. Nat. Comm., 10(1):1-8, 2019.

Figure 1
(Digital Presentation) Electrochemical Deposition of Sn-Cu Alloys for Applications in 3D Stacking in Microelectronics Industry
Authors: Radisic Aleksandar , Inoue Fumihiro , El-Mekki Zaid , Struyf Herbert , Hou Lin , Derakhshandeh Jaber , Beyne Eric , Hsia Chih-Hao , Chang Iris , Kuttner Elisabeth , Fluegel Alexander , Arnold Marco 
Published: July 2022

The use of eutectic Sn-Cu alloys in packaging applications in microelectronics industry is not something entirely new. However, this alloy was mostly used in large features and fabricated using metal powders and metallurgical deposition techniques. The diameter of an individual grain of the eutectic Sn-Cu powder is typically similar in size to the diameter of pillars or bumps currently used in 3D stacking, and if we were to check its usefulness as a solder on this scale, an alternative manufacturing technique had to be used.
We have electrochemically deposited Sn-Cu alloys having up to 10 wt.% Cu and explored its possible benefits when used as a solder in combination with different Under bump metallization (UBM) materials. Sn-Cu alloys were deposited on blanket and patterned coupons, and promising experiments then transferred to a wafer-scale, i.e. Sn-Cu alloys were deposited on 300 mm wafers in an industrial-type plating tool. A typical sample/wafer had a Cu seed with a diffusion barrier (e.g. TiW) underneath and patterned features defined with a photoresist mask. Characteristic dimensions of the patterned features were on the order of mm and cm (lines), (diameter)D50µm × (height)H60 µm (pillars), and D8µm × H15 µm (bumps). Cu, Ni, or Co were used as UBM layers.
Chemical composition of deposited alloys has been examined by using X-ray fluorescence (XRF), Micro X-ray fluorescence (Micro-XRF), Inductively coupled plasma mass spectrometry (ICP-MS), and Electron probe microanalysis (EPMA). Surface morphology and the shape of deposited features have been examined using Scanning electron microscopy (SEM) and Laser scanning microscopy (LSM), while thermodynamic properties have been studied using Differential scanning calorimetry (DSC). Within-wafer (WIW) and within-die (WID) height uniformity of the pillars has been analyzed using Falcon 630 Plus tool (Camtek Ltd), capable of capturing heights of all the structures on the wafer simultaneously. The kinetics of Intermetallic compound (IMC) formation have been studied in the number of selected samples by combining ex-situ Focused ion beam (FIB) and in-situ measurements of resistance change of the features during anneal/thermal ageing [1].
We will discuss possible benefits and drawbacks for use of electrochemically deposited Sn-Cu alloy solders in combination with different UBM layers based on these results.
References:
[1] Lin Hou, Jaber Derakhshandeh, Eric Beyne, and Ingrid De Wolf, “A Novel Resistance Measurement Methodology for in-situ UBM/Solder Interfacial Reaction Monitoring”, DOI 10.1109/TCPMT.2019.2950448, IEEE Transactions on Components, Packaging and Manufacturing Technology.

Figure 1
Optimization of Loading Content of Li4Ti5O12-Hard Carbon Composite Anode for the Fast Charging Li-Ion Battery
Authors: Saneifar Hamidreza , Liu Jian 
Published: July 2022

Fast charge of lithium-ion batteries (LIBs) needs anode and cathode materials operating at high current densities. Li4Ti5O12 (LTO) can enable fast lithium ion (Li+) transport due to its 3D crystal structure. Nonetheless, this material suffers from low specific capacity and high operating voltage. In contrast, Hard Carbon (H.C) with high specific capacity and low practical voltage is one of the promising anode materials for high-energy lithium-ion batteries. However, practical application of this material is compromised with its slow kinetic, and reduced cycling performance associated with irreversibly trapped ions in its structure [1]. In this report, effect of loading ratio of H.C and LTO composite anode on the electrochemical behavior of fast charging lithium ion battery is studied. Electrochemical characterization results show that a certain loading of H.C plays a critical role in improving the electrochemical performance of LTO-H.C composite electrodes. Specifically, superior cycling stability and specific capacity achieved for the composite electrode with 20 wt.% H.C. It is believed that composite electrodes with an optimized ratio can effectively contribute to Li-ion storage and form a robust protective solid electrolyte interface (SEI) on the electrode surface. The latter might minimize further electrolyte decomposition and continuous growth of the SEI layer upon cycling, then improves the cycling stability of the electrode. In addition, the cycling performance and rate capability of LiNiMnCoO2 (NMC) with different nickel (Ni) and manganese (Mn) contents were evaluated and compared. The results clearly suggest that higher Ni content can improve specific capacity (115 mAhg-1for NMC333 vs 149 mAhg-1 for NMC811 at 1C). However, cycling stability deteriorates with increasing the Ni content (77% capacity retention for NMC333 vs 45% for NMC811 after 300 cycles). It is postulated that electrodes with higher Ni content are susceptible to transition metal dissolution and side reactions at electrode-electrolyte interface, which could lead to performance degradation by impeding Li+ diffusion across the electrode, and irreversible consumption of Li+ [2]. Finally, the possibility of use of the optimized anode for fabricating full cell with the selected NMC cathode is investigated.

References:

[1] Weiss, M., Ruess, R., Kasnatscheew, J. et al. Fast Charging of Lithium‐Ion Batteries: A Review of Materials Aspects. Adv. Energy Mater 11,2101126 (2021).
[2] Lin, R., Bak, SM., Shin, Y. et al. Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials. Nat Commun
12, 2350 (2021).
The Influence and Degradation Mechanism of the Depth of Discharge on the Performance of NMC-Based Cathodes for Li-Ion Batteries
Authors: Guo Jia , Li Yaqi , Pedersen Kjeld , Gurevich Leonid , Stroe Daniel-Ioan 
Published: July 2022

Many factors affect the degradation behavior of lithium-ion (Li-ion) batteries and one of these is the depth of discharge (DOD). As Li-ion batteries are used, a reasonable DOD can not only extend their service life (by reducing the degradation rate) but can also reduce the frequency of the re-charging. Therefore, to investigate and clarify the effect of the DOD on cathode performance, we performed cycle aging tests on coin cells considering three DODs. Furthermore, we proposed a degradation mechanism, to account for the influence of the DOD on the cathode performance, through ex-situ post-mortem analysis.
The investigated positive electrode was from a commercial cathode NMC 532, assembled with a lithium metal anode in a 2016 type coin cell. The initial discharge capacity was about 163 mAh g–1 at a 1 C rate (1C taken as 160 mAh g–1). After every certain number of cycles, the 100% DOD (2.75 – 4.3 V) capacity was measured and recorded for all DOD ranges.
Our cycle aging test experiment results (in the below Figure) show that the capacity fades faster in the higher DOD range (i.e., 3.65 – 4.3 V); the capacity of coin cells showed an initial increase due to the initial activation and a rapid decline thereafter. In contrast, the battery capacity faded slower in the two lower DOD ranges (i.e., 2.75 – 4.3 V and 3.55 – 4.3 V). The results also show that the higher DOD makes the battery more active during the initial cycles, as shown in the Figure.
We refined and analyzed the XRD results of different states of the charged cathode to calculate the change in unit cell volume in initial different DOD cycles. By calculating the Li-ion diffusion coefficient through the EIS measurements, it was found that it is larger in the higher state of charge (SOC) state, which explains the higher activity of the cathode in a higher DOD range. Furthermore, we disassembled and analyzed the coin cells, after the same numbers of equivalent full cycles. Surface microcracks of the cathode were observed by SEM, and the cathode-electrolyte interphase (CEI) film was analyzed and quantified by XPS technology.
Based on these results, we concluded that higher DODs enable the material to maintain a faster Li-ion diffusion rate and are always in a highly activated state. At the same time, it leads to a faster cathode decay. The post-mortem analysis showed the detailed mechanism of degradation. Looking at the results of this study, frequent charging, making the battery operation at a higher voltage, aggravates deterioration of the cathode.
Acknowledgments
This project has received funding from the China Scholarship Council (no. 202006370035; no. 202006220024). Furthermore, the authors would like to thank Haidi company for providing the cathode material.

Figure 1
Difluorophosphoric Acid Generation and Crossover Reactions in LiNixCoyMnzO2 Cathodes
Authors: Jayawardana Chamithri , Lucht Brett L. 
Published: July 2022

Layered LiNixCoyMnzO2 (NCM) materials are one of the most widely utilized cathode materials for Lithium-ion batteries (LIB) with their high theoretical capacity and relatively high voltage window. Increasing the Nickel content and the cycling voltage can increase the capacity of these cells at a lower cost. But these high Nickel cathodes cycled to a higher upper cut off voltage have poor cycling stability. The cause of this rapid capacity decrease has been attributed to decomposition of the anode solid electrolyte interphase (SEI) from transition metal deposition on the anode surface and impedance growth on the cathode surface. Recent studies have also attributed this to acidic species generated from oxidative decomposition of the electrolyte and their crossover reactions degrading the SEI, particularly the Difluorophosphoric acid.
In this study the role of transition metal dissolution and Difluorophosphoric acid generation has been investigated through various quantitative analysis techniques including, ICP-MS, XPS, quantitative solution NMR, and EIS. Full cells were constructed using graphite as the negative electrode and NCM cathodes with different Nickel contents as the positive electrode. These cells contain the same base electrolyte formulation (1.2M LiPF6 and EC: EMC, 3:7) and they were cycled at different temperatures and voltages to investigate the correlation between acid and transition metal concentration, cell voltage and capacity fade.
Aryl Diazonium- and Pyrene-Functionalised Graphite for Lithium-Ion Batteries
Authors: Bauer Marina , Pfeifer Kristina , Radinger Hannes , Luo Xianlin , Konnerth Philipp , Bauer Felix , Scheiba Frieder 
Published: July 2022

One of the main reasons for battery aging in lithium-ion batteries (LIBs) is the formation of a solid electrolyte interphase (SEI). SEI formation results in capacity loss and power fading due to irreversible electrochemical decomposition of electrolyte. However, the SEI protects the negative electrode from further parasitic surface reactions with the electrolyte. Therefore, it is of great interest to learn more about factors influencing the SEI and its formation. One approach is to modify the surface of the active material.
Since graphite is commonly used as negative electrode material in LIBs, we modified graphite with anchor molecules featuring functional groups. In particular, we use aryl diazonium salts and pyrenes as anchor molecules to cover a covalent and a non-covalent approach. The influence of different functional groups on the electrochemical properties of graphite electrodes is investigated. Furthermore, the importance of the modification method and the influence of the anchor molecule is addressed. The functional groups of modified graphite electrodes enable further layer growth, which is an important aspect for the design of an artificial SEI.
For surface and electrochemical characterisation of the modified graphite samples, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and galvanostatic cycling are used.
Financial support of the German Research Foundation (DFG) within the project B2 of the Collaborative Research Centre (SFB 1176) is kindly acknowledged.
(Invited) Atom Probe Tomography: A New Tool For the Analysis of Solid Liquid Interfaces?
Authors: Schmitz Guido 
Published: July 2022

Atom probe tomography is an established method for the microsocopic analysis of hard materials, which stands out by combining single-atom sensitivity with a 3D volume reconstruction. The method is based on laser-assisted field evaporation from nanometric emitter tips. In solid state reactions it delivered decisive information to understand the detailed conditions of nucleation and growth of product phases. In recent efforts, we desire to break the materials limitations aiming for application to liquids, softmatter and polymeric materials. To this end, a new instrument has been constructed that joins cryogenic ion beam preparation with a flexible transfer into an atom probe chamber. Meanwhile, we are able to produce nanometric needles from frozen liquids, even from pure water [1]. Studies are performed with aqueous solutions [2], liquids of short alkanes [3], self-assembling monolayers [4]. The talk discusses the field desorption of complex materials and presents time of flight mass spectra and their dependence on field or laser intensity. The complex mechanisms of field desorption from frozen water surfaces are further elucidated by DFT and Monte-Carlo simulation. Finally, by evaluating evaporation probabilities and event correlations, even insight in bonding strength and the stability of molecules in strong electrical fields may be provided.
[1] T. M. Schwarz, E. M. Weikum, K. Meng, E. Hadjixenophontos, C. A. Dietrich, J. Kästner, P. Stender, G. Schmitz, Field evaporation and atom probe tomography of pure water tips, Nature Scientific Reports (2020) 10:20271 | (DOI: 10.1038/s41598-020-77130-x
[2] T. M. Schwarz, C. A. Dietrich, J. Ott, E. M. Weikum, R. Lawitzki, H. Solodenko, E. Hadjixenophontos, B. Gault, J. Kästner, G. Schmitz, P. Stender, 3D Sub-Nanometer Analysis of Glucose in an Aqueous Solution by Cryo-Atom Probe Tomography, Scientific reports 11 (2021) 11607 (DOI: 10.1038/s41598-021-90862-8)
[3] Kuan Meng, Tim Schwarz, Eric Weikum, Patrick Stender, Guido Schmitz, Frozen n-Tetradecane investigated by cryo-Atom Probe Tomography, J. Microsc. Microanal. (2021), 1-11; (DOI:10.1017/S14319276210125)
[4] Helena Solodenko, Patrick Stender, Guido Schmitz, “Atom Probe Study of 1-octadecanethiol self-assembled Monolayers on Platinum (111) and (200) surfaces”, J. Microsc. Microanal. (2021), 1–10. (DOI: 10.1017/S1431927621012654)