bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Comparison of Transition Metal Oxide Ordered Macroporous Materials Used in Battery Electrodes
Authors: McNulty David , O'Hanlon Sally , Carroll Aoife , Lonergan Alex , O'Dwyer Colm 
Published: July 2021

This talk will summarize recent results of ordered macroporous (inverse opal) materials made from a range of transition metal oxides when used as Li-ion battery electrodes. The basic methodology for macroporous material formation will be presented for electrodes fabricated with macroporous ordered materials included TiO2, SnO2, GeO2, V2O5, their mixtures and other compounds.
The talk will compare the basic lithiation response in these porous materials in Li-in battery half cells and detail the electrochemical response of each oxide and porous structure as a function of specific current (rate) and cycle life. Several of these materials offer surprisingly good electrochemical stability during long (>5000 cycles in the case of TiO2) cycle life, in a binder and conductive additive-free electrode formulation. We also summarize limits of some macroporous oxide materials at very high charge and discharge rates when used in Li-ion batteries and compare the influence of phase and structure on reversible lithiation.
Related work and References

O'Hanon, D. McNulty, R. Tian, J. Coleman, and C. O'Dwyer, High Charge and Discharge Rate Limitations in Ordered Macroporous Li-ion Battery Materials, J. Electrochem. Soc. 167, 140532 (2020).

McNulty, H. Geaney, Q. Ramasse, and C. O'Dwyer, Long Cycle Life, Highly Ordered SnO2/GeO2 Nanocomposite Inverse Opal Anode Materials for Li‐Ion Batteries, Adv. Funct. Mater., 2005073 (2020).

McNulty, H. Geaney, D. Buckley, and C. O'Dwyer, High Capacity Binder-free Nanocrystalline GeO2 Inverse Opal Anodes for Li-ion Batteries with Long Cycle Life and Stable Cell Voltage, Nano Energy 43, 11 (2018).

McNulty, E. Carroll, and C. O'Dwyer, Rutile TiO2 Inverse Opal Anodes for Li-ion Batteries with Long Cycle Life, High-rate Capability and High Structural Stability, Adv. Energy Mater. 7, 1602291 (2017).

McNulty, A. Lonergan, S. O'Hanlon, and C. O'Dwyer, 3D open-worked inverse opal TiO2 and GeO2 materials for long life, high capacity Li-ion battery anodes, Solid State Ionics 314, 195 (2018).

Lonergan, D. McNulty, and C. O'Dwyer, Tetrahedral framework of inverse opal photonic crystals defines the optical response and photonic band gap, J. Appl. Phys. 124, 095106 (2018).

O'Hanlon, D. McNulty, and C. O'Dwyer, The influence of colloidal opal template and substrate type on 3D macroporous single and binary vanadium oxide inverse opal electrodeposition, J. Electrochem. Soc. 164, D111 (2017).

O'Dwyer, Colour-Coded Batteries – Inverse Opal Materials Circuitry for Enhanced Electrochemical Energy Storage and Optically Encoded Diagnostics, Adv. Mater. 28, 5681 (2016).
Electrolyte with New Composition for High Nickel Lithium Ion Batteries
Authors: Liao Chen , Yang Jianzhong , Son Seoung-Bum , Rodrigues Marco-Tulio , Abraham Daniel P. 
Published: July 2021

We previously reported1-4 the in situ electrolyte additives to selectively synthesize the beneficial lithium tetrafluorophosphate components in high yield (> 98%) and maximize the battery performance. The in situ method is particularly of interest to scale up electrolyte preparation since it would alleviate any requirements of extra separation and purification of the desired additives.
Here we used a new strategy of change both the composition and materials in the standard electrolyte to formulate advanced electrolytes for lithium ion batteries (LIBs). New electrolytes for high voltage LIBs were demonstrated to be more effective than the previous additives. The LIBs containing Ni-rich cathodes cycled with the new electrolytes in optimal composition rendered better electrochemical performance than cells cycled with the start-of-art Gen2 electrolyte when cycled between 3.0 to 4.2 V, exhibiting effective suppression of the impedance rise during aging. 1H Nuclear Magnetic Resonance spectra of cycled new electrolyte suggested their capabilities in preventing the transesterification reactions on anode surface, while X-ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry analysis indicated its ability to form a stable cathode interface and mitigate structural damage on the cathode surface. Further analysis also indicated the benefits of the new composition electrolyte in protecting the cathode bulk structure.
[1] J. Yang, I. Shkrob, K. Liu, J. Connell, N. L. Dietz Rago, Z. Zhang and C. Liao, Journal of The Electrochemical Society, 2020, 167, 070533.
[2] C. Liao, eTransportation, 2020, 5, 100068.
[3] J. Yang, I. Shkrob, Q. Liu, N. L. Dietz Rago, Y. Liu, K. Liu, Z. Zhang and C. Liao, Journal of Power Sources, 2019, 438, 227039.
[4] I. A. Shkrob, B. Han, R. Sahore, A. P. Tornheim, L. Zhang, D. P. Abraham, F. Dogan, Z. Zhang and C. Liao, Chemistry of Materials, 2019, 31, 2459-2468.
Ni-Rich Li[Ni0.9Co0.045Mn0.045Al0.01]O2 (NCMA) Cathode with Optimized Microstructure for Microstrain Control
Authors: Park Nam-Yung , Yoon Dae Ro , Sun Yang-Kook 
Published: July 2021

Layered Ni-rich cathode materials Li[Ni
x
Co
y
M
1-x-y
]O2 (M = Mn and Al are denoted as NCM and NCA, respectively) has been common cathodes for the batteries of electric vehicles (EVs). Recently, Li[Ni
x
Co
y
Mn
z
Al1-x-y-z
]O2 (NCMA), a hybrid of NCM and NCA cathodes, has received significant attention owing to the announcement by General Motors of its intention to deploy NCMA cathodes for Li-ion batteries (LIBs) in its next EVs.1 The NCMA cathode can provide high discharge capacity with stable cycle life owing to strong Al-O bonding which strengthens the host layered structure. However, an introduction of the high concentration of Al dopant for stabilization of Ni-rich cathodes is restricted as an electrochemically inactive Al lowers the capacity of cathode.
For Ni-rich cathodes, it is well acknowledged that increasing the Ni composition in the cathodes for higher capacity leads to the deterioration in both cycling performance and thermal stability.2 The fast capacity fading of Ni-rich cathode is mostly attributed to the H2–H3 phase transition at the charged state, and the extent of H2–H3 phase transition increases with increasing Ni fraction in the cathodes. As the phase transition induces a lattice volume change generating microcracks in the particles, the alleviation of internal microstrain is required to suppress the microcrack formation in the cathode particles and to improve the cycling stability of Ni-rich cathodes.
To reinforce the mechanical stability of Ni-rich NCMA cathodes, we proposed a hybrid structure cathode in which Li[Ni0.92Co0.04Mn0.03Al0.01]O2 in the interior of the particle is encapsulated by Li[Ni0.845Co0.067Mn0.078Al0.01]O2 that acts as a buffer against the microstrain. Similar to the tempered glass which has different states of stress in the surface and bulk material to increase the strength,3 the proposed cathode structure suppresses the formation of microcracks by creating a non-uniform spatial distribution of microstrain within the cathode particle. The electrochemical performance of the proposed cathode is correlated with the microstructure, and the mechanism suppressing the formation of microcracks in the Ni-rich NCMA cathode is demonstrated.

Reference
s
:

[1] General Motors Co. LYRIQ Show Car Leads Cadillac Into Electric Future, 2020; https://media.gm.com/media/us/en/cadillac/news.detail.html/content/Pages/news/us/en/2020/aug/0806-lyriq.html (accessed December 2020).
[2] H.-J. Noh, S. Youn, C. S. Yoon, Y.-K. Sun, J. Power Sources, 2013, 233, 121.
[3] A. L. Zijlstra, A. J. Burggraaf, J. Non-Cryst. Solids, 1968, 1, 49.
Ni-Rich Li[Ni1−x−YCoxBy]O2 Cathode Materials for Next Lithium Batteries
Authors: Ryu HoonHee , Yoon Dae Ro , Sun Yang-Kook 
Published: July 2021

To achieve a longer driving range of electric vehicles (EVs) per charge, it is necessary that the development of advanced cathode materials, which largely determine the capacity of lithium-ion batteries. Currently, classical cathodes deployed in current EVs, layered Li[NixCoy(Al orMn)1−x−y]O2 (Al = NCA or Mn = NCM) oxide materials, has achieved the best performances for commercialization. However, these cathodes should be further improved to be competitive in the global market.1 Ni-rich NCA and NCM cathodes, delivering ever-closer to their theoretical specific capacity, are considered as promising candidates. However, increasing Ni content compromises battery lifetime and thermal stability due to rapid capacity fading and an abundance of unstable Ni4+ species, as observed in LiNiO2.2,3 Therefore, the development of new cathode materials that can overcome rapid capacity fading is necessary.
In this presentation, we suggest a novel cathode material by introducing boron to the binary system Li[Ni0.9Co0.1]O2 (NC90) to create a new class of layered cathode materials, Li[Ni1−x−yCoxBy]O2 (NCB), to supplement NCM and NCA.4 The microstructure of NCB cathodes was tailored by adjusting the boron fraction, as the shape and dimensions of the primary particles depend on the boron fraction. The dramatic difference between the particle microstructure of an NCB cathode and those of NCA and NCM cathodes was confirmed. The NCB cathode exhibited a higher capacity with outstanding capacity retention, compared to the conventional NCA and NCM cathodes. A series of NCB cathodes with 0.5, 1.0, 1.5, and 2 mol% B systematically characterized to investigate the capacity fading mechanism and to determine the optimal microstructure for better cycling stability.
References

D. Andre, S.-J. Kim, P. Lamp, S. F. Lux, F. Maglia, O. Paschos, B. Stiaszny, J. Mater. Chem. A
2015, 3, 6709.

H.-H. Ryu, K.-J. Park, C. S. Yoon, Y.-K. Sun, Chem. Mater.
2018, 30, 1155.

D.-W. Jun, C. S. Yoon, U.-H. Kim, Y.-K. Sun, Chem. Mater.
2017, 29, 5048.

H.-H. Ryu, N.-Y. Park, D. R. Yoon, U.-H. Kim, C. S. Yoon, Y.-K. Sun, Adv. Energy Mater.
2020, 10, 2000495.
Physics-Based Impedance Model of Lithium Sulfur Batteries
Authors: Teo Linnette , Parke Caitlin D. , Schwartz Daniel T. , Subramanian Venkat R. 
Published: July 2021

Time domain physics-based models for lithium sulfur have been developed with mechanisms of the reaction cascade and precipitation reactions, allowing for a deeper understanding of internal states of the battery.1 Such models are able to capture voltage curves well during discharge. However, there have been challenges to reproduce charging curves accurately. It has been suggested that the charge and discharge reaction pathways are different,2 and/or precipitation rates and expressions to take into account numerical instability associated with dissolution when charging need to be improved.3,4 Since it is challenging for existing physics-based models to demonstrate macro-reversibility, we aim to see if there is evidence of micro-reversibility as impedance modeling would require these mechanistic models to work over much smaller changes in state-of-charge. Applying such models to the frequency domain can also give us detailed insight on proposed mechanisms and processes that occur across a larger range of timescales that are not available during a slow charge/discharge.
Fronczek and Bessler5 have simulated electrochemical impedance spectroscopy (EIS) spectra based on mechanisms in the widely accepted one-dimensional model developed by Kumaresan et al..1 They are the first to demonstrate this with a physics-based modeling approach using a potential step in the time domain and performing FFT on the current relaxation to obtain the impedance. We aim to extend this further by comparing to experimental trends seen in the literature6,7 and explore qualitative features in the EIS spectra based on physical processes. We use a different computational approach by transforming the governing equations in the Kumaresan model to the frequency domain. We present this system of linearized ordinary differential equations and solve them in a manner consistent with numerical approaches demonstrated previously.8

Acknowledgement
This work was supported by the Advanced Battery Material Research (BMR) Program (Battery 500 Consortium).
References

K. Kumaresan, Y. Mikhaylik, and R. E. White, J. Electrochem. Soc., 155, A576 (2008).

Q. Wang et al., J. Electrochem. Soc., 162, A474–A478 (2015).

K. Yoo, M.-K. Song, E. J. Cairns, and P. Dutta, Electrochimica Acta, 213, 174–185 (2016).

N. Kamyab, P. T. Coman, S. K. Madi Reddy, S. Santhanagopalan, and R. E. White, J. Electrochem. Soc., 167, 130532 (2020).

D. N. Fronczek and W. G. Bessler, Journal of Power Sources, 244, 183–188 (2013).

S. Waluś, C. Barchasz, R. Bouchet, and F. Alloin, Electrochimica Acta, 359, 136944 (2020).

Z. Deng et al., J. Electrochem. Soc., 160, A553–A558 (2013).

M. Pathak et al., J. Electrochem. Soc., 165, A1324–A1337 (2018).
(Invited) Designing Intercalation for High-Valent & Uniform Redox Reactions
Authors: Chueh William C. 
Published: July 2021

Many electrochemical materials attain high-valent oxidation state during operation, such as electrocatalysts for oxygen evolution reactions and positive electrodes for lithium-ion batteries. For the latter, the high voltage enabled by high valent redox can further increase the energy density of batteries. In oxides, achieving high oxidation states is typically accompanied by substantial bond contraction as well as participation of the O 2p electronic states, both of which are known to affect the stability and reversibility of the redox reaction. In addition to high valent redox, another desirable characteristic of electrochemical reaction is uniformity. This is especially true for intercalation electrochemistry, since the uniformity directly establishes the mechanical stress within the electrode.
In this talk, I will use lithium- and sodium-intercalating layered oxides as a prototypical system for establishing design rules for high-valent and uniform redox. For the first part of the talk, I will discuss the convergence of three phenomena that control the stability of high valent redox: short covalent bonding, mitigation of local strain energy through point defect formation, and coulombically stabilization of oxidized species. In the second part of the talk, I will rationalize unexpected mesoscale heterogeneities such as apparent phase separation in layered oxides, and provide practical design rules on engineering more uniform electrochemical devices.
Aqueous Li4Ti5O12/LiMn2O4 Cell with a Li-Ion Conducive Solid Electrolyteseparator and an Electrodeposition of Zn to an Anode
Authors: Seki Hayato , Yoshima Kazuomi , Yamashita Yasunobu , Takami Norio , Matsuno Shinsuke 
Published: July 2021

Li-ion batteries (LIBs) with non-aqueous electrolytes have high-energy density, highpower density, and long-cycle performance. However, generally LIBs have a risk due to their flammable organic electrolytes. Until now, a lot of attempt to reduce the risk of LIBs have been conducted such as all-solid-state battery. We have focused on Li-ion batteries with aqueous electrolytes with safer and low cost, but the electrochemical stability window of aqueous electrolytes is narrower than that of the organic electrolytes in LIBs. The stable operating voltage window of an aqueous electrolyte is approximately 1.23 V thermodynamically, beyond which the electrolysis of H2O occurs along with the evolution of H2 or O2 gas. To achieve an aqueous Li-ion battery with high discharge voltage, a suppression of H2 gas on the anode is needed.
In this study, we report the widening of the overall electrochemical stability window with a Li-ion conductive solid electrolyte (SE) separator composed of NASICON-type Li-Al-Ti-P-O glass ceramic and an electrodeposition of Zn to an anode. We utilized a SE separator to suppress the H2 gas evolution on the anode electrode by preventing H+ migration from a cathode electrolyte. And we tried to electrodeposit Zn to the anode, since Zn shows a high hydrogen over voltage. A cathode, an anode, and an aqueous electrolyte was used as LiMn2O4, LiTi4O12, and 12 mol/L LiCl respectively. A Li-ion conductive solid electrolyte with a thickness of 150 μm and the conductivity of 10-4 S/cm at 25°C was used as the SE separator. We fabricated a LTO/LMO cell with the SE separator and a porous separator(1. Typical charge/discharge curves with SE separator and electrodeposition of Zn to LTO anode is shown in Fig. 1 (a). The aqueous LTO/LMO cell exhibited an average discharge voltage of over 2.4 V, a coulombic efficiency of over 94%, and good cycle perfromance. Compared to a cell with porus separator and no electrodeposition of Zn, the evolution of H2 gas on the LTO anode during charge in the LTO/LMO cell was kinetically suppressed and decreased to 1/6 as shown in Fig. 1 (b).

Figure 1
TaN-Based Combined Barrier+Liner Materials to Beat the Interconnect Bottleneck
Authors: Nies Cara-Lena , Kondati Natarajan Suresh , Nolan Michael 
Published: July 2021

In order to prolong the lifetime of Cu as an interconnect metal in CMOS devices, as transistors continue to decrease in size, materials that combine properties of diffusion barriers and seed liners are needed. Such a material will have to allow for successful electroplating of Cu and must be as thin as possible in order to facilitate the coating of high-aspect ratio interconnect vias. One possible way to achieve such a material is presented in this study. Through density functional theory we investigate the behaviour Cu on Ru-doped and Ru passivated ε-TaN (1 1 0). Adsorption and diffusion of one and two Cu atoms on these surfaces were studied initially, in order to understand the early stages of film growth. This showed that while adsorption and surface diffusion were more favourable on the Ru passivated surface, Ru dopants act as a nucleation site for Cu atoms and enhance the metal-surface interaction.
To understand the growth mechanism of Cu films on these surfaces in more detail, and to discover the optimum Ru content for the surface, large Cu sheets are adsorbed to the Ru passivated surface as well as to Ru-doped surfaces with a variety of surface doping concentrations.
On the Ru-doped films, Cu spontaneously transitions into a two-layer structure, while atoms remain in a single layer on the Ru-passivated surface. However, ab initio molecular dynamics and activation energies of pathways for migration of atoms to form further layers show that the Ru dopants inhibit further 3D growth of the Cu structures.
Boosting Static and Dynamic Performance of Integrated Solid-State Diodes By Peripheral Integration of Nanostructured Porous Silicon
Authors: Paghi Alessandro , Strambini Lucanos , Toia Fabrizio , Sambi Marco , Marchesi Marco , Depetro Riccardo , Morelli Marco , Barillaro Giuseppe 
Published: July 2021

Over the past two decades, different nanomaterials have been proposed for the design of novel silicon-based electronic devices or to push the performance of existing ones, leveraging the unique properties of charge carriers traveling in meso-to-nano scale structures.
Porous silicon (PSi) is the nano- (n-PSi) to micro- (m-Psi) structured form of silicon achieved by anodic etching of a silicon wafer in acidic HF-based electrolytes. However, the low mobility and reduced lifetime of charge carriers traveling in n-PSi have been mainly perceived such as a deterioration the bulk silicon properties, thus hampering the use of n-PSi in micro and nano electronics to date.
Here, we show that the integration of n-PSi in specific regions of a solid-state diode significantly improves both static and dynamic electrical performance of the diode, with respect to the unmodified device. Specifically, leveraging the unique mobility and lifetime of charge carriers traveling in the n-PSi layer, we achieve a significant increase of the breakdown voltage (>2x) and reduction of the turn-off time (about 30%). This improvement is shown to be robust with respect to n-PSi preparation conditions and diode typologies. Two dimensional (2D) TCAD simulations further corroborate that the improvement of the electrical performance of n-PSi modified diodes is related to the strong mobility and lifetime reduction of carriers in the nanostructured porous silicon layer. Remarkably, no significant drawbacks are observed after the peripheral integration of n-PSi in solid-state diodes, thus confirming the beneficial effect of n-PSi when employed for the modification of micro and nano electronic devices.
A. Paghi, L. M. Strambini, F. F. Toia, M. Sambi, M. Marchesi, R. Depetro, M. Morelli, G. Barillaro, Peripheral Nanostructured Porous Silicon Boosts Static and Dynamic Performance Of Integrated Electronic Devices, Advanced Electronic Materials 6, 2000615 (2020).
(Invited) Heterogeneous Integration As Enabler for Future Applications and Products
Authors: Braun Tanja , Becker Karl-Friedrich , Töpper Michael , Aschenbrenner Rolf , Schneider-Ramelow Martin 
Published: July 2021

Future electronic systems like autonomous systems using high performance computing (HPC) and edge computing systems, sensor integrated systems and bio-integrated devices will required more and more functions which cannot be managed by a single chip, even if advanced SoC (System on Chip) concepts are used. Heterogeneous integration will be the next step and will pass beyond current SiP (System in Package) approaches. This concept of true heterogeneous integration is highly important for next-gen devices based on future CMOS-nodes, SiGe, SiC, III/Vs like GaAs or GaN and all different kinds of MEMS.
Besides die and package stacking, embedding dies is a key technology for heterogeneous system integration. There are two main approaches for embedded die technologies: Fan-out Wafer and Panel Level integration, where dies are embedded into polymer encapsulants and Chip in Polymer, where dies are embedded into the substrate.
Besides multiple die packaging also the integration of passive components as capacitors or resistors as well as the integration of shielding layers, antennas and e.g. resonators in and on package is a key for future applications. Co-design of chip and package for miniaturized heterogeneous packages will also give benefits especially for high frequency applications as 5G and beyond. The extension of advanced process design kits (PDK) towards packaging technologies including larger process tolerances and a much larger number of materials and processes would also support the approach of chip and package co-design.
Another trend is moving from planar embedding technology to 3D shaped integration. Conformal electronics offer a functional shape adapted system with embedded electronics for e.g. sensors with aligned sensing direction, 3D shaped high frequency antennas or geometrically adapted electronics to the environment.