bluuebunny/crossref_metadata_2025_split huggingface dataset:
Engineering of MnO2 Materials at the Nanoscale By PE-CVD for Photoactivated Technologies
Authors: Bigiani Lorenzo , Barreca Davide , Gasparotto Alberto , Altantzis Thomas , Štangar Urška Lavrenčič , Alessi Bruno , Padmanaban Dilli Babu , Mariotti Davide , Maccato Chiara 
Published: May 2020

Photoactivated processes have been widely recognized as cost effective and environmentally friendly routes for both renewable energy generation and purification/cleaning technologies. Great attention has been devoted to the degradation of persistent pollutants in effluent wastewaters, such as dyes from textile, paper and pharmaceutical industries, into harmless products. In addition, increasing efforts have been focused on photoinduced anti-fogging and self-cleaning applications promoted by suitable functional systems endowed with tuneable hydrophobic/hydrophilic properties.
In this context, the present work [1] is focused on the development of supported MnO2-based nanomaterials as platforms for the above mentioned photo assisted applications.
The selected materials were grown on fluorine-doped tin oxide substrates using plasma enhanced-chemical vapor deposition (PE-CVD) between 100 and 400 °C. This technique allows to gain a fine tuning on the resulting material chemico-physical properties, which, in turn, affect the resulting functional performances. PE-CVD experiments yielded the formation β-MnO2 characterized not only by different hierarchical morphologies (from dendritic structures to quasi-1D nanosystems), but also by a concomitant tailoring of the fluorine content, optical absorptions and band gap values as a function of the adopted growth temperature.
Preliminary photo-induced hydrophilicity/photocatalytic functional tests highlighted the possibility of finely tailoring MnO2 nanomaterial performances, thanks to the interplay between their nano-organization, F content and optical absorption capabilities. In addition, the use of Vis illumination instead of UV one did not result in an appreciable performance decrease, paving the way to the use of natural sunlight to activate the target processes. The obtained results, which, to the best of our knowledge, have no precedents to date on the target materials, open challenging perspectives for the development of multi-functional photocatalysts for self-cleaning and antifogging applications, as well as for wastewater treatment.
References
[1] D. Barreca et al. Nanoscale 2019, 11, 98-108
(Invited) In Situ Studies of the Atomic Structure/Charge Distribution at the Electrochemical Interface
Authors: Grunder Yvonne , Lucas Christopher A. , Joly Yves , Soldo Yvonne - 
Published: May 2020

The presence of specifically adsorbed anions can significally affect the electrochemical reactivity of a metal electrode which is of major interest for galvanic deposition, etching, corrosion and electrocatalysis. Halogens on metal surfaces are prototypic adsorbate systems but the adsorption of halide ions especially on copper is also of major importance for on-chip metallization in ULSI microchip production. Halide ions on Cu surfaces form an inhibiting adsorbate layer with polyethylene glycol (PEG). Even though the influence of the additives combination on the shape evolution of the Cu deposit was subject of numerous studies, their precise role during the elementary steps of the deposition with regards to altering the charge distribution and dipole moment at the interface is largely not understood.
To obtain insights into the influence of the applied potential and the screening by the electrolyte to better understand electrochemical processes and charge transfer during adsorption and deposition is a major goal .[1]
Thus combining x-ray spectroscopy and x-ray diffraction to gain site-specific information about the charge distribution at buried interfaces is a promising tool. [2,3]
We will present studies on the metal-halide interface and how the use of surface x-ray scattering techniques can help to characterise electrochemical interfaces in-situ in order to link, structure and stability. [3] Advances in these directions offer possibilities in elucidating atomic scale models of the electrochemical interface and thus will help to establish structure-stability-reactivity relationships which will help to understand growth kinetics.

References:

[1] Y. Gründer, P. Thompson, A. Brownrigg, M. Darlington, and C. A. Lucas, Journal of Physical
Chemistry C, 2012,116, 6283
[2] Y. Gründer and C. A. Lucas, Physical Chemistry Chemical Physics, 2017, 19, 8416
[3] Y. Joly et al., J. Chem. Theory Comput,. 2018, 14, 973−980
(Invited) The Tool-Box Concept for the Synthesis of Surfactant-Free Colloidal Nanoparticles As Electrocatalysts
Authors: Quinson Jonathan , Arenz Matthias 
Published: May 2020

Our research concept is presented, which focuses on a design approach for supported electrocatalysts in order to optimize their properties independent of each other. In supported electrocatalysts, the active phase consists of metal or alloy nanoparticles distributed over a conducting support, mostly carbon based. Our aim is to elucidate the role of
mesoscopic properties – such as the interparticle distance on the support – for their performance in a comprehensive and systematic manner by combining catalyst synthesis, electrochemical measurements with (ex-situ and in operando) spectroscopy and microscopy. Mesoscopic properties have so far received only little attention in academic electrocatalyst design, yet some few studies demonstrate that they bear significant potential for improving the electrocatalyst performance. A proof of concept has been our pioneering work on the particle proximity effect on size-selected Pt clusters where we could decouple the particle size from the particle loading (interparticle distance).
In the talk focus on the catalyst synthesis via a so-called toolbox concept of surfactant-free colloidal nanoparticles, which plays an important role for the ability to investigate such mesoscopic effects. Different colloidal catalyst synthesis strategies are discussed which consist of two steps: the preparation of the active phase (nanoparticle) as well as the deposition of the nanoparticles onto a suitable substrate (support). To obtain well-defined catalysts, a stable colloidal nanoparticle suspension is key. In the presentation the classic use of surfactants in the colloidal synthesis to obtain stable suspensions is compared to so-called surfactant-free methods, in particular a recent approach from our group using low boiling point solvents [1].
[1] Jonathan Quinson, Sara Neumann, Tanja Wannmacher, Laura Kacenauskaite, Masanori Inaba, Jan Bucher, Francesco Bizzotto, Søren Simonsen, Luise Theil Kuhn, Dajana Bujak, Alessandro Zana, Matthias Arenz, Sebastian Kunz; Angewandte Chemie International Edition 57 (2018) 12338-12341
(Invited) Investigations of Interaction and Molecular Structure of Additives on the Copper Electrodeposited Layer By Combination of Cyclic Voltammetry with Time-of-Flight Secondary-Ion Mass Spectrometry (TOF-SIMS)
Authors: Mroczka Robert , Ładniak Agata , Przykaza Kacper , Słodkowska Agnieszka 
Published: May 2020

Appropriate additives, such as polyethylene glycol, play the essential role of metal deposition suppressors and are required to control the fabrication process of copper electrodepositionon micro and nanoscale devices. Moreover, brighteners, accelerators and levellers are involved in adjusting of functional properties of the electroplating bath influencing roughness and waviness of deposited copper layer. Our recent studies [1] show that TOF-SIMS measurements under static regime can be conducted successfully for the identification of additives such as PEG, SPS, and Cl, accumulated on the copper electrodeposited layer.Especially, evaluation of molecular structure of the large molecules such as polyethylene glycol is very challenging and out of range for techniques such as SERS, widely applied for in situ studies under copper electrodeposition regime. On the other hand, traditional mass spectroscopy such as electrospray mass spectrometry are oriented on evaluation of composition of electroplating bath. Recently, we have developed a new approach for evaluation of additives on the copper layer by combination of cyclic voltammetry (CV) with TOF-SIMS. To determine the molecular structure of polyethylene glycol and its interaction with chloride and acceleratorson the copper electrodeposited layer CV experiment was conductedwhile a nitinol wire as a working electrode was withdrawn at constant speed from a copper electroplating bath. In that way applied potential during CV corresponds to position of the wire withdrawn from the electroplating bath. This approach allows to evaluate of distribution of chemical species in a function of the applied potential by ex situ TOF-SIMS measurements. Moreover,the thickness of the copper layer was controlled by laser scan micrometer. In the presence of brightener and leveler, the roughness was evaluated by atomic force microscopy in a function of length of wire. In that fashion, CV experiment combined with a molecular analysis, thickness and roughness of copper layer measurements bring complementary knowledge to comprehensively understand the processes occurring on the copper surface. This will have an application for the real-world samples in a wide range of thickness copper layer, applied potential and concentration of additives and copper sulfate.
[1] R. Mroczka, R. Łopucki, G. Żukociński, Molecular analysis of additives and impurities accumulated on copper electrodeposited layer by time-of-flight secondary ion mass spectrometry, Applied Surface Science 463 (2019) 412–426
Anisotropic Copper Electrodeposition on Microelectrodes
Authors: Braun Trevor Michael , Moffat Thomas P 
Published: May 2020

Copper electrodeposition is critical to electronics manufacturing, ranging across lengthscales from nanometer damascene plating to 100s of micrometers for through-silicon-vias in 3D interconnect packaging and even millimeter-scale in printed circuit board manufacturing. Essential to this process is formation of void-free copper structures in high aspect ratio cavities, which is achieved with various additives that enable superconformal or bottom-up electrodeposition. When the additive package consists of only a suppressor (polyether) and chloride, the superconformal phenomenon is driven by S-shaped negative-differential resistance (S-NDR), which promotes spatial bifurcation of the electrode surface into active and passive depositing regions. All S-NDR systems involve kinetic suppression, polyether-chloride adsorption in this case, and kinetic activation, potential-driven disruption of the polyether-chloride adlayer. The term S-NDR is derived from the s-shape the i-V curve expresses when cyclic voltammetry (CV) is post-experimentally corrected for ohmic resistance, resulting in a system that expresses a multiplicity of reaction rates (current) for a given driving force (potential).
Electroanalytical measurements using microelectrodes (UMEs) offer an avenue for exploring S-NDR systems without significant iR-drop in solution. In other reaction systems, the reduced electrode dimension of UMEs has shown the ability to frustrate active-passive bifurcation, resulting in a homogeneously reacting electrode surface. Nonetheless, potential-controlled measurements such as cyclic voltammetry restrict S-NDR behavior from fully expressing itself, as the potential is the control parameter throughout the experiment. Current-controlled techniques, however, allow the thermodynamic state (i.e., potential) to dynamically shift as the polyether-chloride suppressing layer is formed and disrupted. In this work, current-controlled measurements in the form of linear galvanodynamic sweeps (GDS) are utilized to explore S-NDR behavior and electrode bifurcation during copper electrodeposition. GDS and CV measurements on UMEs are compared across a range of additive concentrations and polyether types. Influence of the operating mode on pattern formation is evaluated by in-situ optical microscopy on UMEs ranging from 10 μm to 25 μm in diameter. Spatial bifurcation during GDS measurements is further exploited to grow anisotropic copper deposits.
Highly Efficient and Air Stable Ternary Organic Solar Cell Enabled By Employing a Perylenediimide-Based Acceptor
Authors: Ting Yu , Izquierdo Ricardo , Welch Gregory Charles , Ma Dongling 
Published: May 2020

Organic solar cells (OSCs) are regarded as one of the promising photovoltaic technologies to address the issues of energy crisis and environmental pollution all over the world, and are thus considered as the next generation of solar cells. 1 However, the devices power conversation efficiency and stability of the devices are still important factors to limit the commercial application of OSCs. 2 To this end, enhancement of photon absorption is an attractive strategy for the increase of PCE. Recently, developing the ternary OSCs with three materials of complementary absorption spectra is an efficient method to enhance the photon harvesting of single junction devices while having a fairly simple fabrication process. Meanwhile, the morphology of active layers can be finely optimized by selecting the third component and adjusting its contents to improve performance of ternary OSCs. 3 Herein, we synthesized highly air-stable perylenediimide (PDI)-based non-fullerene material and integrated it into common organic solar cells as the third component to form the ternary OSCs. This cascade band structure showed a better energy level alignment and the complimentary absorption, thus demonstrating a high ternary device efficiency of 8.71% that represented 14.6% enhancement with respect to the corresponding binary OSCs. Besides, morphology was characterized by two-dimensional grazing-incidence X-ray diffraction (2D-GIXRD) and photo-induced force microscopy (PiFM) and results suggest improved compatibility between organic materials in OSCs, which could reduce the electronic trap states to inhibit the charge recombination and increase the stability of devices. The ternary OSCs thus exhibited good air stability, photo-stability and humidity. Our work provides a very promising approach to enhance the photovoltaic performance while demonstrating highly stable devices, which could contribute to the future development of the large area manufacturing in an ambient condition and roll-to roll processing on flexible substrates.

Reference

1. Yu T., Xu X. P., Zhang G. J., Wan J. H., Li Y., Peng Q., advanced functional materials, 2017, 1701491.
2. Li P. D., Mainville M., Zhang Y. L., leclerc M., Sun B. Q., Izquierdo R., Ma D. L., small, 2019, 1804671.
3. An Q. S., Zhang F. J., Gao w., Sun Q. Q., Zhang M., Yang C. L., Zhang J., nano energy, 2018, 45, 177-183.
Crystalline-to-Amorphous Phase Transformations As a Key Ingredient to Enhanced Rate Performance and Cycle Life in Mg- and Na-Ion Battery Anodes: Operando X-Ray Scattering Studies
Authors: Welborn Samuel S. , Wang Lin , Li Manni , Qiu Tian , Stach Eric A. , Rappe Andrew , Detsi Eric 
Published: May 2020

The increasing popularity of Li-ion batteries in new applications such as electric vehicles is expected to cause the key resources (Li, Ni and Co) used in these batteries to become scarce. Alternative battery technologies, including Mg-ion, Na-ion, and metal-air batteries are therefore desirable. In this talk, I will discuss the use of operando wide-angle X-ray scattering (WAXS) to study the crystalline to amorphous phase transformations that are key to the outstanding performance of state-of-the-art alloy-type Mg- and Na-ion anodes. The 1st part of the talk will be on the impact of the crystalline-to-amorphous transformation on batteries cycle life. Here I will discuss our novel self-healing Ga/Mg anode, which holds the current record for cycle performance and rate capability in alloy-type Mg-ion battery anodes, owing to a crystalline Mg2Ga5 to amorphous liquid Ga phase transformation occurring near room temperature, preventing the well-known pulverization issue in alloy-type anodes.[1] The 2nd part of the talk will detail the impact of the crystalline-to-amorphous transformation on the rate capabilities of batteries. Here, I will present our nanoporous Sb/Na system, which transforms from crystalline Na3Sb to crystalline Sb, going through an amorphous intermediate. It will be shown using a combination of WAXS, electrochemical characterization, and computational study based on ab initio grand canonical (aiGCMC) simulations that the amorphous intermediate phase favors high rate Na storage in Sb.[2]
[1] Wang, L., Welborn, S. S., Kumar, H., Li, M., Wang, Z., Shenoy, V. B., Detsi, E.: High‐Rate and Long Cycle‐Life Alloy‐Type Magnesium‐Ion Battery Anode Enabled Through (De)magnesiation‐Induced Near‐Room‐Temperature Solid–Liquid Phase Transformation.
Adv. Energy Mater. 2019, 1902086. https://doi.org/10.1002/aenm.201902086

[2] M. Li, T. Qiu, S. S. Welborn, A. Foucher, B. Lesel, E. Stach, A. M. Rappe, E. Detsi: Understanding the Fast Kinetics of Sodium Storage in Antimony (unpublished)
Performance Modeling of Hybrid Battery/Supercapacitor Energy Storage Systems Under Charge-Discharge Regimes
Authors: Zabara Mohammed Ahmed , Uzundal Can Berk , Ulgut Burak 
Published: May 2020

The hybridization of batteries and supercapacitors shows advantages in energy storage applications by improving the power density, energy efficiency and cycle life [1]. Applications involving rapid changes in power consumption/production, such as electric vehicles, wind and solar energy systems benefit the most from the hybridization.
The enhancement is due to the power distribution among the hybrid systems. In a hybrid connection the load distributes according to the electrochemical properties of the energy storage system. Batteries are high specific energy systems (Figure 1(b)) which suffers degradation and capacity fade if utilized in high and oscillating specific power applications. The parallel connection of a battery to a high specific power system such as Super-Capacitor (SC) distributes the power among the two systems in which high currents are presumably handled by the SC.
Accurately predicting the power distribution among the hybrid systems is critical for their utilization in any projected applications. Conclusions regarding the best combination of battery/SC to specific condition or application is dependent on the knowledge of power distribution among them.
In this work, we demonstrate how the current distribution between the battery/supercapacitor systems and their voltage responses to random charge-discharge regimes can be modeled using optimization algorithm and Electrochemical Impedance Spectroscopy (EIS) of each system. First, the current distribution for each system is optimized using Differential Evolution algorithm. Second, the voltage is calculated by complex multiplication of the current by the impedance of each system [2]. The predicted current distributions and the calculated voltage responses show high accuracy with the experimental measurements Figure 1(c).
After obtaining the current distributions and the voltage response, performance parameters such as, peak power and energy efficiency are computed to determine the best combination of battery/SC under the charge-discharge condition. Furthermore, EIS of SC systems with different capacitances are simulated and used to predict the performance of the hybrid combination with Lithium Iron Phosphate (LFP) battery. The results demonstrate the ability to accurately predict the power distribution between the LFP/SC system for any capacitance value. It also enables for the determination of the best capacitance to choose for any charge-discharge condition.
References:
[1] L. Kouchachvili, W. Yaïci, and E. Entchev, “Hybrid battery/supercapacitor energy storage system for the electric vehicles,” J. Power Sources, vol. 374, no. November 2017, pp. 237–248, 2018.
[2] E. Özdemir, C. B. Uzundal, and B. Ulgut, “Zero-Free-Parameter Modeling Approach to Predict the Voltage of Batteries of Different Chemistries and Supercapacitors under Arbitrary Load,” J. Electrochem. Soc., vol. 164, no. 6, pp. A1274–A1280, Apr. 2017.

Figure 1
Electrodeposition of Li Metal onto an Ulta-Micro-Electrode
Authors: Nishikawa Kei , Shinoda Keisuke 
Published: May 2020

Li metal is very attractive candidate for a negative electrode of next-generation rechargeable batteries because Li metal has very large theoretical capacity and the lowest standard electrode potential. In order to utilize Li metal for negative electrode, it is indispensable to control the morphological variation during charging and discharging. However, Li metal forms dendrites very easily in the electrodeposition process. In general, the distribution of the current density will induce the dendrite formation in the electrochemical system. In addition to that, SEI (solid electrolyte interphase) should play an important role for the morphological variation of the electrodeposited Li metal. Many researches were conducted based on the surface chemistry in order to reveal the relationship between the nature of SEI layer and the morphology of electrodeposited Li metal. However, the localization of the electrodeposition sites is an obstacle for the quantitative analysis in order to discuss the dendrite initiation and growth.
In this study, ultra-micro-electrode was utilized to observe the morphological variation of the electrodeposited Li metal. Constant current electrodeposition was conducted to observe the electrodeposited Li metal. All electrochemical experimental was done in super dry room. The dewpoint of the room was kept lower than 213K. After the electrodeposition, the ultra-micro-electrode was rinsed with some solvents very carefully, and transferred to FE-SEM or TEM with transfer vessel without air exposure. Ex-situ SEM and TEM observation was done to discuss the electrolyte effects to the morphology of electrodeposited Li metal. For SEM observation, not only the observation of morphology but also the chemical composition of SEI layer was analyzed by EDS spectra. The SEM observation was conducted in room temperature. For TEM observation, the sample was cooled to be about 100 K in order to minimize the electron beam damage. STEM-EELS analysis was also conducted for analysis of SEI layer on the electrodeposited Li metal.
The electrodeposited Li metal onto a ultra-micro-electrode in 1M LiPF6-EC:DEC=1:1 electrolyte was very smooth and uniform column shape. The chemical composition of the SEI layer on the electrodeposited Li metal was confirmed to be mainly LiF and Li2O by SEM-EDS and STEM-EELS analysis. In this presentation, we would like to discuss the relationship between the SEI layer and morphological variation based on the SEM and TEM observation results.