bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Interplay of Anodic Passivation and Oxygen Evolution of Medium Entropy Alloys in Artificial Seawater
Authors: Wetzel Anncia , Ozcan Ozlem , Witt Julia , Morell Daniel 
Published: February 2024

Medium entropy alloys (MEA) have gained increased interest in both academic and industrial sectors due to their favorable mechanical and anti-corrosion properties, rendering them ideal candidates for engineering and potentially catalytic applications. Although previous studies have shown high current densities at high anodic potentials for MEAs, a lack of understanding on the underlying transpassive dissolution and local corrosion behavior remains.
This project aimed to investigate and compare the passivation behavior of MEAs CrCoNi and FeCrNi (equimolar) under high anodic potentials, focusing on the mechanisms of transpassive dissolution and the oxygen evolution reaction in artificial seawater. The study utilized various techniques such as scanning electrochemical microscopy (SECM) to instantaneously detect evolving metal species and oxygen, and inductively coupled plasma mass spectrocmetry (ICP-MS) to quantify the dissolved metal species. For these investigations, the alloys were subjected to precisely controlled corrosion loads employing potentiodynamic, potentiostatic, and chronoamperometric methods during the SECM experiments and subsequent ICP-MS analysis.
Macroscopic corrosion and passive film properties were studied via potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and X-Ray Photoelectron Spectroscopy (XPS). Finally, in-situ atomic force microscopy (AFM) and scanning Kelvin probe force microscopy (SKPFM) were used to analyze the corrosion morphology and surface potentials before, during, and after passivity breakdown. Overall, this study aimed to provide a comprehensive understanding of the interplay between passivation, anodic dissolution and oxygen evolution of the MEAs in artificial seawater.
A Digital Blueprint for 3D-Printing Lab Scale Aqueous and Organic Redox-Flow Batteries
Authors: Fricke Sebastian , Kortekaas Luuk , Gruenebaum Mariano , Winter Martin , Cekic-Laskovic Isidora 
Published: February 2024

With the ongoing development of renewable energy, the need for large-scale energy storage or energy buffer systems is increasing simultaneously. By separating capacity (i.e. concentration and tank size) and voltage (i.e. electrochemistry of the redox-active species), redox-flow batteries (RFBs) offer an exciting opportunity to address these challenges. Due to the wide range of synthetic possibilities in organic and inorganic chemistry, the number of potential novel RAS or membranes, as well as the optimization of existing ones is constantly increasing. However, the high financial cost of lab scale RFB systems for basic research poses an entry hurdle for small synthesis groups, so that this basic research can either only be carried out by specialized groups or only approximate systems (e.g. H-cell assemblies or active material adsorbed on carbon nanotubes in coin-cells) can be investigated. A simple and cost-efficient lab scale RFB setup would thus be an essential step forward in pushing fundamental RFB research forward.
With its cost-efficient and precise nature, additive manufacturing (3D printing) is a promising technique to overcome these challenges, as it has already found application in several other areas of battery research.
Using this technique, we were able to create a design proposal for a lab scale RFB setup, consisting of the RFB cell itself, the tank and pump system, and an inert gas container for about 220€. We tested the system with both an aqueous electrolyte system and an organic one to investigate its versatility. We tested the system with both an aqueous electrolyte system (K4[FeII(CN)6]/K3[FeIII(CN)6]) and an organic one (Fc/FcBF4) to guarantee its applicability to both electrolyte systems. The goal is to use this template for 3D-printed RFB cell to facilitate independent practical RFB research by small research groups.
Preferential Corrosion in Cold Sprayed Cu Induced by Oxide Inclusions
Authors: Li Xuejie , Filice Fraser , Henderson Jeffrey D. , Behazin Mehran , Ramamurthy Sridhar , Barker Ivan , Noël James J. 
Published: February 2024

Cold spray (CS) deposition is a solid-state deposition technique that finds applications in additive manufacturing, coating, and repairing damaged components. During the cold spray deposition process, feedstock particles are accelerated by compressed gas and impinged onto the substrate at high velocity. Bonding between particles and the surface being coated is established by the high kinetic energy released during collision rather than by added thermal energy. As the particles remain in the solid state during spraying, oxidation is minimized. Despite the partial removal of the native air-formed oxides by the jetting effect, residual oxide debris often remains along the particle boundaries within the sprayed objects as inclusions [1]. The oxide inclusions have attracted attention concerning their influence on the inter-particle bonding strength in the deposit [2]. However, little is known about whether they affect the material’s corrosion behavior.
In this work, we report a preferential corrosion phenomenon observed in a CS Cu-diluted HNO3 system that is caused by the remaining oxide inclusions. A mechanism that integrates Cu-NO3
– catalytic corrosion cycles with confined geometry resulting from the dissolution of the oxide inclusions is proposed. Furthermore, we find that this corrosion phenomenon may be mitigated through microstructure engineering. Annealing the CS Cu at 600 °C consolidated the oxide inclusions with their distribution changed from continuous thin films to isolated spherical particles [3]. The propagation of the preferential corrosion is hence interrupted by the lack of interconnected pathways. Counterintuitively, Cl– can function as an inhibitor for this preferential corrosion. Preferential corrosion did not initiate when 1 mM Cl– was initially present in the solution and slowed down when Cl– was added after the preferential corrosion occurred.

Reference

[1] S. Yin, X. Wang, W. Li, H. Liao, H. Jie, Deformation behavior of the oxide film on the surface of cold sprayed powder particle, Applied Surface Science, 259 (2012) 294-300.
[2] Y. Ichikawa, R. Tokoro, M. Tanno, K. Ogawa, Elucidation of cold-spray deposition mechanism by auger electron spectroscopic evaluation of bonding interface oxide film, Acta Materialia, 164 (2019) 39-49.
[3] J. Tam, B. Yu, W. Li, D. Poirier, J.-G. Legoux, J.D. Giallonardo, J. Howe, U. Erb, The effect of annealing on trapped copper oxides in particle-particle interfaces of cold-sprayed Cu coatings, Scripta Materialia, 208 (2022) 114333.
(Invited) An Overview of the Behavior of the LixNiO2 Electrode at High Voltage
Authors: Delmas Claude , Guignard Marie , Abakumov Artem M. , Fauth Francois 
Published: February 2024

Nickel-rich layered oxides Li(Ni,M)O2 (M = Co,Mn, ..) are widely adopted as electrode materials for electric vehicles. They suffer from a loss of capacity when the cells are charged above 4.15 V vs Li/Li+. This limitation is generally attributed to: (i) sharp decrease of the interslab distance at the end of charge which induces cracks in the particles, (ii) slab gliding leading to the formation of the H4 phase, (iii) reaction with the liquid electrolyte, which leads to formation of a rocksalt type structure. The cycling behavior can be improved by texture optimization (concentration gradient, structural orientation). Doping, coating with various cations lead, in some cases, to significant improvement of the cycling properties when the cells are cycled at high voltage. However, the true mechanisms involved at high voltage are not fully understood. In order to overcome the effect of M cations our work was focused on LiNiO2.
GITT and in situ XRD experiments were performed at very low rate in various voltage range (3.8 -4.3 V). On the "4.2-4.3 V plateau" the R2 phase is transformed simultaneously in R3, R3 with H4 stacking faults and H4. When the cell voltage is extended to 4.6V the H4 phase (NiO2) is formed. Cells were charged up to 4.3, 4.5 and 4.6V with a long potentiostatic step (144 hours).The recovered materials were characterized by S-XRD and HAADF electron microscopy. In all cases a mixture of R3 and H4 phases were obtained. The electron microscopy show that both phase R3 an H4 are mixed inside the whole particles. NiO2 is expected to be an ionic insulator (no Li+) and an electronic insulator (d6 low spin). Since there is no formation of a shell of NiO2 around the particles, the difficulty to deintercalation Li suggests that at high voltage another mechanism must be considered.
To try to have a better understanding of the involved process several electrochemical studies were performed in various experimental conditions. As the charge proceeds above 4.17 V the cell polarization dramatically increases, hindering further Li deintercalation. In discharge, such polarization decreases immediately. Also and upon cycling, the polarization increases at each charge above 4.17 V. In discharge, the capacity and dQ/dV features below 4.1 V remain constant and unaffected, suggesting that the bulk of the material did not undergo significant structural defect.
This study shows that the change in polarization between the charge and the discharge results from the electrochemical behavior of the grain surface rocksalt type phase having very low conductivity above 4.17 V and high conductivity below this threshold. The results presented here open a new approach to monitor the electrochemical behavior of the rocksalt type shell and manage its electrochemical properties, at high voltage, by cationic doping of the surface layer. It can explain the behavior observed with some dopants (usually referred as “infused” coatings) like tungsten.
Screen-Printed Impedance Sensor for Atmospheric Corrosion of Silver
Authors: Itagaki Masayuki , Nawamoto Kanako , Watanabe Hikari , Shitanda Isao 
Published: February 2024

The pitch of wiring on printed circuit boards has become finer for the development of small and lightweight electronic devices. There is a risk of breaking the wiring due to slight corrosion since the pitch of wring becomes finer. A sensor to monitor dew condensation and corrosion of wiring must be developed for preventing these corrosion phenomena. Our group 1,2) developed a corrosion monitoring sensor fabricated by screen printing. This sensor has a silver wiring of comb-shape on plastic sheet. Monitoring of dew condensation environment was conducted by using electrochemical impedance spectroscopy (EIS) because EIS allows information of condensation state from change of impedance. In this study, oxidation rate of silver was monitored by a screen-printed comb-shape wiring sensor. In addition, we developed a portable sheet-type counter electrode with thin gel electrolyte. Qualitative and quantitative analysis for corrosion products on silver wiring was carried out with this portable electrode after the corrosion monitoring, and Ag2S, Ag2O and AgCl were detected.
References

I. Shitanda, A. Okumra, M. Itagaki, K. Watanabe, Y. Asano, Sensor Actuat B-Chem, 139, 292 (2009).

A. Aiba, N. Fujii, Y. Hoshi, I, Shitanda, M. Itagaki, J. Electrochem, Soc., 165, C743 (2018).
(Best Poster Award - 1st Place) Characterisation of the Li Metal|Electrolyte Interface of PEO-Based SPEs with Borate Salts, Using in Situ Li Deposition PES Measurements Aided by AIMD Simulations
Authors: Andersson Edvin Karl Walfrid , Wu Liang-Ting , Bertoli Luca , Weng Yi-Chen , Friesen Daniel , Elbouazzaoui Kenza - , Bloch Sofia , Ovsyannikov Ruslan , Giangrisostomi Erika , Brandell Daniel , Mindemark Jonas , Jiang Jyh-Chiang , Hahlin Maria 
Published: February 2024

Lithium metal and anode-free batteries has the potential to increase the energy density and specific energy of the batteries drastically. However, when regular electrolyte materials are tried for these concepts they are plagued with problems due to degradation of the electrolyte at the interface and processes like dendrite formation which leads to poor capacity retention.[1] A strategy to mitigate these problems is to use Solid Polymer Electrolytes (SPEs), as these have better stability towards lithium metal. In order to find appropriate chemistries to use in SPE-based cells it is important to investigate and understand their anode interface, as this is where the Solid Electrolyte Interphase (SEI) is created from the degradation products during cycling.
This work investigates three polyethylene oxide (PEO)-based SPEs, using lithium tetrafluoroborate (LiBF4), lithium bis(oxalate)borate (LiBOB), and lithium difluoro(oxalate)borate (LiDFOB) as the lithium conducting salts. The interfaces of these SPEs (PEO:LiBF4, PEO:LiBOB, and PEO:LiDFOB) was studied using Photo-Electron Spectroscopy (PES) with in situ lithium deposition, where lithium atoms are evaporated on top of the SPE film. The analysis of the core-level spectra before and after lithium deposition is compared to Ab Initio Molecular Dynamics (AIMD) simulations of the interface, where lithium atoms are gradually added during the simulation. These experimental and theoretical methods are meant to mimic the electrochemical plating of lithium at the lithium|SPE interface during charging of a lithium metal or anode-less cell.
The interfaces of PEO:LiBOB and PEO:LiBF4 show, among other compounds, polyethylene as a breakdown product at the interface. PEO:LiDFOB shows a much lesser degree of degradation compared to the other two systems. The degradation layer is however still effective at protecting the SPE from further breakdown, as PEO:LiDFOB has a relatively high capacity retention compared to PEO:LiBF4 and PEO:LiBOB. Suggested is that the LiF provides a better electrochemical stability, while the boron and oxalate breakdown products provides a higher mechanical stability at the interface.
[1] Huang WZ, Zhao CZ, Wu P, Yuan H, Feng WE, Liu ZY, Lu Y, Sun S, Fu ZH, Hu JK, Yang SJ. Anode‐Free Solid‐State Lithium Batteries: A Review. Advanced Energy Materials. 2022 Jul;12(26):2201044.

Figure 1
The Role of Energy Density for Grid-Scale Batteries
Authors: Reber David , Jarvis Sam R. , Marshak Michael P. 
Published: February 2024

For grid-scale battery energy storage systems it is often presumed that cell level energy density is not too important. Yet, countless publications highlight low energy density as the key limitation of technologies such as redox flow batteries or aqueous alkali-ion batteries that are inherently developed for stationary applications.
Here, we resolve this apparent conflict by quantifying the areal energy density, expressed in kWh m-2, of over forty MWh-scale battery energy storage systems deployed around the world.[1] Via satellite imagery we compare lithium-ion, sodium-sulfur, and flow battery projects and show that the amount of energy that is stored per land area is often comparable between these technologies, even though the energy density on cell level varies by an order of magnitude. We highlight excellent safety and vertical scalability as key untapped advantages of aqueous batteries and provide examples of where they can excel, besides simply competing with state-of-the-art lithium-ion batteries. We show, for example, that MWh-scale aqueous flow batteries can safely be deployed underground and within buildings, feats that due to safety constraints are not possible with current lithium-ion batteries at this scale.
Seeing satellite images of battery installations near solar farms is a humbling experience that every researcher working in the field should come across and we provide the locations of all the examined battery installations in a Google Earth file. Grasping the fantastical scale at which renewables are, and must continue to be, deployed certainly provides some perspective regarding energy density of individual battery cells.

[1] Reber, D., Jarvis, S.R., Marshak, M.P., The role of energy density for grid-scale batteries, ChemRxiv, 2022, doi: 10.26434/chemrxiv-2022-5ddhs
Low-Temperature and Catalyst-Free Plasma Synthesis of Plastics-Derived Graphene Quantum Dots
Authors: Chiang Wei-Hung , Weng Ren-Jie , Kurniawan Darwin 
Published: February 2024

The advanced industrial, social, and technological developments in modern society have rendered the production of around 300 million tons of plastic annually, yet only 50% or even less are being recycled. Moreover, the current recycling process is limited to the conversion of plastic wastes (PWs) into hydrocarbon fuels, which also requires the use of high temperatures and energies, long reaction time, and high-cost platinum-based catalysts. Therefore, there is an urgent need to develop a more sustainable and environmentally friendly method to recycle these PWs and possibly into functional materials for diverse applications.
We introduce non-equilibrium and low-temperature microplasma technologies to convert PWs into graphene quantum dots (GQDs) at ambient conditions without any additional toxic chemicals, expensive catalysts, and sophisticated vacuum technologies. The reactive species generated by the plasma enables not only rapid deconstruction of PWs into small hydrocarbons moieties, but also simultaneous reconstruction of nanographene domain and nucleation into GQDs. GQDs are zero-dimensional carbon nanomaterials with unique quantum confinement and edge effects, which are hybridized by sp2 carbon in a honeycomb network. The quantum confinement and edge effects bestow GQDs with unique, tunable, and stable photoluminescence (PL) properties. Coupled with the biocompatibility, low toxicity, large surface area, and chemical inertness, GQDs can be employed in various applications, including imaging, sensing, optoelectronics, drug delivery, catalysis, and energy related applications. Nevertheless, the current syntheses of GQDs still need the use of high temperatures, strong acids or reducing agents, long reaction time, and tedious synthesis procedures.
Here the utilization of microplasma enables the degradation and conversion of various plastics into functional GQDs with well-controlled structures in one-step at ambient conditions and catalyst-free manner, alleviating the current drawbacks in the GQDs synthesis. Among various PWs, polyethylene terephthalate-derived GQDs (PET-GQDs) exhibit enticing and bright white emission under 365 nm UV irradiation with a Commission Internationale de l’Eclairage 1931 of (0.29, 0.35). Moreover, the colloidal PET-GQDs can be exploited for heavy metal ions detection with a low limit of detection of 8.4 nM, while the composite film state is usable as sensitive temperature tag from 10 – 80 °C and LED panel. Our work provides an insight into the novel technologies for PWs recycling into functional nanomaterials in cost-effective, scalable, and environmentally friendly way.
A Hybrid Direct Ammonia Fuel Cell
Authors: Li Wenzhi , Liu Yun , Pan Zhefei , LIU Yun 
Published: February 2024

Ammonia has emerged as a highly promising energy carrier [1], primarily because it offers a noticeable economic benefit over hydrogen in terms of source-to-tank expenses, owing to reduced transmission, distribution, and dispensation costs [2]. Direct ammonia fuel cells (DAFCs) are capable of directly converting the chemical energy stored in ammonia into electrical energy. With its quick start-up advantage, this fuel cell technology holds great potential in the field of zero-emission transportation [3]. Although promising, this fuel cell performance needs to be much improved before the widespread commercialization becomes possible. The limiting factors include the sluggish kinetics of ammonia oxidation and the poor conductivity of anion exchange membranes. In addition, another important factor that limits the cell performance is that thermodynamically, its theoretical voltage is low (1.17 V). In this work, a hybrid direct ammonia fuel cell is developed, which consists of an alkaline anode, a cation exchange membrane, and an acid cathode. This hybrid fuel cell offers a theoretical voltage of as high as 2.55 V. The experimental results have shown that it exbibits an open-circuit voltage of 1.35 V and a peak power density of 437.1 mW cm−2 at 90 °C.

Acknowledgement

This work was fully supported by a grant from the National Natural Science Foundation of China (Project No. 52022003).

References

[1] B. Wang, M. Ni, K. Jiao, Green ammonia as a fuel, Sci. Bull, 67 (2022) 1530–1534.
[2] Y. Zhao, B.P. Setzler, J. Wang, J. Nash, T. Wang, B. Xu, Y. Yan, An Efficient Direct Ammonia Fuel Cell for Affordable Carbon-Neutral Transportation, Joule, 3 (2019) 2472–2484.
[3] T. Wang, Y. Zhao, B.P. Setzler, R. Abbasi, S. Gottesfeld, Y. Yan, A high-performance 75 W direct ammonia fuel cell stack, Cell Rep. Phys. Sci, 3 (2022) 100829.
(Invited) Strategies for Enhancing the Stability of the Electrode-Electrolyte Interphase in Sulfide-Based Solid-State Batteries
Authors: Kim Jung-Hyun 
Published: February 2024

In recent years, all solid-state batteries (SSBs) have gained significant attention as the next-generation energy storage device due to their high energy density, improved safety, and enhanced stability. Sulfide-based solid electrolytes (SEs) have garnered significant attention among various inorganic materials for their exceptional properties, including high ionic conductivity and robust mechanical properties. These features make them promising candidates for SSBs, ensuring both manufacturability and long-term cycle life. For example, Li-argyrodites (e.g., Li6PS5X, and X = Cl, Br, I) and Na-thioantimonate (e.g., Na2.88Sb0.88W0.12S4) offer high ionic conductivities (> 10-3 S/cm) that are comparable to those of liquid electrolytes. However, its practical application is still under-achieved due to a few technical challenges. Among the various issues, our focus is on the electrode-electrolyte interphase, which degrades the cycle life of the SSBs.
At the cathode-electrolyte interphase, narrow electrochemical window (1.71 V – 2.01 V) of Li6PS5X unwantedly prompt the oxidative decomposition of solid-electrolyte. At the anode-electrolyte interphase, Li-argyrodite SEs can be easily reduced by Li metal or oxidized by cathode active materials because of its narrow electrochemical window (1.71 V – 2.01 V). The resulting byproducts at electrode-electrolyte interphases can unwantedly lead to capacity fading and an increase in cell resistance. Additionally, SSBs made with the Li-argyrodite SEs suffer from Li-dendrite penetration during repeated cycles and consequent internal short circuits.
To address these challenges, we propose strategies for passivating the interphases between the cathode and the solid electrolyte, as well as between the metallic anode and the electrolyte in solid-state batteries (SSBs). Through a combinatorial study, we aim to elucidate the extent and severity of interfacial side reactions in solid-state batteries (SSBs). In addition, the optimal coating strategies of LiNbO3 for cathodes and Li3N coating on metallic Li anode will be discussed. The optimized Li3N as an artificial solid electrolyte interphase (SEI) layer on the metallic Li anode enables more than 5000 cycles without failure in symmetrical cells.
Furthermore, we will also highlight a strategy for passivating the electrode-electrolyte interphases of Na-based solid-state batteries (SSBs) that employ thioantimoniate as the electrolyte material. The approaches to passivate the cathode and metallic Na anode will be presented. Comprehensive electrochemical and spectroscopic studies will be conducted to identify the source of degradation and elucidate the improvement mechanisms associated with each strategy.