bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanistic Insights into the Behavior of Electrolyte Additives That Selectively Suppress Anode Corrosion in Battery Systems
Authors: Phung Theodore , Sinclair Nicholas Scott , Akolkar Rohan
Published: December 2024

Metallic zinc (Zn) is of great interest as a battery anode material due to its very negative reduction potential, high charge storage capacity, low cost, and compatibility with aqueous electrolytes (acidic and alkaline) [1]. Despite these advantages, Zn-metal anodes are known to spontaneously corrode in aqueous electrolytes leading to a significant loss of stored capacity over long storage times [2]. A common approach to suppress this corrosion is to use additives that can adsorb onto the electrode surface, but many of these compromise the performance of the Zn battery [3]. In this talk, a novel additive, benzyldimethylhexadecylammonium chloride (BDAC), is presented that suppresses corrosion of Zn without impacting high-rate Zn deposition or stripping [4]. This behavior is further explored with slow-scan cyclic voltammetry measurements that show significant hysteresis in the presence of BDAC. The hysteresis implies that the electrode surface exhibits multiple steady states. For example, it can either be covered with additive and become passivated or have little-to-no BDAC and be electrochemically active depending on the applied potential or current. A model is then proposed that incorporates the competition between additive adsorption on a metallic Zn surface and additive deactivation based on metal deposition and stripping rates. Numerical analysis using the model corroborates experimental data and displays how different factors such as the transport rate of additive to the surface and applied current density influence the fate of the electrode’s surface in terms of which stable state it prefers. This work paves the way for the design and operation of electrolyte additives that selectively suppress Zn corrosion without harming battery performance.

References:

[1] G. Wang, H. Zou, X. Zhu, M. Ding, and C. Jia, “Recent progress in zinc-based redox flow batteries: A review,” J. Phys. D. Appl. Phys., vol. 55, no. 16, 2022, doi: 10.1088/1361-6463/ac4182.

[2] Q. Li, L. Han, Q. Luo, X. Liu, and J. Yi, “Towards Understanding the Corrosion Behavior of Zinc-Metal Anode in Aqueous Systems: From Fundamentals to Strategies,” Batter. Supercaps, vol. 5, no. 4, 2022, doi: 10.1002/batt.202100417.

[3] J. L. Ortiz-Aparicio, Y. Meas, T. W. Chapman, G. Trejo, R. Ortega, and E. Chainet, “Electrodeposition of zinc in the presence of quaternary ammonium compounds from alkaline chloride bath,” J. Appl. Electrochem., vol. 45, no. 1, pp. 67–78, 2015, doi: 10.1007/s10800-014-0777-9.

[4] T. Phung, N. Sinclair, and R. Akolkar, “Potential–Dependent BDAC Adsorption on Zinc Enabling Selective Suppression of Zinc Corrosion for Energy Storage Applications,” J. Electrochem. Soc., vol. 171, no. 2, p. 023503, 2024, doi: 10.1149/1945-7111/ad2598.
Shining a Light on Osmotic Energy: Innovating Power Generation with Light-Responsive Covalent Organic Frameworks
Authors: Li Ya-Chun , Yeh Li-Hsien
Published: December 2024

The growth of global demand for energy has been increasing, making the energy crisis a worldwide issue. Osmotic energy, characterized by its utilization of an ionic concentration gradient to generate power through an ion-selective membrane, has emerged as a promising avenue. However, the osmotic energy harvesting performance typically suffers from ab imbalance between ion selectivity and permeability. Here, we report a promising light-responsive covalent-organic framework (COF)-based ion-selective membrane for light-enhanced osmotic energy harvesting. We show that benefiting from rich sub-2 nm ion channels, the membrane can generate a high osmotic power density than the commercial benchmark (5 W/m2). Furthermore, the power can be further improved significantly through UV light radiation. We also demonstrate that the membrane can extract energy existing in a concentration gradient created by carbon dioxide (CO2) adsorption, and the performance can be remarkably enhanced by light exposure. This work triggers the hopes for practical osmotic energy conversion from seawater/river water and CO2 adsorption using novel light-responsive COF-based membranes.
Engineering Asymmetric Ion Selective Membranes with Subnano-in-Nano Architectures for Highly Efficient Blue Energy Conversion
Authors: Prasetyo Fery , Yeh Li-Hsien
Published: December 2024

Harnessing clean and renewable energy from salinity gradients using ion selective membranes is a promising solution to the energy crisis. Subnanochannel nanofluidic membranes show great potential as a platform for efficient osmotic energy conversion. This study presents a method for developing a promising ion selective membrane based on synthesizing NH2-functionalized MIL-53 (MIL-53-NH2) metal-organic frameworks (MOFs) in an asymmetric branch-type alumina nanochannel (BANM), to create a subnano-in-nano architecture. The design of the unique structure is validated by many characterizations, such as scanning electron microscope (SEM), fourier-transform infrared (FTIR) analysis, Zeta potential, and water contact angle. Experimental results indicate that the membrane has a continuous and dense structure, with all nanochannels embedded with MIL-53-NH2 MOFs. Moreover, the creation of the subnano-in-nano architecture in an asymmetric BANM renders it with enhanced ion selectivity and ionic diode property, which allows unidirectional ion transport behaving like a biological ion channel membrane. Thus, an ultrahigh power density of approximately 5.75 W/m2 is achieved by mixing an artificial seawater and river water, which increases by ~204% compared to the pure BANM and exceeds the commercial benchmark (5 W/m2). This work not only introduces a novel approach to synthesize a MOF-based ion-channel-mimetic membrane but also opens new ways towards high-performance blue energy harvesting and advanced separation techniques.

Figure 1
(Invited) Progress in Electrochemically Active Components for High-Energy Density Lithium Sulfur Battery Systems
Authors: Kumta Prashant Nagesh , Velikokhatnyi Oleg , Gaikwad Mayur , Blomgren George E
Published: December 2024

Energy storage is becoming increasingly critical for sustaining an energy independent global economy. At present, the major energy eco-system relies primarily on tapping into the earth’s natural oil reserves and gas exports. The Li-ion battery chemistry has evolved over the years since its commercialization by Sony in 1990 and is currently at the forefront of secondary rechargeable battery systems. The field has witnessed burgeoning and an alarming growth in research activity since 1990 with transformative advances made in all areas of cathodes, anodes, and electrolytes. Despite much progress, however, lithiated transition metal oxides and carbon remain the preferred flagship systems that have made it into the commercial arena currently deployed in the hitherto electric vehicles (EVs). The incessant growth and global demand combined with the concomitant emergence of artificial intelligence, countless applications in use and ever evolving, there is an ever-increasing impetus for developing high energy density systems. The intense demand for identifying higher energy density systems has made Li-air and Li-S systems, the preferred actively researched systems of late. The Li-S systems are of particular interest due to the promise of achieving 500 Wh kg-1, a major milestone in meeting the energy density needed for next generation EVs matching and exceeding the performance metrics of the internal combustion engine (ICE).

This presentation will discuss the materials challenges in anode, cathode and the electrolyte areas that must be overcome to reach the grand challenge of 500 Whkg-1. Research progress made in the areas of developing cost-effective and scalable new sulfur and polysulfide confinement systems enabling high sulfur loadings of 4-6 mg/cm2 combined with unique functional electrocatalysts aided by theoretical first principles calculations exhibiting propensities to electro-catalyze Li2S formation will be discussed. Concurrently, progress made in generating new dendrite-free anodes and low-density current collectors for anode free configurations exhibiting areal capacities as high as 15 m Ah/cm2 with stable cycling over 100 cycles as well as electrolyte additives matching the cathode and anode performances will be outlined.
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.
Impact of Structural Motifs on the Ionic Diffusion Mechanism in Sulfide-Based Solid Electrolytes
Authors: Rakib Tawfiqur , Ertekin Elif
Published: December 2024

Sulfide-based solid electrolytes, such as lithium thiophosphate (LPS) with compositions (Li2S)
𝑥
(P2S5)1−

𝑥
and lithium Germanium thiophosphate (LGPS [Li10GeP2S12]), exhibit high ionic conductivity, rendering them promising for solid-state batteries (SSBs). However, their practical application is limited due to their low electrochemical stability and grain boundary resistance. To overcome these challenges, we explore the formation of glass-ceramic phases within the lithium thiophosphate family. Our investigation centers on the mechanism of ionic diffusion in LPS (with three compositions) and LGPS (with two distinct crystal systems) in their crystalline and glass-ceramic phases. Employing ab initio molecular dynamics (AIMD) simulations, we identify and classify the structural motifs responsible for the diffusion of Li-ions. Notably, Li2P2S6 (x = 0.5) exhibits a high activation energy for diffusion, while Li7P3S11 (x = 0.7) demonstrates elevated Li-ion diffusivity in its crystalline phase. Interestingly, the transport properties do not vary with compositions suggesting that the ion mobility is independent of the underlying structural motifs present in the glass-ceramic phases of LPS. Our structural similarity analysis also reveals a similar Li environment in the glass-ceramic phase, regardless of LPS compositions. Furthermore, increasing the crystallinity in glass-ceramic Li7P3S11 increases the amount of P2S7
4- motifs, and its percolation changes the Li environment creating a conduction pathway for Li-ion diffusion. In the case of LGPS, disorder within the glass-ceramic phase significantly diminishes ion transport similar to the behavior observed in LPS. However, the tetragonal and triclinic crystal structures reveal distinct ionic diffusion mechanisms in terms of conduction pathways. Our study emphasizes the importance of structural motifs to devise the optimal strategy for designing solid electrolyte materials.

Figure 1
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.

References:

[1] J. M. Macak et al., Curr.
Opin. Solid State Mater.
Sci.,
2007,1-2, 3.

[2] K. Lee et al., Chem. Rev.,
2014, 114, 9385.

[3] S.P Albu et al., Adv. Mater.
2008, 20, 4135.

[4] A. Dronov et al., Appl. Surf. Sci.,
2018, 434, 148.

[5] M. Motola et al., Electrochem. Commun
.,
2018, 97, 1.

[6] S. So, et al., Energy Environ. Sci.
2015, 8, 849.

[7] D. Beketova et al., ACS Appl. Nano Mater
.,
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, 3, 155.

[8] M. Sepúlveda et al.,
Ceram Int., 2023
, 49, 6764.

[9] M. Sepúlveda et al.,
Frontiers in Environmental Chemistry, 2024
, 5, 1373320.
Mitigating Galvanic Corrosion in Carbon Fiber Reinforced Polymer-AZ31B Dissimilar Joints through Oxide Layer-Coated Rivets
Authors: Lim Yong-Chae , Jun Jiheon , Su Yi-Feng , Wade John E. , Keum Jong , Zhili Feng
Published: December 2024

The major technical hurdles for lightweight multi-material vehicles lie in joining and corrosion, particularly galvanic corrosion of dissimilar material joints. In this study, the friction self-piercing rivet (F-SPR) process was utilized to spot join carbon fiber reinforced polymer (CFRP) to AZ31B Mg alloy at a coupon scale. After fabricating the dissimilar joint samples, a unique corrosion exposure test was performed to investigate galvanic corrosion of AZ31B at the joint in 0.1 M NaCl solution. A novel oxide self-formation technique was employed on alumina forming austenitic (AFA) alloy to electrically insulate the rivet/multi-material interfaces for mitigating galvanic coupling effect in the dissimilar joint. Advanced characterization and electrochemical evaluation techniques were employed to study corrosion behaviors of oxide layer formed AFA alloy. The corrosion volume assessment of AZ31B at the joint revealed that the surface oxide layer formed on AFA alloy rivets significantly reduced galvanic corrosion compared to both the untreated AFA alloy and carbon steel rivets (control).
Exploring the Synergistic Effect of Mesoporous Coating and Loaded Corrosion Inhibitor in Epoxy for Enhanced Durability and Long-Term Protection
Authors: Bahgat Ahmed Bahgat , Shakoor Abdul , Santo Loredana , Al-Qahtani Noora , Hassan Mohammad K
Published: December 2024

This study delves into the realm of advanced corrosion protection by investigating the synergistic impact of mesoporous coating and corrosion inhibitor integrated into epoxy formulations. The research explores the unprecedented levels of corrosion resistance achieved through this novel combination, aiming to unravel the mechanisms and interactions that contribute to enhanced durability. By employing a comprehensive approach, the study aims to provide valuable insights into the long-term protective capabilities of mesoporous-infused epoxy, shedding light on its potential applications in various industries requiring robust corrosion defenses. Prior to the introduction of the epoxy coating, the corrosion inhibition efficiency of triethanolamine (TEA) on carbon steel in saline water was thoroughly explored using different electrochemical and microscopy techniques. The addition of 10-2 M resulted in an inhibition efficiency (IE%) of 70%. The corrosion resistance of the epoxy coating, enhanced with 3 wt.% mesoporous carbon and a corrosion inhibitor, was systematically investigated in saline water over an extended immersion period of 60 days, employing electrochemical impedance spectroscopy (EIS). The initial charge transfer resistance (Rct) of the epoxy coating, loaded with mesoporous carbon, decreased from 190 M Ω cm-2 to 66 M Ω cm-2. Intriguingly, the corrosion resistance of the epoxy coating, fortified with both mesoporous carbon and a corrosion inhibitor, exhibited a significant increase from 240 M Ω cm-2 to an impressive 1.1 G Ω cm-2 after the 60-day immersion period. Furthermore, the mechanical properties of the prepared coating were assessed using a dynamic analyzer, both before and after exposure to UV radiation.
(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.
Impact of Formation Cycle Current Density on the Cycling Stability of Zero-Excess Li-Metal Batteries
Authors: Kim Soochan , Didwal Pravin N. , Fiates Juliane , Dawson James A. , Weatherup Robert S. , De Volder Michael F. L.
Published: December 2024

Zero-excess Li-metal batteries (ZELMBs) are promising candidates for next-generation batteries with high energy densities and improved safety during cell manufacturing. However, the loss of Li that occurs during the initial anode formation hinders the practical application of this system and considerably affects the cycling stability. In this study, we optimize the initial formation of the anode using a formation protocol designed by controlling the charging current density and investigating its effect on cycling stability. This study provides insight into the behavior of ZELMBs and highlights the necessity for a tailored initial formation protocol for each electrolyte.
(Invited) Development of High Entropy Catalysts for Efficient Electrochemical Fuel Production
Authors: Sim Uk
Published: December 2024

Electrochemical fuel production methods, such as water splitting, ammonia, and synthetic hydrocarbon production, are at the forefront of sustainable energy resource development. However, the journey to commercialization is fraught with obstacles, particularly in creating active and stable electrocatalysts. This is a critical area of study, as these catalysts are the foundation of electrochemical water splitting for H2 production, nitrogen (NRR) and nitrate (NitRR) reduction reactions for ammonia production and CO2 reduction reaction (CO2RR) for synthetic hydrocarbon synthesis. Therefore, pursuing higher metal utilization efficiency and developing non-precious elements-based catalysts are crucial to ensure the feasibility of cost-effective hydrogen production systems. High entropy catalysts (HEC) with five or more metals are solid solution alloys with unique structures and electrochemical properties. The noble and non-noble metal-based HEC design strategy with strong metal support interaction (SMSI) and porous surfaces amplifies the extrinsic electrocatalytic activity, ensuring high durability over harsh electrochemical conditions for low maintenance and cost-efficiency. The main challenge lies in enhancing their extrinsic activity via catalyst-support interactions for efficient electrochemical reactions. To address this significant and persistent technical barrier, our research is focused on the intensive search for efficient, durable, and inexpensive HEC with high solar energy conversion efficiency for efficient electrochemical water splitting, hydrocarbon conversion reaction, and electrochemical ammonia production processes, thereby making a substantial contribution to the field of sustainable energy resources.

Figure 1
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.
Understanding Solubility: Zirconium Electrodeposition in Non-Aqueous Electrolytes
Authors: De Silva Umanga , Janusz Jordyn , Jones Ben , Stull Jamie A
Published: December 2024

Non-aqueous electrodeposition entails the process of depositing metals or materials onto electrodes using a solvent or electrolyte that isn't water-based. Researchers have been exploring various techniques such as molten salt, ionic liquids, organic solvents, and deep eutectic solvents for non-aqueous electrodeposition in order to obtain zirconium metal deposition. Our team has directed its attention towards deep eutectic solvents due to their increasing recognition as environmentally sustainable solvents. These solvents boast unique physical and chemical properties, effective dispersal capabilities, high purity, and cost-effectiveness, rendering them suitable for diverse applications. Particularly, they have garnered significant interest in electrodeposition endeavors over the past decade. Despite their advantageous characteristics as electrolytes in electrochemical processes, deep eutectic solvents present challenges such as low conductivity and limited solubility of specific components. Our research has encompassed studies on the solubility of various salts, commonly utilized as supporting electrolytes, alongside zirconium metal salts in deep eutectic solvents, both individually and in combination. We aim to analyze numerous parameters including temperature, pH, ionic strength, and conductivity to determine the optimal composition and parameter settings conducive to zirconium electrodeposition.
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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H. Sheng et al., Advanced Materials, 34, 2108947 (2022).
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
Thiocarbonyls as Performance Enhancing Additives for Lithium-Sulfur Batteries
Authors: Searle Joanne , Kibler Alexander , Walsh Darren Anthony , Johnson Lee R , Saywell Alexander , Newton Graham
Published: December 2024

The lithium-ion battery (LIB) has been key to the electrification of the automotive sector. It is anticipated that electrification of sectors such as haulage and aerospace will require energy storage systems with capacities and performance beyond the capabilities of traditional LIB chemistries.[1] Lithium-sulfur (Li-S) batteries are a front-runner among next generation battery technologies, thanks to their high theoretical capacities (1675 mAh g-1) and impressive gravimetric energy densities (2,700 Wh kg-1).[2,3] Despite their potential, there are numerous chemical challenges (active material dissolution, polysulfide shuttle, dendrite formation etc.) that must be overcome before widespread adoption of the technology.[4] Electrolyte additives have been explored as a means to minimise active material loss within the cell and improve long-term cyclability and cell discharge capacity.[5]

Thiocarbonyl compounds are well known in the polymer science community, behaving as reversible addition fragmentation chain transfer (RAFT) agents.[6] The reactivity of the thiocarbonyl group in the presence of nucleophilic molecules such as polysulfides renders them promising additives for Li-S batteries. Here, we present our studies on ethyl 2-(4-methoxyphenylcarbonothioyl thio)acetate (EM), a thiocarbonyl derivative, as a new type of electrolyte additive that can improve the cycle life of Li-S batteries. A variety of electrochemical and analytical techniques, combined with computational density functional theory (DFT) calculations, have been employed to assess the suitability of EM as an additive in Li2S cells. We have built an understanding of its interactions with active materials in a Li-S cell, with results proving that EM chemically reacts with and aids the oxidation of Li2S. Galvanostatic cycling has allowed us to corroborate our electrochemical and computational findings with cell cycling performance. We observe a significant enhancement in long-term cycling capacity when the additive is introduced to the electrolyte.

Figure 1. A blot plot displaying the discharge capacities at specific cycle numbers for standard (light grey) and EM (dark grey) cells to provide a statistical comparison.

References:

[1] T. Kim, W. Song, D.-Y. Son, L. K. Ono and Y. Qi, J. Mater. Chem. A, 2019, 7, 2942–2964.

[2] A. Fotouhi, D. J. Auger, L. O’Neill, T. Cleaver and S. Walus, Energies, 2017, 10.

[3] S. Gifford and J. Robinson, Faraday Insights, 2020, 1-5.

[4] A. Manthiram, Y. Fu, S.-H. Chung, C. Zu and Y.-S. Su, Chem. Rev., 2014, 114, 11751–11787.

[5] J. M. Cameron, C. Holc, A. J. Kibler, C. L. Peake, D. A. Walsh, G. N. Newton and L. R. Johnson, Chem. Soc.
Rev., 2021, 50, 5863–5883.

[6] S. Perrier, Macromolecules
, 2017, 50, 7433–7447.

Figure 1
Binary Mixture–Based Electrolytes Using Imidazolium-Based Ionic Liquids for Enhanced Safety and Electrochemical Performance of Lithium-Ion Batteries
Authors: Kakibe Takeshi , Hirai Daichi , Matsuda Satoshi , Nakamura Tatsuya , Kishi Hajime
Published: December 2024

In recent years, secondary lithium-ion batteries (LIBs) have become critical components for portable devices and large power source systems such as electric vehicles (EVs) and hybrid EVs (HEVs).[1],[2] However, conventional LIBs typically use flammable nonaqueous liquid electrolytes, posing a serious safety risk. Our previous study[3] demonstrated that one promising approach for safe LIBs involves using electrolytes based on a series of ionic liquids (ILs) with branched alkyl imidazolium cations. The introduction of bulky branched alkyl groups enhances charge delocalization in imidazolium cations, thereby improving the electrochemical reduction stability. Herein, we evaluated the compatibility and electrochemical performance of two types of ILs: branched alkyl functional and electrochemically polymerizable ILs. Moreover, binary mixture–based electrolytes based on their ILs were investigated for use in LIBs.

We synthesized two types of ILs: reduction-stable and polymerizable ILs (Fig. 1). An IL-based electrolyte was mixed with various compositions of reduction-stable and polymerizable ILs, with LiFSA (LiFSA molal concentration: ca. 1.5 mol/kg) serving as the Li ion source. The characteristics of the involved battery were examined using a graphite electrode | IL–LiFSA mixture–based electrolyte | Li metal half-cell configuration. The graphite electrode sheets comprised NMC powder (86 wt%) as the active material, acetylene black (7 wt%) as an electrically conductive additive, and poly(vinylidene fluoride) (7 wt%) as a binder. The graphite electrode sheet, separator, IL–LiFSA mixture–based electrolyte, and Li were assembled into a battery cell. Performance tests for charge–discharge rates were conducted at 303 K, with the involved rates varying from 0.1 to 0.5 C.

Fig. 2 shows the first charge–discharge profiles of the graphite | Li half-cells with [EPisoIm][FSA]–, [APisoIm][FSA]–, and [EPisoIm]0.8[APisoIm]0.2[FSA]–based electrolytes. During the first charge with the [APisoIm][FSA]– and [EPisoIm]0.8[APisoIm]0.2[FSA]–based electrolytes, a plateau was observed at approximately 0.5 V, attributed to the reduction decomposition and polymerization of [APisoIm] cations on graphite. The presence of [APisoIm] cations enabled the formation of a stable solid electrolyte interface, an electron-insulating, lithium-ion-conducting film.

[1] M. Wakihara, “Recent developments in lithium ion batteries”, Mater. Sci. Eng., R, 33, 109 (2001).

[2] D. D. Lecce, R. Verrelli, and J. Hassoun, “Lithium-ion batteries for sustainable energy storage: recent advances towards new cell configurations”, Green Chem., 19, 3442 (2017).

Figure 1
Insights on Structure and Redox Activity Enabling Outstanding Performance of Co-Free and Mn-Rich O2-Li0.75[Li0.15Ni0.15Mn0.7]O2 Cathode
Authors: Yu Jun Ho , Myung Seung-Taek
Published: December 2024

Layered O3 type cathode materials are notable alternatives for lithium-ion batteries due to their advantageous lithium-ion migration, operating voltage range, capacity, and cyclability. Ni-rich cathodes offer high capacities and voltages but face various issues like cation mixing, particle cracking, high exothermic reactivity, and presence of surface lithium residues, which negatively impact performance. Moreover, the heavy use of Ni and Co raises cost, supply, and ethical concerns. To address aforementioned issues, replacement with Mn is favorable for its abundance, cost-effectiveness, and enhanced structural stability by reducing oxygen generation and delaying phase transitions to a spinel phase. However, replacing Ni with Mn can lead to the formation of unwanted LiMnO2 phases which has stability issues due to existence of Mn3+ ions. Recent studies show Mn's effectiveness in sodium-ion batteries, highlighting operating voltage and capacity benefitting from lattice oxygen redox reactions. Work on O2 type Li2/3[Ni1/3Mn2/3]O2 obtained from Na2/3[Ni1/3Mn2/3]O2 via ionic exchange demonstrated stable capacity without phase transitions, attributed to the O2 layer structure that prevents Mn migration and phase changes. Herein, we report the O2 structured cathode, Li-excess O2 Li0.75[Li0.15Ni0.15Mn0.7]O2 (LLNM) shows promising results, including high capacity and stable cyclability, with significant contributions of charge compensation from O2-/O2
n- redox pairs at the high operating voltage. This research refined the crystal structure of LLNM and explored its charge transfer mechanisms, revealing a high discharge capacity (≈ 284 mAh g-1) without phase transitions and stable oxygen involvement in charge compensation (85% of initial capacity after 200 cycles). The study also discusses the LLNM material's structural and electrochemical stability, paving the way for high-capacity cathode development beyond NCM and Li-rich alternatives.

Figure 1