bluuebunny/crossref_metadata_2025_split huggingface dataset:
MLIP-DFT Combined High-Throughput Screening of Alkaline Stable Lithium Conductors
Authors: Li Zhuohan , Jun KyuJung , Ceder Gerbrand 
Published: December 2024

Solid-state Li-air batteries can prevent the parasitic reaction between the highly reactive discharge product Li2O2 and the organic electrolytes, which is a common challenge for the conventional dry Li-O2 battery. Using humidified air can further improve the battery performance by converting the discharge product to LiOH –– a less reactive and more reversible product. To achieve such solid-state humidified Li-air batteries, it is highly desirable to design Li ion conductors that can withstand humid and highly alkaline environment established by the highly saturated LiOH solution on the material surface.
In this work, we combine the pre-trained universal machine learning interatomic potential (MLIP) –– Crystal Hamiltonian Graph neural Network (CHGNet) –– and the density functional theory (DFT) calculations to conduct a large-scale hierarchical high-throughput computational screening of Li conductors. Our screening strategy is to choose a known Li superionic conductor framework and to optimize the compositions by examining the material stabilities targeting for the real battery operating conditions. We developed specific design criteria to achieve better stability in alkaline environments.
CHGNet structural relaxations are performed in the first screening stage to evaluate the energy of several hundred thousand different compositions. These candidate compositions are screened based on the various stability criteria. The structures of candidates passed the CHGNet screening (stage-1 candidates) are further relaxed with DFT to obtain energies with higher accuracy. The candidates are re-evaluated with stricter stability conditions, leading to the identification of lithium conductors characterized by both high synthesizability and robust stability against the operating conditions of humidified Li-air battery (stage-2 candidates).
Our screening campaign demonstrates that owing to the recent development of universal MLIP with near-quantum accuracy, it is now possible to conduct computational evaluation of compositions with orders of magnitude larger chemical space than what conventional ab-initio high-throughput screening was capable of. Our final candidates not only include some of the known lithium superionic conductors, but also the new compositions with high alkaline stability, indicating the effectiveness of using MLIP for pre-screening purposes. Our strategy can be easily transferred to different material frameworks or other materials applications. We anticipate that with a continuous improvement of MLIPs, the scalability of in-silico material design can be significantly enhanced.
Anodic TiO2 Single Nanotubes with Fe3O4 Nanoparticles: Advanced Photocatalytical Applications
Authors: Sepúlveda Sepúlveda Lina Marcela , Saldan Ivan , Sopha Hanna , Macak Jan M. 
Published: December 2024

Self-organized TiO2 nanotube (TNT) layers, formed by electrochemical anodization of Ti foils, have attracted tremendous scientific and technological attention, due to their remarkable properties such as the tunability of dimensions, their directionality, high surface area, high stability, and the ability to absorb a significant amount of incident light [1,2].
The most widely used electrolyte to develop TNT layers is based on ethylene glycol containing small amounts of water and fluoride ions. However, TNT layers prepared in these electrolytes present a double-walled structure. The outer wall consists of almost pure TiO2, and the inner wall consists of TiO2 contaminated with carbon and fluoride species [3,4]. In recent years, the selective etching of the inner nanotube wall of the TNT layer enabled the synthesis of single-wall nanotubes that showed superior photo-electrochemical performance compared to their double-walled counterparts [5,6]. Modification of the etching process by prolonging and optimizing the etching conditions also enabled the synthesis of single-tube TiO2 powders, which offer various new prospects compared to the TNT layers. At first glance, these powders can be effectively decorated with Fe3O4 nanoparticles to act as magnetically guidable photocatalysts, which is exactly what we recently exploited [7,8,9].
The presentation will discuss the synthesis of these TiO2 nanotube morphologies and their performance in the photocatalytic degradation of model dye in the liquid phase and model drugs that are unwanted in wastewater. We will demonstrate how photocatalytic performance is influenced by single nanotubes and single nanotubes decorated with Fe3O4 magnetic particles. Experimental details and photocatalytic results will be presented and discussed.
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(Invited) Advancing Sodium-Ion Battery Electrolyte Technologies through Multidisciplinary Approaches
Authors: Ban Chunmei 
Published: December 2024

My research work in the field of batteries has spanned across various areas such as electrode development, solid-state and liquid electrolyte synthesis. In the development of advanced batteries, we recognize the complex and interconnected nature of the endeavor. Multidisciplinary approaches exemplified by collaboration with Dr. M. Doeff and others have been pivotal in my research journey.
In my presentation, I will discuss our recent research efforts in developing electrolytes for sodium-ion batteries. The discussion will include the synthesis of both fluorine and fluorine-free salts. I will use this as an example to highlight the importance of multidisciplinary approaches and collaboration in advancing energy storage solutions. Our focus extends beyond conventional electrolyte salts to explore the synthesis of low-cost borate-based electrolytes and their implications for the electrode-electrolyte interface. Together, our collective efforts are dedicated to enhancing safety and sustainability, driving us towards a cleaner and more efficient energy future.
Electrodeposition and Characterization of Platinum Coatings on Titanium Porous Transport Layers for PEM Electrolyzers
Authors: Leimbach Martin , Kurniawan Mario , Fritz Mathias , Bund Andreas 
Published: December 2024

Hydrogen production by electrolysis offers significant advantages over established and more common processes such as steam reforming with regard to carbon dioxide emissions, in particular through the use of electrical energy from renewable sources and the establishment of a decentralized supply structure. The advantages of PEM (proton exchange membrane) electrolysis include high power density, scalability, and the high purity of the produced hydrogen. However, so far the manufacturing of PEM electrolyzers is time consuming, which makes their widespread use difficult and is a significant cost driver for this technology. A promising strategy for the cost-effective production of the cell components is functionalization of low-cost materials with protective coatings. In the framework of the publically funded flagship project H2Giga, coating systems for the bipolar plates (BPP) and porous transport layers (PTL) are developed and tested under real conditions in an electrolyzer stack.
The anode PTL is facing very low pH and high anodic potentials as it is in close proximity to the anode catalyst layer. Therefore, the PTL is made of titanium which is proven to be long term stable under these conditions. However, titanium forms a passive layer under anodic polarization leading to an increase of contact resistance and ohmic drop in the cell. The passivation can be suppressed by electrodeposition of platinum at the interface to the catalyst layer. To ensure a good adhesion of the platinum and low material loss during electrolyzer operation, a pretreatment of the titanium surface is crucial. A state-of-the-art fluoride-containing etching solution was compared to fluoride-free processes in terms of stability of the subsequent platinum coating. Investigations on the morphology by SEM and FIB show a good correlation to polarization experiments. The results are further validated by operando testing in a five cell test stack. The fluoride-free solutions are very promising for industrial applications, but so far only provide limited activation of the titanium surface and need to be further optimized to ensure a reliable coating adhesion.
Electrodeposition of Sb on FTO and Conversion to Sb2S3 for Photovoltaic Applications
Authors: Milano Lorenzo , Magagnin Luca 
Published: December 2024

Electrodeposition is a cost-effective and scalable technique for the synthesis of thin films and coatings suitable for large areas and involving low temperatures, compared to hot-dip coating, vacuum-based techniques and thermal spraying.
Antimony (Sb) is a metalloid mostly used as additive in different applications and recently gaining relevance for the development of semiconducting materials to be employed in photovoltaic applications as light absorber. Among these, there are materials belonging to the category of chalcogenides (e.g. Sb2S3, CuSbS2, AgSbS2) and chalcohalides (e.g. SbSI, SbSeI) that are often tested in solar cells and photocathodes for photoelectrochemical (PEC) water splitting. In this field the use of transparent electrodes is often necessary to allow light to reach the absorber layer, therefore being able to synthesize the latter directly on materials like fluorine-doped tin oxide (FTO) or indium-doped tin oxide (ITO) can lead to multiple advantages: (i) allow different fabrication routes for the device; (ii) couple multiple solar cells in a tandem configuration; (iii) harvest incoming photons from both sides of the solar cell/photoelectrode.
Here, the synthesis of Sb on FTO via galvanostatic electrodeposition from an aqueous solution is presented, starting with the characterization of the electrolyte and followed by structural and morphological analyses on the deposited films. To estimate the conductivity of the electrolyte and to understand the growth mechanism and limiting process, the solution is analyzed with typical electrochemical methods.
The deposited film is first characterized from a morphological point of view, with an emphasis on how the deposition potential affects the grain size and the roughness (via scanning electron microscopy (SEM) and atomic force microscopy), secondly by identifying the crystalline phase formed through X-ray diffraction (XRD). Time-thickness relationships are drawn from cross-sectional SEM images to estimate the growth rates, moreover a critical deposition time is also identified (for longer depositions the deposit detaches from the substrate).
To showcase the potential advantages of this technique, an FTO/Sb2S3/ZnO/Pt composite photocathode is made and tested for PEC water splitting.
The efficacy of the sulfurization process to convert Sb into Sb2S3 is evaluated by XRD while how the morphology of the underlying Sb precursor affects the one of the formed Sb2S3 is studied by SEM. The optical band gap of the sulfide is evaluated through Tauc plots on data obtained via UV-vis spectroscopy.
The PEC performances of the composite photocathode are tested via linear sweep voltammetry in a three electrode setup with a Pt counter electrode under AM1.5G illumination.
Activated Mesoporous N-Doped Carbon Nanospheres As Scaffolds for Li-S Battery Cathodes with High Capacity Retention
Authors: Li Qijun , Berestok Taisiia , Ortlieb Niklas , Camarada Maria Belen , Fischer Anna 
Published: December 2024

Currently, lithium-ion batteries rely on critical metals from third-world countries, which raises environmental and ethical concerns despite their popularity due to long device life and high capacity. Lithium-sulfur batteries (LSB) with sulfur as a cathode material, provide a compelling alternative. They offer high theoretical capacity and energy density, 3-5 times greater than lithium-ion batteries [1]. Sulfur, the fifth most abundant element on Earth, make LSBs cost-effective and environmentally friendly. However, LSBs have some critical drawbacks, such as low conductivity, volume expansion and cathode degradation, and irreversible loss of active materials due to polysulfides shuttle. To overcome these challenges, our group has developed activated nitrogen-doped mesoporous carbon nanospheres (MPNC) with high surface area [2,3] to load and encapsulate sulfur. In this work, we systematically explored the impact of the MPNC pore sizes, i.e. in meso- and micropore size range, on the performance of LSBs cathodes.
The S@MPNC cathodes exhibited excellent cycling stability, retaining between 92 to 97% of the initial capacity over 200 cycles with a coulombic efficiency higher than 96 %, even at a high current density of 0.5 mAh·cm−2, among the best results reported to date. Cathode materials based on smaller pore sizes resulted in an increased initial capacity. However, larger pore sizes of MPNC can operate with higher sulfur loadings, better retaining their capacity than smaller pore S@MPNC nanocomposites due to the facilitated ion diffusion.
In summary, the MPNC porous carbon structure provides enough space to host large amounts of sulfur to enhance the stability, accommodate the volume change of sulfur during cycling, and mitigate the dissolution of polysulfide intermediates.
Influence of Transition-Metal Order of Lnmo Spinel on Li Ion Diffusion and Thermodynamics of LNMO
Authors: Glibo Albina , Reda Mahmoud , Surace Yuri , Kahr Juergen , Flandorfer Hans , Cupid Damian Marlon 
Published: December 2024

A key strategy to enhance the energy density and improve the sustainability of cathode active materials for lithium-ion batteries (LIBs) is to develop more cost-effective, cobalt-free, higher-energy-density alternatives. The LiNi0.5Mn1.5O4 (LNMO) spinel phase is a promising cathode active material for LIBs as it is Co-free chemistry and exhibits a high specific energy density of 650 Wh/kg, which is attributed to its high operating voltage of approximately 4.7 V vs. Li+/Li. LNMO exists in two phases depending on the ordering of transition metals (TM) in the crystal lattice. In the disordered phase, Ni and Mn ions are randomly distributed on the 16d sites of the Fd3̅m cubic unit cell, whereas in the ordered phase, the Ni and Mn atoms occupy the 4b and 12d sites of the P4332 cubic cell, respectively. In this work, a commercially available, disordered LNMO sample was used as the starting point of the investigations. To initiate the ordering of the Ni and Mn ions, the disordered LNMO was subjected to heat-treatment at 650°C in air. The impact of transition metal (TM) ordering on fundamental parameters such as the unit cell size, electrode expansion, and Li-ion diffusion coefficients at different states of charge were explored using in-operando x-ray diffraction (XRD), in-situ dilatometry, galvanostatic intermittent titration technique (GITT), and electrochemical impedance spectroscopy (EIS) measurements. The electrodes for these studies were prepared using both PVDF and water-based binders in order to gain key insights into the effect of aqueous electrode processing on the Li+-ion transport parameters, interface resistances, and electrode expansion during cycling.
Furthermore, a thermodynamic dataset containing the Gibbs free energy description of the LNMO phase was used to calculate the open circuit voltages and lattice parameters of crystalline LNMO as a function of state of charge and Ni and Mn contents in LNMO. The results of the calculations were compared to those from our experimental investigations to assess the predictive quality of the thermodynamic simulations. Our results show a good agreement between the calculated and quasi-equilibrium open circuit voltages measured by GITT and during cycling. In addition, the experimentally determined volume change of the crystal lattice during intercalation and de-intercalation of Li, as measured by in-operando XRD, was well reproduced by the thermodynamic simulation. Therefore, the second aspect of this work, focused on the thermodynamics of LNMO, shows that Gibbs free energy descriptions of cathode active materials can be used to model and assess their electrochemical performance and structural behaviour during cycling.
Air-Induced Lithium Extraction from the Near-Surface NMC Family Materials
Authors: Winkowska-Struzik Magdalena , Buchberger Dominika , Glaszczka Alicja , Jasinski Jacek Bogdan , Struzik Michal , Czerwinski Andrzej 
Published: December 2024

In recent years, a type of layered oxide, LiNixMnyCozO2, shortly NMCxyz (where x+y+z=1), has become the preferred cathode material for electric vehicle (EV) batteries. Despite some disorder in the crystal structure due to Li+/Ni2+ cation mixing, the composition offers a high specific capacity of up to 200 mAh g-1 at 4.3 V vs. Li/Li+ 1. Despite offering high discharge capacity, Ni-rich NMCs have some disadvantages, such as lattice oxygen release and material degradation during deep discharge. Moreover, nickel-rich NMCs can react with ambient air, forming impurities on the surface, which complicates slurry preparation and further battery performance 2–4. The objective of this study is to comprehensively evaluate the structural, morphological, and electrochemical changes in the NMC family (111, 622, and 811) after being stored in ambient conditions for at least one month. The findings of our study hold immense significance as they focus on the possible challenges that may arise due to ambient-air lithium extraction from NMC materials.
However, there is no consensus in the literature on whether lithium on the NMC surface can harm the material's structural and electrochemical properties, reduce performance and safety concerns, or benefit its protective properties, especially for Ni-rich NMC 5–7. An in-depth analysis of the electrode materials helps to understand the lithium extraction pathway and develop treatment protocols for each NMC family member leading to enhanced long-term performance and safety. Here with this presentation, we would like to underline another aspect not being considered in the literature before, regarding morphological evolution upon ambient conditions and its impact on electrochemical performance.

The authors would like to acknowledge the Initiative Excellence Research University of University of Warsaw for financially supporting this work.

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Synergistic Effect of Ni/TiO2 Heterostructures on Performance Enhancement of Lithium-Sulfur Batteries
Authors: Baikalov Nurzhan , Konarov Aishuak , Mentbayeva Almagul , Bakenov Zhumabay 
Published: December 2024

Lithium-ion batteries (LIBs) opened new opportunities for rapid development of modern portable devices. LIBs use mainly the intercalation cathodes represented by transition metal oxides and phosphates as cathodes, which are incapable of fulfilling the requirements of electric vehicles and high energy storage systems due to their limited energy density (less than 400 W h kg-1). Moreover, intercalation type cathodes have several drawbacks associated with high cost of materials and safety issues which also limit their use in electric vehicles and large-scale power systems. Therefore, implementation of alternative systems with higher specific capacity, energy density and inexpensive sources is required to meet high demands. In this regard, lithium sulfur (Li-S) batteries are considered as one of the most promising energy systems due to high theoretical specific capacity, which results in a theoretical energy density of 2600 Wh kg−1[1]. Moreover, sulfur has low cost, considerably less environmentally impact and abundant resources [2]. However, the implementation of Li-S batteries is hindered due to several drawbacks such as low conductivity of sulfur, complicated redox reactions, shuttle of soluble intermediates (polysulfides, LiPS), dendrite growth on lithium anode and volumetric expansion of cathode upon reduction to Li2S2/Li2S which leads to structural degradation and lower the cycle life of batteries [3].
The shuttle effect can be suppressed via encapsulation of sulfur into carbon matrices, synthesis of conductive sulfur composites with polymers, etc. In our recent works we reported on carbon materials with metal -oxides, -sulfides and -nitrides as sulfur immobilizers exhibiting strong affinity to LiPSs. Despite such strong immobilization effect of metal compounds, the conversion of sulfur to the end products needs to be enhanced by introduction of electrocatalysts. In this work, the synergistic effect of heterostructures with double functions, titanium dioxide as LiPSs immobilizer with Ni nanoparticles as electrocatalysts were prepared and analyzed as an effective sulfur host material.
The present study focuses on the implementation of composite compounds with dual effects on the performance enhancement of Li-S batteries.

Acknowledgements

This research was funded by a research grant No. AP23490764 and BR21882402 from the Ministry of Science and Higher Education of the Republic of Kazakhstan.

Figure 1