bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemically Modulated CO2 Removal from Oceanwaters
Authors: Kim Seoni , Rufer Simon , Lake Jack , Nitzsche Michael , Kang Jin Soo , Varanasi Kripa , Hatton T. Alan 
Published: November 2022

As the concentration of carbon dioxide is continuously increasing, there have been a lot of efforts to remove CO2 from various sources. While most of the attention has been focused on CO2capture at point sources followed by geological storage, interest in negative emission strategies also increased recently. One of the promising approaches for negative emissions is removing CO2 from ocean water. The world ocean is the largest carbon sink, containing 120 times higher concentration compared to the atmosphere. Therefore, by removing CO2 from ocean water, we can expect a reduction in CO2 concentration in the atmosphere.
Considering that the CO2-reduced oceanwater should be returned to the ocean, the addition of chemicals, and the formation of undesirable compounds should be avoided. In this respect, the electrochemical approach can be a good choice because it does not require additional chemicals, and the control of voltage can tune the reactions in the system. Until now, several approaches have been made by using the electrodialysis process. However, the use of bipolar membrane for water dissociation makes this process expensive, making the application of this process sluggish.
In this talk, we will present a new membrane-free approach based on electrochemical modulation of the pH to release the CO2 from ocean water. After removing CO2, the treated water is alkalized before being returned to the ocean. Using an electrochemical pH swing approach, we could successfully remove the CO2 from ocean water without employing expensive membrane or additional chemicals.
(Invited) Management Systems for Lithium-Ion Batteries
Authors: McCann Gerry 
Published: November 2022

Battery management systems (BMS) for large Li-ion batteries are, of themselves, complex systems. The complexity starts with voltage measurement for individual cells. Large batteries may have 96, 192, or more, series connected cells, so requiring complex wiring harnesses. The high noise environment provides additional challenges for wiring and also analog front end and analog to digital conversion system design. For safety, and to help with state-of-charge (SOC) estimation, temperature sensors must be located throughout the battery. A computational infrastructure estimates SOC for each cell. The estimate is typically based on cell voltage, measured current, estimated cell resistance, integrated current and temperature. Additionally, cell capacity imbalance, whether present from the start or evolved over time, must be corrected.
This talk will attempt to provide some insight into BMS design for mass-produced large batteries. The applications, whether for electric vehicles (EV) or stationary storage, are generally safety critical, so placing additional demands on the BMS. Typically, the BMS also manages the interaction between the battery and the remainder of the system. It sets limits for allowed charge and discharge currents and can interrupt current and disconnect the battery if limits are exceeded. This area will also be addressed, with a particular focus on fusing challenges for EV applications. Power transfer of 500 kW or more may be required. Depending on the application this may be for only a few seconds, or it may be indefinite. In additional to safety, reliability is also critical. For example, the many required cell connections must remain intact for the intended service life of the installation. This will be addressed, touching also on design of the overall battery pack.
(Invited) The Long Reach of Impedance Measurements: From Flow Cells and Dielectrics to Experimental Artifacts
Authors: Vanysek Petr 
Published: November 2022

The motivation for this presentation is to bring into perspective experience in collecting and interpreting impedance data and put this in interesting and relevant form in front of specialists in electronic materials and processing.
Impedance spectroscopy became very popular among electrochemists ever since most modern potentiostats started incorporating hardware for collecting impedance and software, for interpretation of putative equivalent circuits. The popularity stems both from usefulness of the method, when judiciously applied, and from the ease to obtain graphs suitable for pondering their meaning. In fact, the method became so commonplace that it acquired the acronym EIS which electrochemists somewhat vainly explain as the electrochemical impedance spectroscopy even though in many situations, it is spectroscopy just electrical as there may not be electrochemical processes even going on.
The current turnkey potentiostats give capable electronic instrumentation to hands of people who do not need to be experts in electronic circuitry. This can lead to overinterpretation of data, particularly at higher frequencies. We will show on a case study how real-life input impedance of the instrument, which is typically and often successfully, ignored in data interpretation, can contribute to appearance of additional elements in fitted equivalent circuits.
With the turnkey hardware is also provided powerful software as a tool for assignment of physical or chemical properties of the studied sample. On a case study of a dielectric electronic material with a leakage we will show how interpretation with overlooked leakage contribution leads to incorrect interpretation of material permittivity, indicating its frequency dependence.
The attached figure shows impedance response of an active mass in a lead-acid battery studied for purpose of modern application for energy recuperation. This is one data set for an active lead acid mass 80 % discharged from a series of a full set of 0-100% discharged and 0-100% charged steps. The interpretation complication arises from the high frequency data (emphasized in the inset), where an inductor as an element in equivalent circuit might be called for. We will demonstrate how this response can be contributed to the real-life behavior of the impedance analyzer itself.

Figure 1
(Invited) Atomically-Precise Surface Processes: From Molecular Mechanisms to Realistic Devices
Authors: Teplyakov Andrew 
Published: November 2022

The atomic-level precision in designing surfaces and nanostructures is quickly making its way from the one-off laboratory investigations into chemical manufacturing. However, in order to make the applications feasible, fundamental understanding of the mechanisms of surface reactions leading to the formation of the desired surface structures is needed. A great deal of progress has been made over the years in uncovering reactions behind atomic layer deposition (ALD), but much more limited information is available about atomic layer etching (ALE), although both processes are often required to build the components of present and future microelectronics.
This talk will highlight recent work on understanding the reactions for metal and metal oxide deposition on functionalized (and patterned) surfaces and on recent advances in ALE of complex materials, specifically focused on tertiary alloys, such as CoFeB, used in magnetic tunnel junctions. I will outline the work needed to understand the mechanisms of these processes that can be further used to improve the control over atomically-precise manufacturing methods and to reduce the use of hazardous procedures. The relatively well-understood ALE procedures that include oxidation or chlorination as the first half-cycle of ALE of such materials and introduction of a bidentate ligands (such as acetylacetonates) to remove complex materials uniformly and with atomic-level control will be extended to describe the potential use of much milder conditions and reagents. A combination of experimental and computational methods will be used to make this analysis possible.
(Invited) Nm-Scale Patterns and Selectivity: A Blessing or a Curse
Authors: Clerix Jan-Willem , Delabie Annelies 
Published: November 2022

Area-selective deposition (ASD) is a promising technique for semiconductor device manufacturing. The replication of nanoscale patterns by ASD can simplify device fabrication process flows by reducing the number of lithography, etch and chemical-mechanical polishing steps. In addition, ASD could eliminate pattern overlay errors. ASD is of special interest as device dimensions scale and has recently been shown as viable approach for the fully self-aligned via, to enable interconnect scaling beyond the 3 nm node [1]. However, the dependence of the selectivity of ALD and CVD processes on the patterning process and pattern dimensions is poorly documented. This aspect will be investigated in the current presentation. We will discuss the fundamental mechanisms of ALD growth mechanisms and how they influence selectivity. Next, we will discuss an example of Ru ASD with defect mitigation in nm-scale patterns on full 300-mm wafers [2].
[1] Chen et al., IEDM21, 486-489.
[2] Clerix et al., Adv. Mater. Interfaces 2021, 2100846.
(Invited) Advances in Atomic Layer Processing of Hafnia-Zirconia Ferroelectrics
Authors: Lomenzo Patrick D. , Alcala Ruben , Materano Monica , Richter Claudia , Mikolajick Thomas , Schroeder Uwe 
Published: November 2022

The limits of integrating ferroelectric materials on commercial semiconductor chips were demolished the moment ferroelectricity in hafnia and zirconia films was reported in 2011. This breakthrough moment in the history of ferroelectric materials was made possible by the fortuitous interplay between advances in atomic layer processing and the strong surface energy dependence of crystal phases in HfO2 and ZrO2. Aided by commercial investment in using both materials as high-k gate and DRAM dielectric materials, atomic layer deposition (ALD) processes are beginning to take full advantage of the completely solid-soluble hafnia-zirconia (Hf1-xZrxO2) ferroelectric system with new precursors and new insights obtained by systematically evaluating film growth conditions. The capability to precisely adjust the compositional profile and to alter oxidation conditions during atomic layer deposition film growth are giving an unprecedented level of control to engineer Hf1-xZrxO2 and doped HfO2 thin films for ferroelectric applications.
The latest advances in atomic layer processing of Hf1-xZrxO2 and doped-HfO2 are presented where the dynamic interaction between composition and film growth conditions provide an engineering roadmap to adjust the physical and structural properties of the dielectric films. Metal precursors play a crucial role in the ensuing film properties. The adjustability of the electrical and structural properties of Hf1-xZrxO2 with ozone exposure during ALD film growth is discussed with respect to the important role oxygen and oxygen vacancies have in the overall phase stability of these novel ferroelectric materials, as well as C incorporation caused by ALD precursors. Just as atomic layer deposition has proven to be instrumental in the discovery and stabilization of the ferroelectric phase in HfO2-based thin films, atomic layer etching (ALE) of HfO2/ZrO2-based layers is now being used to preserve ferroelectricity while pushing the thickness dimension to new limits, yielding high performance films for ferroelectric tunnel junction applications. Further innovations in atomic layer processing will continue to be a harbinger of high performance ferroelectrics in the coming years based on the current status and future outlook for ferroelectric Hf1-xZrxO2 and other emerging ferroelectric materials.
Electrocatalytic Applications of 2D Molybdenum Dichalcogenides By Atomic Layer Deposition
Authors: Zazpe Raul , Sopha Hanna , Rodriguez Pereira Jhonatan , Macak Jan M. 
Published: November 2022

2D semiconductor transition metal dichalcogenides have attracted considerable attention due to their layered structure, suitable band gap, electrochemically active unsaturated edges and relatively good stability against photocorrosion. These properties result promising for different applications including, Li-ion batteries, photocatalysis and hydrogen evolution reaction (HER). Apart from the widely studied 2D MoS2, 2D selenide and telluride equivalents, MoSe2 and MoTe2, have recently gained considerable interest due to their higher electrical conductivity, wider inter-layer distance and narrower bandgap as compared to MoS2, high surface area and close to zero Gibbs free energy edges for hydrogen adsorption.
Unlike sulfide dichalcogenides, the lack of Se and Te precursors have prevented the synthesis of selenide and telluride dichalcogenides by ALD. In order to surpass such impediment, we present a set of novel in-house synthesized Se and Te compounds, which were successfully combined with commercial Mo precursor to synthesize MoSe2 and MoTe2 by ALD [1-5]. The as-deposited ALD MoSe2 and MoTe2 on substrates of different nature were extensively characterized by different techniques, which confirmed the chemical composition and revealed the growth of 2D flaky nano-crystalline MoSe2 and MoTe2.
In parallel, MoSe2 and MoTe2@TiO2 nanotube layers (TNTs) heterostructures were fabricated in a simple and fast fashion to explore and exploit the MoSe2 and MoTe2 photo- and electrocatalytic properties. TNTs act as excellent photoactive supporting material providing a high surface area, unique directionality for charge separation, and highly effective charge collection.
The presentation will introduce and describe the synthesis of the 2D Mo dichalcogenides, the corresponding physical and electrochemical characterization and encouraging results obtained in HER [4,5], photocatalysis [4-6] and Li-ion batteries [7].
[1] R. Zazpe et al, FlatChem (2020) 21 100166
[2] J. Charvot et al, Chempluschem (2020) 85 576
[3] J. Charvot et al, RSC Adv. (2021) 11 22140
[4] R. Zazpe et al, ACS Appl. Nano Mater. (2021) 3 12 12034
[5] R. Zazpe et al, Appl. Mater. Today (2021) 23 101017
[6] M. Motola et al, Nanoscale (2019) 11 23126
[7] H. Sopha et al FlatChem (2019) 17 100130
The Physicochemical Structure of Inorganics in PIM-1/Alox Hybrid Membranes Synthesized Via Vapor Phase Infiltration (VPI)
Authors: Jean Benjamin , Liu Yifan , Mcguinness Emily , Losego Mark D 
Published: November 2022

Polymers of intrinsic microporosity (PIMs) represent a unique class of polymer membranes defined by their inherent microporosity, leading to excellent separations ability. However, the poor solvent stability of these organic membranes limits their use for organic solvent separations. Vapor phase infiltration (VPI) is an emerging technique adapted from atomic layer deposition (ALD) processes that infiltrates inorganic clusters into polymeric materials, generating hybrid organic-inorganic materials with improved chemical stability. VPI treated polymer of intrinsic microporosity 1 (PIM-1) has shown dramatically improved resistance to solvent dissolution while maintaining its microporosity, making it a much more robust membrane. However, the lack of clarity around the structure of the inorganic clusters within VPI synthesized hybrid materials limits the ability to design these hybrid membranes to optimize potential trade-offs between chemical stability, permeance, and separation performance.
Currently, most VPI literature refers to the inorganic components within the hybrid as “metal oxides” or “MOx”. This oversimplification does not fully describe the possible cluster structure or inorganic-to-organic bonding characteristics likely present in these hybrid structures. Moreover, the atomic-scale and long-range disorder of these inorganic clusters make them difficult to describe with traditional methods used for inorganic crystals or polymeric solids. Thus, a more sophisticated understanding of the inorganic structure is needed to inform both process and function design of these hybrid materials. This talk will discuss combined experimental and computational efforts to clarify the structure of inorganic clusters in VPI treated PIM-1/AlOx membranes. XPS and FTIR in conjunction with DFT calculations indicate that the final inorganic species is an oxyhydroxide species. Further, solid state NMR suggests the final inorganic cluster is a 6-coordinate species that is at least dimerized, with water molecules coordinating to the structure to fill out the coordination sphere. DFT calculations validate this claim as the lowest energy structure compared to the monomer form as well as other aluminum oxyhydroxide species. This interdisciplinary work explores the structural characteristics of PIM-1/AlOx hybrid membranes and its impact on the VPI treated material properties such as solvent stability.
Understanding How Organosilicon Additives Delay Electrolyte Decomposition on LiNi0.8Mn0.1Co0.1O2 (NMC 811) Cathodes Using in Situ Techniques
Authors: Ortiz-Ledon Cesar , Morris Louis Vincent , Hamers Robert J 
Published: November 2022

Cathode materials such as LiNi0.8Mn0.1Co0.1O2 (NMC811) are of great interest for Li-ion battery (LIB) systems. By increasing the Ni content, the price decreases since Co is an expensive transition metal. In addition, NMC811 offers higher capacity and operating at high voltages, compared to other cathode materials (i.e., LCO, LMO, etc.). However, this cathode material suffers degradation from different sources. One of the main detrimental processes is oxygen loss from the lattice, which can cause decomposition of electrolyte components such as cyclic carbonates and further generate undesirable gassing in LIB systems. Several different organosilicon (OS) compounds have been reported to decrease gassing during storage with NMC622/Gr multi-layer pouch cells. Besides reducing gassing, OS compounds have been reported to increase the thermal stability of PF6
- and reduce HF, which is detrimental for LIB systems. Currently, the exact mechanism for how OS additives alleviate these undesired electrolyte degradation reactions is not well known.
In this study we performed a mechanistic investigation on the effects of OS3 (organosilicon additive) during Li the intercalation/deintercalation processes on NMC811. First, we explored how OS3 affects the electron transfer kinetics by performing variable scan rate cyclic voltammetry. Second, we studied the mass accumulated on NMC811 surfaces during the first cycle as a function of applied potential using in situ electrochemical quartz crystal microbalance (EQCM). Finally, we analyzed the chemical composition of the cathode surface layer and how it evolves as a function of potential using in situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) at stepwise points during the first cycle. Together, these techniques provide a comprehensive study of the reactions occurring at the NMC811 electrode surface during the first cycle, including lithium intercalation kinetics, mass deposition and dissolution, and the chemical composition of surface decomposition species as a function of potential, it was found that OS3 delays the onset of mass accumulation and therefore delays electrolyte degradation during the first cycle on NMC811 cathode materials as confirmed by the presence of new absorbance features on in situ ATR-FTIR. We successfully identified a potential mechanism of action of how organosilicon additives help to prevent the carbonate-based electrolyte to decompose on NMC811 surfaces. These studies further provide new insights into the mechanisms of performance enhancement observed with OS additives.
(Battery Division Research Award) Structure-Property Relationships: A Journey From LFP to Lithium Metal
Authors: Yamada Atsuo 
Published: November 2022

Conceptual importance of “Matastable Phase Diagram” and “Liquid Madelung Potential” will be demonstrated by picking up some of my mechanism-solving works on LFP and lithium metal.
In Li
x
FePO4, the ground state phase separation and metastable solid solution are energetically competitive, and the solid solution phase is induced in a non-equilibrium electrochemical reaction, playing critical role for fast kinetics. However, there had been no discussion or experimental report of the crystal structure, optical and transport properties of the metastable solid solution phase due to the extreme technical difficulties; the solid-solution phase Li
x
FePO4 is metastable during electrochemical process and disappears within a few seconds. We overcame this limitation by quenching Li
x
FePO4 (x = 2/3) at 350 °C to room temperature. This quenched phase remained stable for a couple of weeks, which enabled sufficient time to measure the several intrinsic properties, including polaron-crystallized superstructure, optical properties with emerging inter-valence charge transfer absorption, and enhanced conductivity over 103 in order.
Since the Li/Li+ redox potential (E
Li/Li+) positions outside of the thermodynamical potential window of the present electrolyte, suppressing side reactions is essential, which can be realized not only by kinetic suppression by SEI but also by thermodynamic stabilization viz. upshift of E
Li/Li+. Remarkable improvement of Coulombic efficiency is exemplified in (locally) salt-concentrated electrolyte, where E
Li/Li+ largely upshifts over 0.6 V. We revealed that the unusual upshift of E
Li/Li+ is primarily dominated by Coulombic energy penalty of Li+ in the electrolytes rather than the simple Nernst equation with extremely high Li+ activity coefficient.[1] Overall energetics was verified and directly quantified by introducing the “liquid Madelung potential (E
LM)” analogous to the conventional concept in solid-state science.[1] Namely, Li+ is electrostatically more stabilized by electron-localized solvents, while relatively less stabilized by electron-delocalized larger sized anion, thus decreasing the overall Coulombic energy gain of Li+ under progressive anion coordination.[1]
[1] N. Takenaka, S. Ko, A. Kitada, and A. Yamada, submitted (2022)

Figure 1