bluuebunny/crossref_metadata_2025_split huggingface dataset:
Understanding the Mechanism of Li-Mediated Nitrogen Reduction Reaction
Authors: Zhou Yuanyuan , Norskov Jens 
Published: September 2023

Green ammonia production is a key environmental goal. As a crucial step towards this goal, a direct electrocatalytic N2reduction (eNRR) by protons and electrons emerges as a highly desirable alternative. However, all pragmatic attempts to develop such an electrochemical route have so far been hindered by invariably low selectivities and large overpotentials. The most reliable method presently is the lithium-mediated eNRR (LiNR) in non-aqueous electrolytes.1 Despite significant progress made to achieve high FE and current density2, 3,the mechanism of LiNR is yet not fully understood due to so many intricate processes involved ranging from the atomic scale to the macroscopic scale. Moreover, most Li-NRR studies have the limitations of using a sacrificial solvent as proton donors and difficulties in scaling up production in batch reactors. The talk will, address the long-term stability and high activity of PtAu in the HOR process by suppressing the unwanted THF oxidation and improving the tolerance towards CO-poison. Moreover, we investigate the mechanism of the LiNR from the ab initio atomistic reaction process, mean-field microkinetics, to the mass-transport simulations, explicitly achieving an improved understanding the dynamic change of the solid-electrolyte interphase in different LiNR reaction conditions and the effect on the performance.
Reference:
1 J. Choi et al, Nat. Commun.
11, 1–10 (2020)
2 K. Li, et al, Science 374, 1593-1597 (2021)
3 S. Li, et al, Joule, 6, 2083-2101 (2022)
Modeling of the Solid-Electrolyte Interphase: Transport Mechanisms and Mechanics
Authors: Köbbing Lukas , Latz Arnulf , Horstmann Birger 
Published: September 2023

The solid-electrolyte interphase (SEI) considerably affects the performance and lifetime of lithium-ion batteries. Although the SEI has been investigated for many years, various central aspects of this thin passivation layer are still ambiguous due to its generic complexity. Therefore, we thoroughly investigate the growth mechanisms and the mechanical behavior of the SEI.
The long-term growth of the SEI is the main reason which determines the shelf-life of state-of-the-art lithium-ion batteries. Nonetheless, the relevant transport mechanism responsible for the continued growth of the SEI is still highly debated in the literature. Thus, we carefully compare the two mostly considered mechanisms, namely electron diffusion and solvent diffusion [1]. We investigate whether the two mechanisms can describe the observed state-of-charge (SOC) dependence and the typical square-root behavior in time for capacity loss during open-circuit battery storage. We demonstrate that the electron diffusion mechanism reproduces both the SOC dependence as well as the time dependence. Contrarily, we show that solvent diffusion can describe either the SOC dependence or the typical behavior in time. We demonstrate that there is no intermediate regime between the reaction-limited and the transport-limited regimes, which reproduces both dependencies at the same time. In addition, we examine the interdependence of the SOC and square-root time behavior of SEI growth. Due to self-discharge, the combination of both aspects leads to deviations from the typical square-root behavior in time. Our simulations of capacity fade account for this effect and reasonably match capacity fade experiments.
Another substantial aspect of lithium-ion battery research is the transition to next-generation anode materials. As a promising candidate with a high theoretical capacity, silicon receives a lot of research interest. Two major drawbacks of this material are the massive volume expansion and the observed open-circuit voltage hysteresis. Similar to graphite, the SEI covers silicon anodes and has to withstand the expansion and shrinkage of the anode during lithiation and delithiation [2]. We check whether the plasticity of the silicon particle will contribute substantially to the voltage hysteresis. Further, we examine the impact of stress and plastic deformations of the SEI on the volume expansion and the voltage hysteresis. We demonstrate that the mechanics of both silicon anode and SEI will determine the observed voltage hysteresis.

Köbbing, L.; Latz, A.; Horstmann, B. Preprint arXiv 2022, DOI: 10.48550/arXiv.2209.10854

Kolzenberg, L.; Latz, A.; Horstmann, B. Batter. Supercaps 2022, 5. DOI: 10.1002/batt.202100216

Figure 1
In-Situ Raman Spectroscopy of Defined Copper Oxide Surfaces Formed by Electrochemically Controlled High-Temperature Oxidation
Authors: Stadt Michael Georg , Nelhiebel Michael , Larisegger Silvia , Fafilek Guenter 
Published: September 2023

The oxidation processes of copper are of great importance since its occurrence leads to various problems, both in further processing and in operation of electronic devices and other technical applications. Extensive research on the thermal oxidation of copper has demonstrated that temperature and oxygen partial pressure affect the formation of oxides, oxidation rates and the chemical composition.
In this work powerful electrochemical methods for controlled oxidation are presented, where the oxygen partial pressure on the metal surface can be varied over a range of 10-25 to 100 bar in a single experiment. A specific arrangement of the setup extends its capabilities to enable in-situ Raman spectroscopy measurements of the produced oxide.
Controllable oxidation states are achieved in a solid-state electrochemical cell by polarizing a copper sample in contact with a single crystal of yttria-stabilized zirconia, which is conductive for oxygen ions at high temperatures. Optical transparency of the single crystal allows the Raman laser to pass through the crystal to measure the copper oxide formed on the copper-electrolyte interface.
Cyclic voltammograms contain kinetic and thermodynamic information about the oxidation processes. Thus, the various oxidation reactions are controlled by the potential that corresponds to the oxygen partial pressure, while the current measures the rate of layer growth as well as the thickness of the oxide layer. In situ Raman measurements allow more detailed analyses of the oxides. The combined data will be used to build a model for oxide layer growth, with particular attention to the defect chemistry of the copper oxide.
Probing Lattice Oxygen Oxidation in Perovskite Electrocatalysts By Resonant Inelastic X-Ray Scattering
Authors: Bosse Jan , Akbashev Andrew 
Published: September 2023

During water electrolysis, the hydrogen evolution reaction that generates hydrogen gas is unavoidably accompanied by the anodic reaction that generates oxygen via the oxygen evolution reaction (OER). However, under OER conditions, many electrocatalysts undergo structural degradation and can become amorphous. Lattice oxygen oxidation was proposed as one of the possible causes for amorphization of perovskite oxides. However, because lattice oxygen oxidation is notoriously challenging to probe in experiments, its unambiguous detection in oxide electrocatalysts has been elusive so far.
Here, I will show how oxygen oxidation can be detected in single-crystalline (model) oxide electrocatalysts using high-resolution resonant inelastic X-ray scattering (RIXS). Specifically, I will present our case study of perovskite materials where the emergence of oxidized oxygen depends on the transition metal and the applied potential. An insight into the chemical environment of the oxidized oxygen and how it can be accommodated in the perovskite lattice will be provided based on the results of DFT and molecular dynamics. Finally, I will discuss how lattice oxygen oxidation is related to the degradation of oxide electrocatalysts during OER.
Ultrathin, Smooth Li-Metal Anode Via Electrodeposition for Stable Cycling of Li-Betal Batteries Under Practical Conditions
Authors: Seo Jiyeon , Lim Minhong , Lee Hongkyung 
Published: September 2023

Lithium (Li) metal anodes (LMAs) with high specific capacity (3860 mAh g–1) and lowest redox voltage (–3.04 V vs SHE) are considered superlative candidates for high energy batteries. Ultra-thin, large-area LMA is crucial for building Li-metal batteries (LMBs) that can deliver high volumetric and gravimetric energy density in practice. As the charging and discharging continue, the growth of Li dendrite is regarded as one of the significant challenges. The surface nature of LMAs is the main aspect of Li dendrite formation and interface reaction. However, most studies overlooked the initial condition of LMA surface. Native passivation layer (NPL) of commercial Li foils is inherently uneven composed of Li2CO3, LiOH, and Li2O, and its chemical nature is mostly determined under manufacturing conditions. Incomplete passivation at an initial stage can trigger sporadic Li dendrite growth and chemical/structural deterioration of LMAs, adversely affecting the cycling stability of LMBs.
This work presents the electrochemical pre-passivation to build an electrolyte-derived native layer (electro-native layer, E-NPL) through Li electrodeposition method. Electrodeposited LMA (ed-LMA) was prepared by pre-deposition at the Cu foil using localized high-concentration electrolyte (LHCE) and post calendaring for smooth LMA surface. As-prepared ed-LMA has 4.13 mAh cm-2 of areal capacity with ~22 µm, and reduced roughness, which is much lower than that of manufactured LMA (m-LMA). Particularly, the E-NPL derived by LHCE can tailor the LMA surface by enriching the inorganic SEI compounds such as LiF, and N-SOx. In addition, decreased amount of passivated components such as Li2CO3, LiOH, and hydroxide were found in XPS analysis of the anodes. Compared to manufactured LMA (m-LMA), the ed-LMA exhibited lower overpotential for Li plating/stripping cycles and enhanced capacity retention. Benefiting from better compatibility with newly plated Li, it showed higher plating density without electric isolation from beneath Li surface, mitigating the anode swelling during subsequent cycling. We successfully demonstrated battery cycling stability of Li||NMC622 cells exploiting ed-LMA (195 cycle at 80% retention), superior to m-LMA (110 cycle at 80% retention) under stringent conditions.
Voltammetric Detection of Explosive Nitroaromatic Compounds Using Boron-Doped Carbon Nanowall Electrodes
Authors: Dettlaff Anna , Kaczmarzyk Iwona , Sobaszek Michal , Prasuła Piotr 
Published: September 2023

Nitroaromatic highly energetic explosive compounds were widely used during the I and II World Wars. Some of them, like 2,4,6-trinitrotoluene (TNT), are still used in military munitions or in industrial applications i.e., underwater blasting, mining, deep well or dye production. The worldwide use of nitroaromatic compounds led to widespread pollution of the environment causing a danger to living organisms due to their high toxicity and possible carcinogenicity. The most commonly used techniques for the detection of explosive nitroaromatics are high-performance liquid chromatography or high-resolution gas chromatography coupled with different detectors like mass spectrometers. Both methods require: expensive instrumentation, complex sample preparation which is crucial to analysis, and well-trained staff to perform the experiments. Therefore it is difficult to implement chromatography in the field. Electrochemical sensing is emerging as a fast, sensitive and relatively simple technique for detecting explosive materials. To date, various materials have been used as working electrodes for this purpose, however, carbon materials are particularly promising [1-2]. Among carbonaceous materials, boron-doped carbon nanowall (B:CNW) electrodes are particularly attractive for the sensitive and rapid detection of nitro-based compounds [3] due to the high content of sp2 phase, wide electrochemical working potential window (from -1.6 V to 1.2 V in 0.5 M KCl) and high values of heterogeneous electron transfer rate constant.
In this work, we present electrochemical detection of chosen nitroaromatic explosive compounds like TNT on boron-doped carbon nanowall electrodes in aqueous solutions using voltammetric electrochemical techniques (differential pulse voltammetry, square-wave voltammetry, cyclic voltammetry). B:CNW electrodes were obtained using microwave plasma-assisted chemical vapour deposition in a one-step growth process. B:CNW electrode show enhanced electrocatalytic activity towards nitro moieties attached to aromatic rings, resulting in improved sensitivity toward detecting these groups. Hence, it is an attractive nanocarbon surface for nitroaromatic compound determination.

References
[1] M. Goh et al., Anal Bioanal Chem 2011, 399, 127–131. Doi: 10.1007/s00216-010-4338-8
[2] A. Dettlaff et. al, Microchimica Acta, 2022, 189:270. Doi: 10.1007/s00604-022-05371-w
[3] A. Dettlaff et al., J. Hazard. Mater. 2020, 387, 121672. Doi: 10.1016/j.jhazmat.2019.121672

Acknowledgements
The research leading to these results has received funding from the Norway Grants 2014-2021 via the National Centre for Research and Development within research grant no. NOR/SGS/NITROsens/0011/2020-00
Detection of H2O2 using Carbon Nanotubes Covalently Attached to Nanostructured Au Electrode
Authors: Huseinov Artur , Nawarathne Chaminda P , Alvarez Noe T 
Published: September 2023

Detection of hydrogen peroxide (H2O2) has practical significance in various fields, including pharmaceutical, clinical and food industries. The enzyme based H2O2 biosensors allow for the detection at lower potentials, thus avoiding possible interference from reducing agents. However, this type of sensors is inherently less stable, difficult to fabricate and more expensive. Due to high electroactive surface area and electrocatalytic properties, gold nanoparticles and their combination with carbon nanotubes (CNTs) are commonly used in H2O2 sensor design.
To avoid fabrication inconveniences and improve stability of a H2O2 sensor, we designed a new hybrid material in which CNTs are covalently attached to a gold surface. First, a highly homogeneous nanostructured gold surface was formed on top of the SiO2 substrate with an intermediate layer of Ti, using E-beam evaporation technique. The average height of the gold nanostructures was 3.9 nm. The gold surface was then electrochemically grafted with aminophenyl groups. Further, plasma-functionalized densified CNT film made from CNT array was attached to the gold surface via amide formation reaction. An introduction of CNTs led to a 40-fold increase in current response. Formation of nanostructured gold surface without actual attachment of nanoparticles to the substrate, as well as covalent bonding of CNTs to the surface, provide a very high stability of the fabricated material, which, in turn, improves the repeatability of measurements.
A designed electrode was used for non-enzymatic H2O2 detection. Under optimized parameters of square wave voltammetry and optimum pH, analysis of H2O2 can be performed using 5 independent oxidation peaks. The presence of multiple peaks is due to oxidation of gold, CNTs and H2O2 itself. All peaks increase when H2O2 is added in solution, because of chemical reduction of CNT and gold surfaces, and their consecutive electrochemical oxidation. Using the peak at -0.6 V allows for the H2O2 detection at very low potential, that can minimize interference from various reducing agents. For the -0.6 V peak, the limit of detection was 1.4 mM. Using the peak at -0.05 V allows for much higher sensitivity with the limit of detection of 500 nM.
Almost no signal deterioration was observed after 200 measurements, proving high stability of the fabricated electrodes.
Light Addressable Electroanalysis with Semiconductor/Metal Junctions
Authors: O'Neil Glen D 
Published: September 2023

Light addressable electrochemical sensing (LAES) is a photoelectrochemical sensing technique that uses light to activate a faradaic electrochemical reaction at the surface of a semiconducting photoelectrode. Using LAES we can confine an electrochemical reaction to a microscopic portion of a macroelectrode using focused illumination, enabling photoelectrochemical imaging of biological processes. LAE sensors use semiconductors as the light-absorbing electrode material, and as a result understanding and controlling the electrochemical response of these sensors is considerably more challenging than with metallic electrodes. These challenges are due to the nature of the band structure of the semiconductor, the interfaces between the semiconductor/electrolyte, and the nature of charge transfer across these interfaces. Moreover, when silicon is used as the electrode material, steps must be taken to protect the sensor from corrosion in aqueous electrolytes.
Here we present recent results from our group showcasing semiconductor/metal junctions as LAE sensors. We show that Schottky junctions formed between nSi and Au, Pt, or Ni nanoparticles are excellent candidates for LAE sensors. These junctions can be prepared with a simple benchtop electrodeposition procedure and demonstrate excellent electrochemical properties with near-reversible cyclic voltammetry observed with a number of outer-sphere redox couples. We apply these sensors to the detection of sub-µM concentrations of neurotransmitters and other biologically relevant species (e.g., H2O2). We will also show how alternative voltammetric waveforms can be used to provide richer electrochemical information about the interface and increase sensitivity of the sensors.
Influence of Frictional Heat on Hydrogen Permeation Measurements
Authors: Reinbold Jasmin , Boiadjieva-Scherzer Tzvetanka , Stache Heiko , Vengudusamy Balasubramaniam , Fafilek Guenter 
Published: September 2023

Hydrogen transport properties in metals are often investigated in electrochemical Devanathan-Stachurski double cells (DS) or modifications thereof. A DS setup consists of input and output cells which are divided by a metal membrane. The hydrogen oxidation current measured in the output cell is proportional to the permeation rate of hydrogen through the metal membrane. In certain applications of lubricated tribocontacts, steel is susceptible to damages by uptake of hydrogen. For investigation of the friction-generated hydrogen uptake a lubricated sliding contact in the input cell of the DS setup is realized.
Related low hydrogen permeation current signals are significantly affected by the steel membrane temperature. As an example, frictional heating of the steel membrane leads to additional release of residual hydrogen from the steel. To investigate the temperature effect, tests with an oil containing a hydrogen promotor, a PFPE oil and without lubrication were conducted. The results indicate that the permeation signal is strongly influenced by frictional heating. Such measured currents must not be misinterpreted as hydrogen generated by lubricants. A thermodynamic and kinetic model of the hydrogen diffusion and trapping reveals the correlation between current signal and temperature change.
Strategies on Enabling High Areal Sulfur Loading in Lithium Sulfur Batteries
Authors: Motevalian Saeme , Nazir Aqsa , Claus Ana , Jahan Georgina , Hamal Dambar , Awadallah Osama , El-Zahab Bilal 
Published: September 2023

Needs for energy storage devices in modern-day applications such as electric vehicles and other high energy consuming portable electronics make the Lithium sulfur batteries (LSBs) to be one of the most attractive types since they offer a high theoretical energy density (2600 Wh kg-1), which is about an order of magnitude higher than the theoretical specific capacity of the lithium ion batteries. In addition, Sulfur is one of the most abundant materials in nature and moreover, a non-toxic element which makes the lithium sulfur battery a suitable candidate for commercialization. However, obstacles to overcome include the loss of active sulfur due to various phenomena mainly represented by polysulfide diffusion and reactivity on the lithium anode. Another serious issue observed in so many ways is the low electronic conductivity of Sulfur and its products such as Li2S as a result of cycling. These problems are often exacerbated at higher sulfur loading and lower electrolyte to sulfur ratios (E/S). One way to increase the sulfur loading is to increase the thickness of the cathode which in return increases the risk of low utilization of active material because of the high thickness and low wettability by electrolyte. Another way is to increases the ratio of the sulfur in respect to conductive host material without increasing the thickness of the cathode. By doing so, sulfur is going to fill all the pores existing in the host material and therefore, this structure cannot provide enough volume expansion during discharge process and as a result, the cathode structure may collapse and the whole cell fail. Therefore, to come up with a high performance and stable battery during cycling, there is no doubt that we have to focus on the structure of the cathode and the host material to effectively confine the sulfur and produced polysulfide and at the same time, alleviate the way of the electron transfer through the conductive network.
In this research, we investigate some of the most influential parameters mainly associated with the morphology of the cathode to improve capacity retention. Optimizing the sulfur loading, E/S content, pore structure and pore volume, and the thickness of the cathode lead to an overarching understanding of the physical transitions that occur during the discharge and charge operation of the battery. In addition, various electrochemical testing to evaluation the loss of activity of the cathode surface is also carried it to correlate to the proposed physical model.