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Alcaraz, Lorena, Carlos Díaz-Guerra, Joaquín Calbet, María Luisa López, and Félix A. López. "Obtaining and Characterization of Highly Crystalline Recycled Graphites from Different Types of Spent Batteries." Materials 15, no. 9 (April 30, 2022): 3246. http://dx.doi.org/10.3390/ma15093246.
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Spent batteries recycling is an important way to obtain low-cost graphite. Nevertheless, the obtaining of crystalline graphite with a rather low density of defects is required for many applications. In the present work, high-quality graphites have been obtained from different kinds of spent batteries. Black masses from spent alkaline batteries (batteries black masses, BBM), and lithium-ion batteries from smartphones (smartphone black masses, SBM) and electric and/or hybrid vehicles (lithium-ion black masses, LBM) were used as starting materials. A hydrometallurgical process was then used to obtain recycled graphites by acidic leaching. Different leaching conditions were used depending on the type of the initial black mass. The final solids were characterized by a wide set of complementary techniques. The performance as Li ion batteries anode of the sample with better structural quality was assessed.
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Mamatkarimov, O., B. Uktamaliyev, and A. Abdukarimov. "PREPARATION OF POLY (METHYL METHACRYLATE)-BASED POLYMER ELECTROLYTES FOR SOLID-STATE FOR Mg-ION BATTERIES." SEMOCONDUCTOR PHYSICS AND MICROELECTRONICS 3, no. 4 (August 30, 2021): 16–19. http://dx.doi.org/10.37681/2181-1652-019-x-2021-4-2.
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It is known that the new metal-based solid polymer electrolyte batteries are characterized by high energy and power density, low cost, simplicity of manufacturing technology and long-term non-discharge. Therefore, the technology of their preparation is considered in this study
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Maier, Joachim, and Ute Lauer. "Ionic Contact Equilibria in Solids-Implications for Batteries and Sensors." Berichte der Bunsengesellschaft für physikalische Chemie 94, no. 9 (September 1990): 973–78. http://dx.doi.org/10.1002/bbpc.19900940918.
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Kanno, Ryoji, Satoshi Hori, Keisuke Shimizu, and Kazuhiro HIkima. "(Invited) Development and New Perspectives in Lithium Ion Conductors and Solid-State Batteries." ECS Meeting Abstracts MA2024-02, no. 8 (November 22, 2024): 1085. https://doi.org/10.1149/ma2024-0281085mtgabs.
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All-solid-state batteries, which consist entirely of solid components, are being developed as the energy storage devices for the next generation. In the presentation, after showing the history, current status, and challenges of solid-state battery development, our research on the solid-state electrolyte exploration and solid-state battery development will be presented. We investigated the solid electrolytes to improve the performance of solid-state batteries, and the battery reactions using model-type solid-state batteries. We have explored new solid electrolytes and found a material Li10GeP2S12(LGPS) with conductivity comparable to or higher than the ionic conductivity of Li-based organic solvent electrolytes. It was found that the power density of batteries can be dramatically increased by utilizing the solid-electrolytes of superior ionic conductivity. Based on the LGPS material developments, the intrinsic advantages of the solid-state battery, fast ion diffusion mechanism in the LGPS solids, and challenges of developing the technology needed to produce practical batteries will be discussed. We have developed model battery system based on the idea that battery reactions can be observed more in detail when batteries are solid-state. Battery reactions proceed at the electrode/electrolyte interface. It is not well understood how the electrochemical reactions at the interface and the changes in the electronic structure of the electrode proceed during charging and discharging. In solid-state batteries, the electrode-electrolyte interface can be considered as a heterojunction interface in semiconductors. Spectroscopic methods can reveal the electronic structure of the battery during charge-discharge reactions. As solid-state batteries become practical devices, the battery science and technology will also progress.
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Alcántara, Ricardo, Carlos Pérez-Vicente, Pedro Lavela, José L. Tirado, Alejandro Medina, and Radostina Stoyanova. "Review and New Perspectives on Non-Layered Manganese Compounds as Electrode Material for Sodium-Ion Batteries." Materials 16, no. 21 (October 30, 2023): 6970. http://dx.doi.org/10.3390/ma16216970.
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After more than 30 years of delay compared to lithium-ion batteries, sodium analogs are now emerging in the market. This is a result of the concerns regarding sustainability and production costs of the former, as well as issues related to safety and toxicity. Electrode materials for the new sodium-ion batteries may contain available and sustainable elements such as sodium itself, as well as iron or manganese, while eliminating the common cobalt cathode compounds and copper anode current collectors for lithium-ion batteries. The multiple oxidation states, abundance, and availability of manganese favor its use, as it was shown early on for primary batteries. Regarding structural considerations, an extraordinarily successful group of cathode materials are layered oxides of sodium, and transition metals, with manganese being the major component. However, other technologies point towards Prussian blue analogs, NASICON-related phosphates, and fluorophosphates. The role of manganese in these structural families and other oxide or halide compounds has until now not been fully explored. In this direction, the present review paper deals with the different Mn-containing solids with a non-layered structure already evaluated. The study aims to systematize the current knowledge on this topic and highlight new possibilities for further study, such as the concept of entatic state applied to electrodes.
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Mauger, Julien, Paolella, Armand, and Zaghib. "Building Better Batteries in the Solid State: A Review." Materials 12, no. 23 (November 25, 2019): 3892. http://dx.doi.org/10.3390/ma12233892.
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Most of the current commercialized lithium batteries employ liquid electrolytes, despite their vulnerability to battery fire hazards, because they avoid the formation of dendrites on the anode side, which is commonly encountered in solid-state batteries. In a review two years ago, we focused on the challenges and issues facing lithium metal for solid-state rechargeable batteries, pointed to the progress made in addressing this drawback, and concluded that a situation could be envisioned where solid-state batteries would again win over liquid batteries for different applications in the near future. However, an additional drawback of solid-state batteries is the lower ionic conductivity of the electrolyte. Therefore, extensive research efforts have been invested in the last few years to overcome this problem, the reward of which has been significant progress. It is the purpose of this review to report these recent works and the state of the art on solid electrolytes. In addition to solid electrolytes stricto sensu, there are other electrolytes that are mainly solids, but with some added liquid. In some cases, the amount of liquid added is only on the microliter scale; the addition of liquid is aimed at only improving the contact between a solid-state electrolyte and an electrode, for instance. In some other cases, the amount of liquid is larger, as in the case of gel polymers. It is also an acceptable solution if the amount of liquid is small enough to maintain the safety of the cell; such cases are also considered in this review. Different chemistries are examined, including not only Li-air, Li–O2, and Li–S, but also sodium-ion batteries, which are also subject to intensive research. The challenges toward commercialization are also considered.
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Cheong, Do Sol, and Hyun-Kon Song. "Organic Ice Electrolytes for Lithium Batteries." ECS Meeting Abstracts MA2024-02, no. 8 (November 22, 2024): 1100. https://doi.org/10.1149/ma2024-0281100mtgabs.
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Solid-state ionic conductors are being actively developed for batteries employing lithium electrochemistry. Lithium battery cells based on solid electrolytes are believed to be free from concerns found in conventional lithium ion batteries (LIBs) based on liquid electrolytes. Solid electrolytes are expected to be non-volatile and nonflammable without electrolyte leakage, suppressing dendritic growth of lithium metal. The benefits of solid electrolytes come from their immobile and mechanically hard state distinguished from the mobile and fluidic state of liquid electrolytes. Solid electrolytes popularly employed for lithium batteries, including inorganic oxides and sulfides as well as organic polymers, are classified as network solids (e.g., Li7La3Zr2O12, garnet in oxides and Li6PS5Cl, argyrodite in sulfides) based on covalent and/or ionic bonds. A building unit of network solids, the atomic ratio of which is described by chemical formula, is repeatedly extended to form a continuous network throughout the material. On the other hand, the possibility of molecular solid electrolytes, the phases of which are determined by the inter-molecular interactions, has rarely been suggested. Recently, an example of molecular solid electrolyte was presented by Guo, Z. et al. (2019). When 1 m Li2SO4 (aq) was frozen, the ionic conductivity of the solid ice electrolyte was 0.1 mS cm-1 at -17 oC. Such an ionically conductive ice electrolyte was not easily expected from the practical wisdom in LIB field: LIBs do not work when their electrolytes are frozen. For example, carbonate-based mixture electrolyte, ED(=1 M LiPF6 in ethylene carbonate/dimethyl carbonate) was frozen at -30oC and the cell used that electrolyte could not delivered any charging/discharging capacity at all. In contrast, each solvent of components of ED, a cyclic carbonate (ethylene carbonate, EC) and a linear carbonate (dimethyl carbonate, DMC) were theoretically expected to have Li+-conductive channels in their frozen crystal structures. Experimentally, the high-t Li+ (Li+ transference number) frozen-solid electrolytes (EC or DMC based single-solvent electrolyte) successfully drove lithium metal batteries below their freezing points (fp) even if their mixture did not work as an ionic conductor in its frozen state. Interestingly, the t Li+ of the electrolytes sharply increased below fp, declaring that the conduction mechanism changed from vehicular conduction to hopping conduction of Li+ through crystal structure with low diffusion energy barrier (0.28 eV at -20 oC vs. 0.32 eV of LLZO at RT). From the lessons from the carbonates, we proposed a cyclic sulfone (sulfolane, SL) as another solvent for molecular-solid electrolytes. The frozen SL electrolyte at -30 oC allowed its LMB cells to deliver the capacity equivalent to that of a conventional carbonate liquid electrolyte that is not frozen at the same -30 oC (EC+EMC where EMC = ethylmethyl carbonate). More importantly, the LMB cells with the frozen SL was longer-lasting than the liquid cells. The frozen organic ice electrolyte effectively and totally suppressed dendritic growth of lithium metal by utilizing its own mechanical hardness, high t Li+ and interface-specific anion-derived SEI layer.
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Kim, Sangtae, Shu Yamaguchi, and James A. Elliott. "Solid-State Ionics in the 21st Century: Current Status and Future Prospects." MRS Bulletin 34, no. 12 (December 2009): 900–906. http://dx.doi.org/10.1557/mrs2009.211.
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AbstractThe phenomenon of ion migration in solids forms the basis for a wide variety of electrochemical applications, ranging from power generators and chemical sensors to ionic switches. Solid-state ionics (SSI) is the field of research concerning ionic motions in solids and the materials properties associated with them. Owing to the ever-growing technological importance of electrochemical devices, together with the discoveries of various solids displaying superior ionic conductivity at relatively low temperatures, research activities in this field have grown rapidly since the 1960s, culminating in “nanoionics”: the area of SSI concerned with nanometer-scale systems. This theme issue introduces key research issues that we believe are, and will remain, the main research topics in nanoionics and SSI during the 21st century. These include the application of cutting-edge experimental techniques, such as secondary ion mass spectroscopy and nuclear magnetic resonance, to investigate ionic diffusion in both bulk solids and at interfaces, as well as the use of atomic-scale modeling as a virtual probe of ionic conduction mechanisms and defect interactions. We highlight the effects of protonic conduction at the nanometer scale and how better control of interfaces can be employed to make secondary lithium batteries based on nanoionics principles. Finally, in addition to power generation and storage, the emergence of atomic switches based on cation diffusion shows great promise in developing next-generation transistors using SSI.
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Ota, Hiroki. "(Invited) Application of Liquid Metals in Battery Technology." ECS Meeting Abstracts MA2024-02, no. 35 (November 22, 2024): 2502. https://doi.org/10.1149/ma2024-02352502mtgabs.
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Stretchable devices have many potential applications, including wearable electronics, robotics, and health monitoring. These mechanically adaptable devices and sensors can seamlessly integrate with electronics on curved or soft surfaces. Given that liquids are more deformable than solids, sensors and actuators utilizing liquids encased in soft templates as sensing elements are particularly suited for these applications. Such devices, leveraging ultra-flexible conductive materials, are referred to as stretchable electronics. Liquid metals (LMs) have emerged as one of a leading material in this field. In recent years, interest in liquid metals has surged, notably in flexible and soft electronics. When considering liquid metals, mercury often comes to mind due to its fluid state at room temperature. However, its high toxicity precludes its use in wearable technology. Instead, gallium-based liquid metals are preferred due to their safety in such applications. Gallium alone melts at about 30°C, but an alloy of 75% gallium and 25% indium lowers the melting point to 15°C. Adding 10% tin further reduces it to -19°C. These gallium-based liquid metals, which form low-viscosity eutectic alloys, have extremely low melting points and high biocompatibility. In addition, they rapidly form a thin oxide layer on their surface, which complicates patterning on substrates. To address this, metal nanoparticles like nickel can be blended using ultrasonic probing to create a malleable paste. These materials are still under research to explore additional functionalities. Liquid metals are particularly promising for self-healing materials and advanced wiring technologies for sensors and smart devices in stretchable electronics. More recently, their application in battery technologies in addition to sensors and wiring has been proposed. With ongoing advancements in flexible and stretchable electronics, the flexibility of lithium-ion batteries, essential for powering these devices, is also under investigation. This presentation discusses research on flexible battery electrodes using liquid metal and on materials for stretchable battery packages. In our first study, liquid metal served as a battery electrode, integrating the reaction and current collecting layers into a single process, thus simplifying manufacturing. However, this integration results in lower conductivity compared to traditional two-layer electrodes. By employing materials such as Li4Ti5O12 (LTO) or Li2TiS3 (LTS) with liquid metal, we developed a high-conductivity, printable liquid metal electrode ink that combines both functions. In a second application, liquid metal was used as an package for stretchable batteries. Recent studies on batteries have primarily focused on enhancing their stability and lifespan, with less attention to packaging. Conventionally, aluminum laminate film is used to prevent moisture and gas permeation in highly deformable batteries. Our study introduced a novel approach using a layer-by-layer technique to apply a thin liquid metal coating on a gold-coated thermoplastic polyurethane film, resulting in a stretchable packaging film with excellent gas barrier properties. This innovation not only enhances the battery's operational stability but also allows it to function reliably in atmospheric condition. The applications for liquid metals are extensive and hold promise for further exploration in various fields.
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Yang, Jinlin, Jibiao Li, Wenbin Gong, and Fengxia Geng. "Genuine divalent magnesium-ion storage and fast diffusion kinetics in metal oxides at room temperature." Proceedings of the National Academy of Sciences 118, no. 38 (September 14, 2021): e2111549118. http://dx.doi.org/10.1073/pnas.2111549118.
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Rechargeable magnesium batteries represent a viable alternative to lithium-ion technology that can potentially overcome its safety, cost, and energy density limitations. Nevertheless, the development of a competitive room temperature magnesium battery has been hindered by the sluggish dissociation of electrolyte complexes and the low mobility of Mg2+ ions in solids, especially in metal oxides that are generally used in lithium-ion batteries. Herein, we introduce a generic proton-assisted method for the dissociation of the strong Mg–Cl bond to enable genuine Mg2+ intercalation into an oxide host lattice; meanwhile, the anisotropic Smoluchowski effect produced by titanium oxide lattices results in unusually fast Mg2+ diffusion kinetics along the atomic trough direction with a record high ion conductivity of 1.8 × 10−4 S ⋅ cm−1 on the same order as polymer electrolyte. The realization of genuine Mg2+ storage and fast diffusion kinetics enabled a rare high-power Mg-intercalation battery with inorganic oxides. The success of this work provides important information on engineering surface and interlayer chemistries of layered materials to tackle the sluggish intercalation kinetics of multivalent ions.
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Doménech-Carbó, Antonio, Jan Labuda, and Fritz Scholz. "Electroanalytical chemistry for the analysis of solids: Characterization and classification (IUPAC Technical Report)." Pure and Applied Chemistry 85, no. 3 (December 16, 2012): 609–31. http://dx.doi.org/10.1351/pac-rep-11-11-13.
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Solid state electroanalytical chemistry (SSEAC) deals with studies of the processes, materials, and methods specifically aimed to obtain analytical information (quantitative elemental composition, phase composition, structure information, and reactivity) on solid materials by means of electrochemical methods. The electrochemical characterization of solids is not only crucial for electrochemical applications of materials (e.g., in batteries, fuel cells, corrosion protection, electrochemical machining, etc.) but it lends itself also for providing analytical information on the structure and chemical and mineralogical composition of solid materials of all kinds such as metals and alloys, various films, conducting polymers, and materials used in nanotechnology. The present report concerns the relationships between molecular electrochemistry (i.e., solution electrochemistry) and solid state electrochemistry as applied to analysis. Special attention is focused on a critical evaluation of the different types of analytical information that are accessible by SSEAC.
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Morales, Yam, Nelson Herrera, and Kevin Pérez. "Lithium carbonate sedimentation using flocculants with different ionic bases." Chemical Industry 75, no. 4 (2021): 205–12. http://dx.doi.org/10.2298/hemind201128020m.
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Lithium has become a metal of enormous interest worldwide. The extensive use of recharge-able batteries for a range of applications has pushed for rapid growth in demand for lithium carbonate. This compound is produced by crystallization, by reaction with lithium chloride (in solution) and by adding sodium carbonate. Low sedimentation rates in the evaporation pools present a problem in the crystallization process. For this reason, in this work, mineral sedimen-tation tests were carried out with the use of two flocculant types with different ionic charges. The tests were carried out at a laboratory level using different dosages for each flocculant and measurements were performed to obtain the increase in the content of solids in the sediment. The anionic flocculant had better performance as compared to that of the cationic flocculant, increasing the sedimentation rate of lithium carbonate by up to 6.5. However, similar solids contents were obtained with the use of the cationic flocculant at 3.5 times lower dosage making it the flocculant of choice regarding the economic point of view.
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Gao, Xiang, Daining Fang, and Jianmin Qu. "A chemo-mechanics framework for elastic solids with surface stress." Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences 471, no. 2182 (October 2015): 20150366. http://dx.doi.org/10.1098/rspa.2015.0366.
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Elasticity problems involving solid-state diffusion and chemo-mechanical coupling have wide applications in energy conversion and storage devices such as fuel cells and batteries. Such problems are usually difficult to solve because of their strongly nonlinear characteristics. This study first derives the governing equations for three-dimensional chemo-elasticity problems accounting for surface stresses in terms of the Helmholtz potentials of the displacement field. Then, by assuming weak coupling between the chemical and mechanical fields, a perturbation method is used and the nonlinear governing equations are reduced to a system of linear differential equations. It is observed from these equations that the mechanical equilibrium equations of the first two orders are not dependent on the chemical fields. Finally, the above chemo-mechanics framework is applied to study the stress concentration problem of a circular nano-hole in an infinitely large thick plate with prescribed mechanical and chemical loads at infinity. Explicit expressions up to the third order are obtained for the stress and solute concentration fields. It is seen from these solutions that, different from the classical elasticity result, the stress concentration factor near the nano-hole depends on the surface stress, applied tensile load and prescribed solute concentration at infinity.
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Cardoza, Neal Amadeus, Mary Qin Hassig, Taber Yim, Gregory R. Schwenk, Michel W. Barsoum, and Vibha Kalra. "Dopamine Functionalized TiO2 1D Lepidocrocite Mesoporous Particles As a Sulfur Host." ECS Meeting Abstracts MA2024-01, no. 1 (August 9, 2024): 109. http://dx.doi.org/10.1149/ma2024-011109mtgabs.
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Lithium sulfur batteries are attractive because of their high specific capacities. However, a variety of issues, chiefly polysulfides and the polysulfide shuttle still hinder their development. In our past work we demonstrated a new form of titania-based nanomaterials which we labelled 1 dimensional lepidocrocite nanofilaments (1DLs) as a sulfur (S) host for Li-S batteries1. 1DL is synthesized using a facile bottom-up scalable reaction, directly from commercial 3D bulk solids at ambient pressures and near ambient temperatures2. Moreover, these materials self-assemble into a plethora of microstructures – from individual 1D nanofilaments 5x7 Å2 in cross-section to 2D flakes to mesoscopic particles, all comprised of 1DL - depending on the synthesis and washing parameters. The multitude of structures allows for a variety of applications like electrocatalysis and hydrogen production3. Here we introduce a new structure of 1DLs - mesoporous particles - as S hosts. We further show that by employing a facile, aqueous, 1-step surface functionalization with dopamine – confirmed through changes in the FTIR peaks and an increase in the d-spacing in XRD (inst in Fig 1b) – we increase their interaction with S. The surface functionalization results in a reduction of the 1DL bandgap energy, Eg, to ~1.84 eV, which is a ≈ 50% reduction over un-functionalized 1DL. Additionally, the surface functionalization renders a more conformal coating of S on the 1DL, leading to increased S utilization and interaction with the 1DL, seen in a 20% reduction in of polysulfide shuttle current and 750 mAh.gs -1 at 0.5 C at a loading of 2 mg.cm-2 (seen in Fig 1a and 1b). This is further seen in the increased interactions of the thiosulfate species and Lewis acid-base interactions, shown in our prior work with S and 1DL. References Cardoza, N. A.; Badr, H. O.; Pereira, R.; Barsoum, M. W.; Kalra, V. One-Dimensional, Titania Lepidocrocite-Based Nanofilaments and Their Polysulfide Anchoring Capabilities in Lithium–Sulfur Batteries. ACS Appl. Mater. Interfaces 2023, 15 (44), 50973–50980. Badr, H. O.; Cope, J.; Kono, T.; Torita, T.; Lagunas, F.; Castiel, E.; Klie, R. F.; Barsoum, M. W. Titanium Oxide-Based 1D Nanofilaments, 2D Sheets, and Mesoporous Particles: Synthesis, Characterization, and Ion Intercalation. Matter 2023, 6 (10), 3538–3554. Badr, H. O.; Natu, V.; Neațu, Ștefan; Neațu, F.; Kuncser, A.; Rostas, A. M.; Racey, M.; Barsoum, M. W.; Florea, M. Photo-Stable, 1D-Nanofilaments TiO2-Based Lepidocrocite for Photocatalytic Hydrogen Production in Water-Methanol Mixtures. Matter 2023, 6 (9), 2853–2869. Figure 1
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Xiao, Chuanlian, Chia-Chin Chen, and Joachim Maier. "Discrete Modeling of Ionic Space Charge Zones in Solids." ECS Meeting Abstracts MA2022-01, no. 45 (July 7, 2022): 1905. http://dx.doi.org/10.1149/ma2022-01451905mtgabs.
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In this contribution discrete modeling of space charge zones in solids is presented, which is a sensible approach for handling pronounced space charge potentials as well as non-idealities in realistic solid state system1. At interfaces in charge-carrier containing systems, individual charge carriers redistribute, which leads to transport but also storage anomalies2. Such space charge zones are usually described by a continuum picture based on classic Gouy-Chapman (or Mott-Schottky) models. In addition to issues of internal consistency, this continuum approach is questionable if extremely steep profiles close to the interface occur, and analytical corrections are not very helpful. We show how discretization remedies a variety of such short-comings, allows for a straightforward taking account of non-idealities, and even provides surprising insight into double layer capacitance and conductance effects. Combining discrete modeling with the continuum description provides a particularly powerful method with the help of which non-idealities in the first layers (variation in structure, elastic effects, saturation effects, changes in dielectric constant) can be directly addressed. Various examples of practical value for functional ceramics and batteries are discussed. We believe that such discretization represents a substantial progress in the field of space charge theory being advantageous over introducing corrections into the already overstrained Gouy-Chapman function. References C. Xiao; C.-C. Chen; J. Maier, Discrete modeling of ionic space charge zones in solids, submitted. C.-C. Chen, J. Maier, Decoupling electron and ion storage and the path from interfacial storage to artificial electrodes, Nature Energy 2018, 3 (2), 102-108.
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Xi, Dawei, Zheng Yang, Abdulrahman Alfaraidi, and Michael J. Aziz. "Single-Membrane pH-Decoupling Aqueous Battery Using Proton-Coupled Electrochemistry for pH Recovery." ECS Meeting Abstracts MA2024-02, no. 1 (November 22, 2024): 12. https://doi.org/10.1149/ma2024-02112mtgabs.
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Aqueous redox flow batteries (ARFBs) constitute a promising technology for cost-effective and scalable storage of intermittent renewable energy from sources like wind and solar. For long discharge-duration storage (> 8 h), these batteries offer a unique advantage by decoupling energy storage from power generation, providing a level of design versatility and scalability that traditional rechargeable batteries can hardly match. Typically, the negolyte and posolyte of ARFBs exhibiting long-term operation have roughly the same pH. In contrast, pH-decoupling aqueous redox flow batteries (ARFBs) utilize different pH values in the negolyte and the posolyte, enabling the cell to achieve higher cell voltages and support a broader range of redox pair combinations. Managing the crossover of acid and base, along with an economical and straightforward method to recover their crossover, is critical for long-term operation of pH-decoupling ARFBs. We have previously investigated the crossover of acid and base in multichamber pH-decoupling ARFBs and developed a small, but adequately-sized bipolar membrane (BPM) sub-cell for pH recovery.1 Here, we introduce a new pH-decoupling design utilizing a conventional single-membrane ARFB architecture. This approach reduces the ohmic area-specific resistance while maintaining an acceptably low level of acid-base crossover. We explore various electrolyte pairs, ranging from solutions to semi-solids, anions to cations, acids to bases, showing that this design allows flexibility in electrolyte combinations. The setup can result in improved energy efficiency, higher areal power density, and reduced capital costs. Along with different cells, we demonstrated how proton-coupled electrochemical reactions can serve as proton pumps, enabling in-situ or ex-situ pH recovery in these pH-decoupling setups and discussed its relationship to BPM pH recovery. 1. Xi, D., Alfaraidi, A.M., Gao, J. et al. Mild pH-decoupling aqueous flow battery with practical pH recovery. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01474-1 Figure 1
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Bistri, Donald, and Claudio V. Di Leo. "A Thermodynamically Consistent, Phase-Field Electro-Chemo-Mechanical Theory with Account for Damage in Solids: Application to Metal Filament Growth in Solid-State Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 523. http://dx.doi.org/10.1149/ma2022-024523mtgabs.
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Solid-state batteries (SSBs) present a promising technology and have attracted significant research attention owing to their superior properties including increased energy density (3860 mAh), wider electrochemical window (0-5V) and safer electrolyte design. From a safety standpoint, SSBs are particularly appealing in that replacement of flammable conventional organic electrolytes with highly conductive, mechanically stiff inorganic solid-state electrolytes (SSEs) can alleviate failure due to short circuit or ignition. However, operation of SSBs is hampered by numerous chemo-mechanical challenges [1 - 4], the most critical one associated with metal filament growth across the SSE. Filament protrusions can initiate at perturbations of the interface or microstructural heterogeneities and subsequently grow through the SSE, causing the battery to short-circuit. It is critical to understand from both an experimental and modeling perspective the interplay of various mechanisms including morphology of the SSE microstructure, elastic-viscoplastic behavior of Li-metal, critical current density and stack pressure on the morphology of filamentary protrusions across the SSE. While much has been done to understand the interplay of aforementioned mechanisms from an experimental standpoint [5,6], theoretical frameworks on modeling of filaments growth in SSBs are still at their infancy and typically simplify dendrites as pressurized cracks under a linear-elastic fracture mechanics (LEFM) approach [7-8]. In this work, we propose a thermodynamically consistent phase-field reaction-diffusion-damage theory to investigate the morphology of filament growth across the SSE under varying chemo-mechanical operational conditions. The theory is fully coupled with electrodeposition at the Li metal-SSE interface impacting mechanical deformation, stress generation and subsequent fracture of the SSE. Conversely, electrodeposition kinetics are affected by mechanical stresses through a thermodynamically consistent, physically motivated driving force that distinguishes the role of various chemical, electrical and mechanical contributions. Concurrently, the theory captures the interplay between crack propagation and electrodeposition phenomena by tracking the damage and reaction field using separate phase-field variables such that metal growth is preceded by and confined to damaged regions within the SSE accessible by Li-metal. This is a critical feature of the theory and confirms experimental observations that the crack front propagates ahead of Li. We specialize the theory and study the role of variations of chemo-mechanical properties (i.e. applied electric potential, SSE fracture energy) on the morphology of metal filament growth and map operational conditions to distinguish between domains of i) stable vs. unstable growth ii) intergranular vs. transgranular growth mode. In doing so, the proposed framework provides a quantitative understanding on mechanisms dictating metal filament growth in SSEs and identifies mitigation strategies to employ in future SSB designs for successful operation. References: [1] Zhang, Fangzhou, et al. "A review of mechanics-related material damages in all-solid-state batteries: Mechanisms, performance impacts and mitigation strategies." Nano Energy 70 (2020): 104545. [2] Bistri, Donald, Arman Afshar, and Claudio V. Di Leo. "Modeling the chemo-mechanical behavior of all-solid-state batteries: a review." Meccanica 56.6 (2021): 1523-1554. [3] Wang, Peng, et al. "Electro–chemo–mechanical issues at the interfaces in solid‐state lithium metal batteries." Advanced Functional Materials 29.27 (2019): 1900950 [4] Bistri, Donald, and Claudio V. Di Leo. "Modeling of Chemo-Mechanical Multi-Particle Interactions in Composite Electrodes for Liquid and Solid-State Li-Ion Batteries." Journal of The Electrochemical Society 168.3 (2021): 030515. [5] Ren, Yaoyu, et al. "Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte." Electrochemistry Communications 57 (2015): 27-30. [6] Cheng, Eric Jianfeng, Asma Sharafi, and Jeff Sakamoto. "Intergranular Li metal propagation through polycrystalline Li6. 25Al0. 25La3Zr2O12 ceramic electrolyte." Electrochimica Acta 223 (2017): 85-91. [7] Klinsmann, Markus, et al. "Dendritic cracking in solid electrolytes driven by lithium insertion." Journal of Power Sources 442 (2019): 227226. [8] Bucci, Giovanna, and Jake Christensen. "Modeling of lithium electrodeposition at the lithium/ceramic electrolyte interface: the role of interfacial resistance and surface defects." Journal of Power Sources 441 (2019): 227186.
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Giorgetti, Marco. "A Review on the Structural Studies of Batteries and Host Materials by X-Ray Absorption Spectroscopy." ISRN Materials Science 2013 (May 9, 2013): 1–22. http://dx.doi.org/10.1155/2013/938625.
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This review highlights the use of the X-ray absorption spectroscopy (XAS) as a local structural tool for selected atoms in several host materials. The main characteristics of XAS to be element-sensitive and its applicability to all states of matter, including crystalline solids and amorphous and liquid states, permit an in-depth study of the structural properties of a large variety of materials. This includes intercalation materials where a host structure can accommodate guest species. Host guest equilibria are at the basis of a large variety of technological applications; in particular they have been used for energy storage, ion-exchange membranes, electrochromism, and analytical sensing. A selection of XAS experiments conducted in the field of batteries, mainly on cathodes, and applications in the field of metal hexacyanoferrates and double layered hydroxides are outlined.
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Katerine, Igal, Arreche Romina A, Sambeth Jorge E, Bellotti Natalia, Vega-Baudrit José R, Redondo-Gómez Carlos, and Vázquez Patricia G. "Antifungal activity of cotton fabrics finished modified silica-silver- carbon-based hybrid nanoparticles." Textile Research Journal 89, no. 5 (February 19, 2018): 825–33. http://dx.doi.org/10.1177/0040517518755792.
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In this work, the one-pot sol-gel synthesis of novel siliceous matrixes doped with carbon from spent batteries is reported. The obtained solids with silver nitrate were characterized by their antifungal activity against Aspergillus sp., Cladosporium sp. and Chaetomium globosum, three well-known cellulolytic microorganisms responsible for the deterioration of cotton fabric. In this research it was possible to develop a methodology for the impregnation of cotton fabrics (brin type) and to evaluate the antifungal efficacy. Cotton fabric containing the highest amount of carbon showed the highest antifungal activity against C. globosum and Aspergillus sp. This may be because as the amount of carbon in the silica increases, there is an increase in the surface area that facilitates an effective distribution of the active phase to act, inhibiting the fungal growth.
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Szpakiewicz-Szatan, Aleksander, Szymon Starzonek, Tomasz K. Pietrzak, Jerzy E. Garbarczyk, Sylwester J. Rzoska, and Michał Boćkowski. "Novel High-Pressure Nanocomposites for Cathode Materials in Sodium Batteries." Nanomaterials 13, no. 1 (December 30, 2022): 164. http://dx.doi.org/10.3390/nano13010164.
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A new nanocomposite material was prepared by high pressure processing of starting glass of nominal composition NaFePO4. Thermal, structural, electrical and dielectric properties of the prepared samples were studied by differential thermal analysis (DTA), X-ray diffraction (XRD) and broadband dielectric spectroscopy (BDS). It was demonstrated that high-pressure–high-temperature treatment (HPHT) led to an increase in the electrical conductivity of the initial glasses by two orders of magnitude. It was also shown that the observed effect was stronger than for the lithium analogue of this material studied by us earlier. The observed enhancement of conductivity was explained by Mott’s theory of electron hopping, which is more frequent in samples after pressure treatment. The final composite consisted of nanocrystalline NASICON (sodium (Na) Super Ionic CONductor) and alluaudite phases, which are electrochemically active in potential cathode materials for Na batteries. Average dimensions of crystallites estimated from XRD studies were between 40 and 90 nm, depending on the phase. Some new aspects of local dielectric relaxations in studied materials were also discussed. It was shown that a combination of high pressures and BDS method is a powerful method to study relaxation processes and molecular movements in solids. It was also pointed out that high-pressure cathode materials may exhibit higher volumetric capacities compared with commercially used cathodes with carbon additions.
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Kleefoot, Max-Jonathan, Jens Sandherr, Marc Sailer, Sara Nester, Jiří Martan, Volker Knoblauch, Malte Kumkar, and Harald Riegel. "Investigation on the parameter dependency of the perforation process of graphite based lithium-ion battery electrodes using ultrashort laser pulses." Journal of Laser Applications 34, no. 4 (November 2022): 042003. http://dx.doi.org/10.2351/7.0000757.
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Perforation of lithium-ion battery electrodes has recently become an increasing interest in science and industry. Perforated electrodes have shown improved electrochemical properties compared to conventional, nonperforated electrodes. It has been demonstrated that through perforation, the fast-charging capability and the lifetime of these batteries can be significantly improved. The electrodes for lithium-ion batteries consist of a copper foil onto which the electrode material is applied as a porous layer. This layer is mainly composed of active material particles, which are bound together by a binder phase. Here, synthetic graphite was used as an active material. Up to now, it has been shown that an advantageous and precise perforation geometry can be produced by ultrashort laser pulse ablation. Since the ablation volumes during perforation of the porous electrode material with ultrashort laser pulses are unusually high compared to solids, this work investigates the parameter dependency on the ablation mechanisms in detail. For this purpose, in particular, single-pulse ablation was investigated with respect to the ablation thresholds at different pulse durations. The pulse durations were varied over a large range from 400 fs to 20 ps. By varying the number of pulses per perforation up to 50 and the single-pulse energy up to 45 μJ, it could be shown that a homogeneous ablation down to the conductor foil through the 63 μm thick active material layer can be achieved.
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Zhang, Yirui, Dimitrios Fraggedakis, Tao Gao, Shakul Pathak, Ryan Stephens, Martin Z. Bazant, and Yang Shao-Horn. "Lithium-Ion Intercalation By Coupled Ion-Electron Transfer Mechanism." ECS Meeting Abstracts MA2024-02, no. 2 (November 22, 2024): 221. https://doi.org/10.1149/ma2024-022221mtgabs.
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Ion intercalation in intercalation solids is crucial for energy storage device, including Li-ion batteries. Despite significant advancements in understanding Li-ion diffusion and discoveries of new electrodes and electrolytes, the molecular process of ion intercalation across electrode-electrolyte interfaces remains poorly understood. Li intercalation kinetics has been traditionally treated by the empirical Butler-Volmer kinetics, but remains poorly measured and understood. In this study, we developed experimental electrochemical methods to probe Li+ (de-)intercalation kinetics, and provided unique experimental evidence to support the microscopic mechanism of Li+ intercalation, described by the coupled ion-electron transfer mechanism. Current-voltage responses and reaction-limited capacities, indicative of small and large overpotentials, respectively, were measured across various electrode materials, including common LixCoO2 and NMCs, and were consistent with the proposed theory. A universal dependence of the intercalation rate on the lithium-ion filling fraction was revealed, as well as temperature and electrolyte effects, consistent with the theoretical description that classical ion transfer from the electrolyte is coupled with quantum-mechanical electron transfer from the electrode. Our findings suggest that the proposed mechanism applies to a variety of intercalation materials used in energy storage, and governs the power density at low and moderate applied current densities. The possibility of modifying the reaction-limited current with electrodes and electrolytes opens new directions for interfacial engineering of Li-ion batteries.
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Cardenas, Jorge Antonio, John Paul Bullivant, Bryan R. Wygant, Laura C. Merrill, Igor V. Kolesnichenko, Aliya S. Lapp, Timothy N. Lambert, et al. "3D Printing of Conversion Cathodes for Enhanced Custom-Form Lithium Batteries." ECS Meeting Abstracts MA2023-02, no. 1 (December 22, 2023): 101. http://dx.doi.org/10.1149/ma2023-021101mtgabs.
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Additive manufacturing techniques can enable the fabrication of batteries in nonconventional form factors, enabling higher practical energy densities due to improved power source packing efficiency. Furthermore, energy density can be improved by transitioning from conventional Li-ion materials to lithium metal anodes and conversion cathodes. Iron disulfide (FeS2) and iron trifluoride (FeF3) are two promising conversion cathodes of commercial and academic interest, but the 3D printing of inks made from these materials for custom-form battery applications has yet to be demonstrated. In this work, the deposition of FeS2 and FeF3 inks are investigated and optimized using direct-ink-write (DIW) 3D printing, in addition to the development of printable separators and packages to produce custom-form batteries. Two distinct custom form-factors, one on wave-shaped current collectors and the other on cylindrical rod current collectors, are demonstrated and shown to exhibit performance similar to coin cells when conventional Celgard separators are used. Additionally, FeF3 cells were integrated with a DIW printed separator consisting of an electrolyte exchanged PVDF-HFP based ionogel [1]. In the case of FeS2, it was found that cathodes with a ridged surface, produced from the filamentary extrusion of highly concentrated inks (60-70% solids w/w%) exhibited optimal power, uniformity, and stability [2]. Finally, progress toward fully-printing custom-form batteries using metal powder bed printed cases and stereolithographically printed gaskets is demonstrated. Overall, the additive manufacturing of conversion electrodes, separators, and battery packaging is shown to be a viable path toward the making of custom-form cells. More broadly, electrode ridging is found to optimize rate capability, a finding that may have broad impact beyond FeS2, FeF3 and additive manufacturing. [1] A.S. Lapp, L.C. Merrill, B.R. Wygant, D.S. Ashby, A.S. Bhandarkar, A. Zhang, E.J. Fuller, K.L. Harrison, T.N. Lambert, and A.A. Talin. Room Temperature Pseudo-Solid State Iron Fluoride Conversion Battery with High Ionic Conductivity. ACS Applied Materials & Interfaces 15, 893-902, 2022. [2] J.A. Cardenas, J.P. Bullivant, I.V. Kolesnichenko, D.J. Roach, M.A. Gallegos, E.N. Coker, T.N. Lambert, E. Allcorn, A.A. Talin, A.W. Cook, and K.L. Harrison. 3D Printing of Ridged FeS2 Cathodes for Improved Rate Capability and Custom-Form Lithium Batteries. ACS Applied Materials & Interfaces 14, 45342-45351. 2022.
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Helms, Brett. "Molecular Engineering for Redox-Flow Batteries Designed for Long-Duration Energy Storage." ECS Meeting Abstracts MA2023-01, no. 3 (August 28, 2023): 776. http://dx.doi.org/10.1149/ma2023-013776mtgabs.
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Electrochemical energy storage solutions for long-duration use-cases should feature active materials with exceptional stability in their charged state. In this presentation, I will discuss how molecular engineering is a powerful toolbox for tailoring the properties of organic redox-active molecules used as active materials in redox-flow batteries, particularly long-term stability as a function of redox potential in electrolyte. Instability can come from a variety of fundamental physical phenomena in the flow cell: desolvation of charged active materials in the electrolyte over time, producing solids; disproportionation and other parasitic reactions, including those between actives and the electrolyte; degradation and fouling of polymer membranes in contact with highly oxidizing or highly reducing catholytes and anolytes, respectively. To manage these risks, I will offer potential solutions from the atomic to macromolecular scales in the active materials and polymer membranes, where there is vast opportunity to gain access to cell chemistries that meet target requirements for the technology. I will also offer a perspective on how to scale to meet cost targets set forth in the Long-Duration Energy Storage Grand Challenge and Technology Roadmap.
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Steinle, Dominik, Fanglin Wu, Guk-Tae Kim, Stefano Passerini, and Dominic Bresser. "PEO-based Interlayers for LAGP-type Solid-State Lithium-Metal Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 375. http://dx.doi.org/10.1149/ma2022-024375mtgabs.
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Solid-state electrolytes (SSEs) are expected to play a decisive role for the realization of safer rechargeable batteries and may, additionally, allow for the employment of lithium-metal anodes, thus, paving the way for significantly higher energy densities. 1, 2 There are essentially two main groups of SSEs: (i) polymer and (ii) inorganic solids. The latter can be divided, e.g., into sulfide and oxide based electrolytes. 3 Among the oxides, the so-called NASICON-type electrolytes such as LAGP (lithium aluminum germanium phosphate) are considered as attractive low-cost alternative compared to sulfides. 4 Nonetheless, the incompatibility of LAGP with lithium metal accompanied by the formation of highly resistive interfacial reaction products, detrimentally affecting cycle life and rate capability, remain a great challenge. 5 To overcome this issue, the introduction of polyether (e.g., polyethylene oxide, PEO) as protective interlayer between the lithium-metal anode and the LAGP SSE was proposed. 6, 7, 8 The successful use of such interlayers, however, requires a fast and efficient charge transfer across this interlayer. Herein, we present a comprehensive investigation of PEO-based interlayers comprising varying amounts of ionic liquid-based electrolytes, which consist ofN-butyl-N-methyl pyrrolidinium-based and lithium cations as well as bis(fluorosulfonyl)imide (FSI-) and bis(trifluoromethanesulfonyl)imide (TFSI-) anions. Optimized compositions and the incorporation of selected additives further enhances the charge transfer across this interlayer and the two interfaces with the LAGP electrolyte and lithium metal, enabling long-term stable cycle life and good rate capability of the resulting lithium-metal battery cells. References 1. Gao, Z. et al. Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries. Adv. Mater. 30, 1705702 (2018). 2. Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S. & Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18, 1278–1291 (2019). 3. Fan, L., Wei, S., Li, S., Li, Q. & Lu, Y. Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries. Adv. Energy Mater. 8, 1702657 (2018). 4. Bachman, J. C. et al. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction. Chem. Rev. 116, 140–62 (2016). 5. Hartmann, P. et al. Degradation of NASICON-Type Materials in Contact with Lithium Metal: Formation of Mixed Conducting Interphases (MCI) on Solid Electrolytes. J. Phys. Chem. C 117, 21064–21074 (2013). 6. Wang, C. et al. Suppression of Lithium Dendrite Formation by Using LAGP-PEO (LiTFSI) Composite Solid Electrolyte and Lithium Metal Anode Modified by PEO (LiTFSI) in All-Solid-State Lithium Batteries. ACS Appl. Mater. Interfaces 9, 13694–13702 (2017). 7. Bosubabu, D., Sivaraj, J., Sampathkumar, R. & Ramesha, K. LAGP|Li Interface Modification through a Wetted Polypropylene Interlayer for Solid State Li-Ion and Li–S batteries. ACS Appl. Energy Mater. 2, 4118–4125 (2019). 8. Wang, L., Liu, D., Huang, T., Geng, Z. & Yu, A. Reducing interfacial resistance of a Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte/electrode interface by polymer interlayer protection. RSC Adv. 10, 10038–10045 (2020).
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Li, Yuanchao, Joshua Abbey, and Trung Van Nguyen. "Precipitation Mechanism of VOSO4 in Oversaturated Electrolytes of the Solid-Liquid Storage Method in Vanadium Redox Flow Batteries." ECS Meeting Abstracts MA2023-01, no. 3 (August 28, 2023): 735. http://dx.doi.org/10.1149/ma2023-013735mtgabs.
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Redox flow batteries (RFBs)-based storage systems have the unique feature of separate power generating and energy storage units that can be individually sized. RFBs can be used for days-long energy storage, but because of the low solubility of most ions and molecules in both aqueous and non-aqueous solvents,[1,2] scaling these RFB systems for days-long applications requires a lot of storage tanks and floor area. Our team has developed a new storage method that can significantly increase energy storage density while still maintaining the traditional flow battery design.[3] This method involves storing the reactants in both soluble ions and undissolved solid form, and only the liquid containing the soluble ions is circulated through the batteries. A larger than 4X improvement in storage energy density may be achieved with this strategy. The feasibility of this method was demonstrated in a hydrogen-vanadium (VI/V) RFB.[4] From the study, a major factor in achieving high performance with this hybrid storage system is the rates of the precipitation of the saturated electrolyte and dissolution of the solid precipitate. It was discovered that not all vanadium sulfate solids have precipitation rates fast enough to generate the active ions at the rate needed in the electrode reaction. Only the low crystallinity solid generated by rapid precipitation by the use of a suitable nucleation material was found to have the dissolution rate needed. This presentation will discuss the role of the molecule structures and the mechanism of the precipitation process in the formation of solids that have slow and fast dissolution rates. References [1] V. Singh, S. Kim, J. Kang, and H. R. Byon, Nano Res., 12, 1988-2001 (2019). [2] K. Gong, F. Xu, J. B. Grunewald, X. Ma, Y. Zhao, S. Gu, and Y. Yan, ACS Energy Lett., 1, 89-93 (2016). [3] Y. Li and T. V. Nguyen, Provisional US patent application number 62/941,064 filed 2019/11/27, International Application No. PCT/US20/61455 filed 2020/11/20 (WO2021108244A1). [4] Y. Li and T. V. Nguyen, J. Electrochem. Soc., 169, 110509 (2022).
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Palluzzi, Matteo, Akiko Tsurumaki, Henry Adenusi, Maria Assunta Navarra, and Stefano Passerini. "Ionic liquids and their derivatives for lithium batteries: role, design strategy, and perspectives." Energy Materials 3, no. 6 (2023): 300049. http://dx.doi.org/10.20517/energymater.2023.48.
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Lithium-ion batteries (LIBs) are the predominant power source for portable electronic devices, and in recent years, their use has extended to higher-energy and larger devices. However, to satisfy the stringent requirements of safety and energy density, further material advancements are required. Due to the inherent flammability and incompatibility of organic solvent-based liquid electrolytes with materials utilized in high energy devices, it is necessary to transition to alternative conductive mediums. The focus is shifting from molecular materials to a class of materials based on ions, including ionic liquids (ILs) and their derivatives such as zwitterionic ILs, polymerized ILs, and solvated ILs, which possess high levels of safety, stability, compatibility, and the ability to rationally design ILs for specific applications. Ion design is crucial to achieve superior control of electrode/electrolyte interphases (EEIs) both on anode and cathode surfaces to realize safer and higher-energy lithium-metal batteries (LMBs). This review summarizes the different uses of ILs in electrolytes (both liquid and solids) for LMBs, reporting the most promising results obtained during the last years and highlighting their role in the formation of suitable EEIs. Furthermore, a discussion on the use of deep-eutectic solvents is also provided, which is a class of material with similar properties to ILs and an important alternative from the viewpoint of sustainability. Lastly, future prospects for the optimization of IL-based electrolytes are summarized, ranging from the functional design of ionic structures to the realization of nanophases with specific features.
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Cui, Zhiwei, Feng Gao, and Jianmin Qu. "Interface-reaction controlled diffusion in binary solids with applications to lithiation of silicon in lithium-ion batteries." Journal of the Mechanics and Physics of Solids 61, no. 2 (February 2013): 293–310. http://dx.doi.org/10.1016/j.jmps.2012.11.001.
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Kalra, Charanjit Singh, Ankur Mohan, and Gurkiran Kaur. "An unusual case of Ayurvedic tablet as foreign body cricopharynx." International Journal of Otorhinolaryngology and Head and Neck Surgery 6, no. 3 (February 24, 2020): 592. http://dx.doi.org/10.18203/issn.2454-5929.ijohns20200643.
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<p class="abstract">A cricopharyngeal foreign body is a common emergency to any otolaryngologist in their clinical practice. Coins, button batteries, pencil tips, screws, tooth brush, safety pin are usually found in children but are rarely seen in adults in the cricopharynx. We present an unusual case of ayurvedic tablet as a foreign body in a 40-year-old female who swallowed an Ayurvedic tablet. She complained of absolute dysphagia to both solids and liquids. Such tablets are usually radiolucent and are not visualised on routine radiographs. Unexpectedly, on the X-ray lateral view of the neck, cricopharynx area showed a circular radio opaque shadow radio opaque shadow. Foreign body was removed by hypopharyngoscopy and patient was discharged with no complaints. Ayurvedic tablet as radio opaque shadow is a rare presentation and only one similar case has been reported so far.</p>
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Kong, Dexu, Eny Kusrini, and Lee D. Wilson. "Binary Pectin-Chitosan Composites for the Uptake of Lanthanum and Yttrium Species in Aqueous Media." Micromachines 12, no. 5 (April 22, 2021): 478. http://dx.doi.org/10.3390/mi12050478.
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Rare-earth elements such as lanthanum and yttrium have wide utility in high-tech applications such as permanent magnets and batteries. The use of biopolymers and their composites as adsorbents for La (III) and Y (III) ions were investigated as a means to increase the uptake capacity. Previous work has revealed that composite materials with covalent frameworks that contain biopolymers such as pectin and chitosan have secondary adsorption sites for enhanced adsorption. Herein, the maximum adsorption capacity of a 5:1 Pectin-Chitosan composite with La (III) and Y (III) was 22 mg/g and 23 mg/g, respectively. Pectin-Chitosan composites of variable composition were characterized by complementary methods: spectroscopy (FTIR, 13C solids NMR), TGA, and zeta potential. This work contributes to the design of covalent Pectin-Chitosan biopolymer frameworks for the controlled removal of La (III) and Y (III) from aqueous media.
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Ohno, Saneyuki, and Zheng Huang. "(Invited) New Class of Halide-Based Na-Ion Conducting Solids and a Critical Role of the Anion Framework." ECS Meeting Abstracts MA2024-02, no. 8 (November 22, 2024): 1052. https://doi.org/10.1149/ma2024-0281052mtgabs.
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All-solid-state sodium-ion (Na-ion) batteries are promising candidates for the post-lithium-ion (Li-ion) batteries owing to their improved safety and earth abundance, enabled by less- to non-flammable solid electrolytes (SEs). Extensive research efforts have been devoted to the development and exploration of new and better-performing ion conducting solids for decades, and numerous solid electrolytes, particularly sulfides, and oxides, have been discovered. Ion-conducting halides are an emerging class of materials for solid electrolytes that may satisfy all requirements with their balanced ionic conductivity (> 1 mS cm–1 at room temperature), oxidation stability (~ 4 V), and room temperature processability. Ion-conducting halides first stepped into the spotlight in 2018 with the report of mechanochemically synthesized Li3YX 6 (X = Cl, Br). Up to date, a wide variety of Li-ion conducting halides have been reported, e.g., Li3 M 3+ X 6 (M 3+ = In, Sc, Ti, Y, Ho, Er, Yb and X = Cl, Br, I), Li2 M 4+ X 6 (M 4+ = Zr, Hf and X = Cl, Br, I), LiM 5+Cl4O (M 5+ = Nb, Ta) and LaCl3-based Li-ion conductor. Many exhibits room-temperature ionic conductivity higher than 1 mS cm–1 and demonstrated stable cycling with the state-of-the-art cathode active materials operating > 4 V. Despite the success in Li-ion conducting halides, only a few Na-ion conducting halides have been found to date, e.g., Na3 M 3+Cl6 (M 3+ = Y, Er, In), Na2ZrCl6 and NaAlCl4, and their reported room-temperature ionic conductivity are mostly less than 0.1 mS cm–1. With the less polarizing nature of Na ions, Na-ion conducting SEs tend to possess higher ionic conductivity than their Li-analogues, and indeed, higher ionic conductivity is generally reported in Na-ion conducting oxides and sulfides than those in Li-ion conducting counterparts. Inspired by the fact that the known Na-ion conducting halide-based SEs exhibit much inferior ionic conductivity to the Li-analogues, here we explore the new Na-ion conducting halides, NaM 5+Cl6 (M 5+ = Nb, Ta), achieving 0.1 mS cm-1 at 30 °C. This high ionic conductivity is attributed to the beneficial inductive effect and improved migration entropy and is one of the highest among the crystalline monoanionic Na-ion conducting halides. Figure 1
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Wang, Yan. "(Invited) Towards Automated Materials Discovery for Next-Generation Batteries with Solid-State Electrolytes." ECS Meeting Abstracts MA2024-02, no. 8 (November 22, 2024): 1101. https://doi.org/10.1149/ma2024-0281101mtgabs.
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Solid-state batteries are increasingly seen as essential for next-generation energy applications in consumer electronics and electric vehicles. The key component of solid-state batteries is the solid-state electrolytes with high ionic conductivity and great interfacial stability against battery electrodes. Traditional discovery of solid-state electrolyte materials for high ionic conductivity often proceeds based on trial-and-error without an understanding of underlying structure-composition-property relationships, and so far only a handful of lithium and sodium conductors have been discovered with desired conductivity. Computational modeling based on density functional theory has become a cornerstone of materials design, by providing insights into fundamental processes that are not easily accessible in experiments, and enabling fast and efficient prediction even before material synthesis [1-2]. Such predictive power has made computational modeling a critical tool to design new solid-state ionic conducting materials with desired properties and accelerate the development of next-generation batteries with solid-state electrolytes. In this talk, I will present our recent findings in the physical and chemical design principles for solid-state materials with high ionic conductivity and stability [3]. More specifically, I will discuss crystallographic features which would enable fast ionic transport in inorganic solids, such as body-centered-cubic in sulfides [1] and corner-shared-polyhedron frameworks in oxides [4], and demonstrate how high-throughput calculations can be applied with such features in the design and discovery of new ionic conductors. I will also discuss our most recent efforts at Samsung Advanced Materials Lab, where we are developing an automation platform for inorganic battery materials discovery by combining high-throughput computation and robotic synthesis [5]. [1] Y. Wang et al., “Design principles for solid-state lithium superionic conductors,” Nature Materials, 14, 1026-1031, (2015). [2] G. Ceder, S. Ong, Y. Wang, “Predictive modeling and design rules for solid electrolytes.” MRS Bulletin, 43(10), 746-751 (2018). [3] Y. Xiao, Y. Wang, G. Ceder, et. al., “Understanding interface stability in solid-state batteries”, Nature Review Materials, 5, 105 (2020). [4] K. Jun, Y. Wang, G. Ceder, et. al., “Lithium superionic conductors with corner-sharing frameworks”, Nature Materials 21, 924 (2022) [5] J. Chen, S. R. Cross, Y. Wang, W. Sun, et. al., “Navigating phase diagram complexity to guide robotic inorganic materials synthesis”, Nature Synthesis, 1-9, 2024
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Godinez Brizuela, Omar Emmanuel, Daniel Niblett, and Kristian Etienne Einarsrud. "Pore-Scale Micro-Structural Analysis of Electrode Conductance in Metal Displacement Batteries." ECS Meeting Abstracts MA2022-01, no. 1 (July 7, 2022): 148. http://dx.doi.org/10.1149/ma2022-011148mtgabs.
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Metal displacement batteries (MDBs), or liquid metal batteries, are an emerging technology with significant potential in providing high capacity, low-cost energy storage solutions, capable of addressing many of the challenges associated with storing energy from renewable sources. The key characteristic of metal displacement batteries is that at least one of the electrodes is in liquid state and a molten salt is used as an electrolyte. Since its original proposal in the 1960’s liquid metal batteries have re-emerged in recent years and different battery chemistries and designs have been explored, including Ca-Bi, Na-Sb, and many others [2,10]. Recently, Na-Zn liquid metal batteries have been studied as an alternative to other configurations, showing significant potential in achieving good performance for large-scale energy storage, while avoiding the high cost associated with some electrode materials such as Nickel or Lithium [7,8]. In past years, alternatives to all-liquid cells have emerged in the form of designs where the cell materials are a mixture of solids and liquids. Examples of this include the commercially available Zebra battery, where a Na-NiCl electrode pair is used [1,6]. These designs offer some of the advantages of all-liquid cells, while simultaneously mitigating many of the disadvantages of handling and operating a very high temperature system. Na-Zn have also been proposed for solid cathode designs, taking advantage of the lower cost of Zn over Ni [4,3]. The cathode in these designs is composed of a porous structure, within which multiple chemical species can co-exist. Electrolyte components share the space with metal deposits,salt crystals, and other electrochemical reaction products. As a result, the micro-porous structure of this composite system is an important factor in determining the performance of the cell, as the spatial distribution of different materials can have an impact on the effective conductivity of the electrode [5,9]. The porous structure hosts complex multi-component mass transfer phenomena as well, potentially having an impact on the mass-transfer overpotential of the cell. This work aims to study the impact of the microstructural properties of the solid electrode in a liquid displacement battery, and their importance to the effective conductivity of the system. We have developed a computational tool that enables us to create randomized microstructures in 3D, representing the electrode-electrolyte assembly. We are able to preserve the desired physical characteristics by using target pore-size distributions and volume fraction input as seed parameters. We use this tool to generate representative structures and analyze their effective bulk conductivity by solving Laplace’s equation over the resulting domain, accounting for the different local conductivity of each material. This methodology is applied to a novel Na-Zn cell in order to assess the importance of the pore-scale properties of the cathode, as well as its material components, including solid Zn metal, solid NaCl deposits, and molten salt components. It is expected that different material arrangement configurations will induce heterogeneous current distributions in this system. Furthermore, the ionic composition of the electrolyte would be different at different charge levels, leading to additional variation through its charge/discharge cycle. Using this methodology, the range of different electrode phase configurations produced during operation can be studied in the absence of microstructure imaging data. A representative elementary volume for the Zn electrode assembly is analyzed to determine the best approach for up-scaled performance predictions of the Na-Zn cell. With this method, it is possible to acquire data to elucidate desirable or undesirable electrode structure properties of this system, providing insight which can be used for improving manufacture and operation of the cell. [1] Dustmann. “Advances in ZEBRA batteries”. J. Power Sources (2004). [2] Kim et al. “Liquid metal batteries: Past, present, and future”. Chemical Reviews (2013). [3] Lu et al. “An Intermediate-Temperature High-Performance Na-ZnCl2 Bat- tery”. ACS Omega (2018). [4] Lu et al. “Liquid-metal electrode to enable ultra-low temperature sodium- beta alumina batteries for renewable energy storage”. Nature Communications (2014). [5] Qiu et al. “Pore-scale analysis of effects of electrode morphology and electrolyte flow conditions on performance of vanadium redox flow batteries”. J. Power Sources (2012). [6] Sudworth. “The sodium / nickel chloride ( ZEBRA ) battery”. J. Power Sources (2001). [7] Xu et al. “Electrode Behaviors of Na-Zn Liquid Metal Battery”. Journal of The Electrochemical Society (2017). [8] Xu et al. “Na-Zn liquid metal battery”. Journal of Power Sources (2016). [9] Zhang et al. “Progress in 3D electrode microstructure modelling for fuel cells and batteries: transport and electrochemical performance”. Progress in Energy (2019). [10] Zhang et al. “Liquid Metal Batteries for Future Energy Storage”. Energy Environmental Science (2021). Figure 1
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Falco, Marisa, Gabriele Lingua, Silvia Porporato, Ying Zhang, Mingjie Zhang, Matteo Gastaldi, Francesco Gambino, et al. "An Overview on Polymer-Based Electrolytes with High Ionic Mobility for Safe Operation of Solid-State Batteries." ECS Meeting Abstracts MA2023-02, no. 4 (December 22, 2023): 604. http://dx.doi.org/10.1149/ma2023-024604mtgabs.
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Liquid electrolytes used in commercial Li-ion batteries are generally based on toxic volatile and flammable organic carbonate solvents, thus raising safety concerns in case of thermal runaway. The most striking solution at present is to switch on all solid-state designs exploiting polymer materials, films, ceramics, low-volatile, green additives, etc. The replacement of liquids component with low-flammable solids is expected to improve the safety level of the device intrinsically. Moreover, a solid-state configuration is expected to guarantee improved energy density systems. However, low ionic conductivity, low cation transport properties and issues in cell manufacturing processes must be overcome [1]. Electrochemical performance in lab-scale devices can be readily improved using different RTILs or specific low-volatile additives. Here, an overview is offered of the recent developments in our labs on innovative polymer-based electrolytes allowing high ionic mobility, particularly attractive for safe, high-performing, solid-state Li-metal batteries, and obtained by different techniques, including solvent-free UV-induced photopolymerization. Cyclic voltammetry and galvanostatic charge/discharge cycling coupled with electrochemical impedance spectroscopy exploiting different electrode materials (e.g., LFP, Li-rich NMC, LNMO, Si/C) demonstrate specific capacities approaching theoretical values even at high C-rates and stable operation for hundreds of cycles at ambient temperature [2,3]. Direct polymerization procedures on top of the electrode films are also used to obtain an intimate electrode/electrolyte interface and full active material utilization in both half and full-cell architectures. In addition, results of composite hybrid polymer electrolytes [4] and new single-ion conducting polymers [5] are shown, specifically developed to attain improved ion transport and high oxidation stability for safe operation with high voltage electrodes even at ambient conditions. References [1] Ferrari, S.; Falco, M.; Muñoz-García, A.B.; Bonomo, M.; Brutti, S.; Pavone, M.; Gerbaldi, C. Solid-State Post Li Metal Ion Batteries: A Sustainable Forthcoming Reality? Adv. Energy Mater. 2021, 11, 2100785. [2] Falco, M.; Simari, C.; Ferrara, C.; Nair, J.R.; Meligrana, G.; Nicotera, I.; Mustarelli, P.; Winter, M.; Gerbaldi, C. Understanding the Effect of UV-Induced Cross-Linking on the Physicochemical Properties of Highly Performing PEO/LiTFSI-Based Polymer Electrolytes. Langmuir 2019, 35, 8210-8219. [3] Lingua, G.; Falco, M.; Stettner, T.; Gerbaldi, C.; Balducci, A. Enabling safe and stable Li metal batteries with protic ionic liquid electrolytes and high voltage cathodes. J. Power Sources 2021, 481, 228979. [4] Falco, M.; Castro, L.; Nair, J.R.; Bella, F.; Bardé, F.; Meligrana, G.; Gerbaldi, C. UV-Cross-Linked Composite Polymer Electrolyte for High-Rate, Ambient Temperature Lithium Batteries. ACS Appl. Energy Mater. 2019, 2 1600-1607. [5] Lingua, G.; Grysan, P.; Vlasov, P.S.; Verge, P.; Shaplov, A.S.; Gerbaldi, C. Unique Carbonate-Based Single Ion Conducting Block Copolymers Enabling High-Voltage, All-Solid-State Lithium Metal Batteries. Macromolecules, 2021, 54, 6911-6924. Acknowledgements The Si-DRIVE project has received funding from the EU's Horizon 2020 research and innovation program under GA 814464. The PSIONIC project has received funding from the European Union's Horizon Europe Research and Innovation Programme under Grant Agreement N. 101069703.
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Li, Wenyue, Shiqi Li, Ayrton A. Bernussi, and Zhaoyang Fan. "3-D Edge-Oriented Electrocatalytic NiCo2S4 Nanoflakes on Vertical Graphene for Li-S Batteries." Energy Material Advances 2021 (March 22, 2021): 1–11. http://dx.doi.org/10.34133/2021/2712391.
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Polysulfide shuttle effect, causing extremely low Coulombic efficiency and cycling stability, is one of the toughest challenges hindering the development of practical lithium sulfur batteries (LSBs). Introducing catalytic nanostructures to stabilize the otherwise soluble polysulfides and promote their conversion to solids has been proved to be an effective strategy in attacking this problem, but the heavy mass of catalysts often results in a low specific energy of the whole electrode. Herein, by designing and synthesizing a free-standing edge-oriented NiCo2S4/vertical graphene functionalized carbon nanofiber (NCS/EOG/CNF) thin film as a catalytic overlayer incorporated in the sulfur cathode, the polysulfide shuttle effect is largely alleviated, revealed by the enhanced electrochemical performance measurements and the catalytic function demonstration. Different from other reports, the NiCo2S4 nanosheets synthesized here have a 3-D edge-oriented structure with fully exposed edges and easily accessible in-plane surfaces, thus providing a high density of active sites even with a small mass. The EOG/CNF scaffold further renders the high conductivity in the catalytic structure. Combined, this novel structure, with high sulfur loading and high sulfur fraction, leads to high-performance sulfur cathodes toward a practical LSB technology.
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Allen, Jan L. "(Keynote, Digital Presentation) Mixed Electronic-Ionic Conduction in Spinel-Structured Solid Electrolyte-Electrodes for Li-Ion Batteries." ECS Meeting Abstracts MA2022-01, no. 38 (July 7, 2022): 1653. http://dx.doi.org/10.1149/ma2022-01381653mtgabs.
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Solid Li-ion conducting electrolytes are one pathway towards future, energy-dense, intrinsically-safe solid-state batteries. Thus, it is of interest to study novel fast Li-ion solid electrolyte materials. Here we report the synthesis and characterization of a family of spinel structured oxide solid electrolytes[1]. Further, we will report on the interface and mixed electronic-ionic conductivity of the spinel structured solid solution which is formed upon reaction with spinel structured Li-ion battery electrode materials. We detail the compositions that were explored and give the results of the synthesis, densification and the structural, physical and electrochemical characterization. The properties of the new materials will be compared and contrasted to well-known solid Li electrolytes such as garnet and NASICON structured materials. References 1. Allen, J.L.; Crear, B.A.; Choudhury, R.; Wang, M.J.; Tran, D.T.; Ma, L.; Piccoli, P.M.; Sakamoto, J.; Wolfenstine, J. Fast Li-Ion Conduction in Spinel-Structured Solids. Molecules 2021, 26, 2625. https://doi.org/10.3390/molecules26092625 Figure 1
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Greene, Samuel M., and Donald J. Siegel. "Computational Investigations of Features for Predicting Ionic Conductivity in Multivalent Solid Electrolytes." ECS Meeting Abstracts MA2024-02, no. 9 (November 22, 2024): 1428. https://doi.org/10.1149/ma2024-0291428mtgabs.
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A significant challenge hindering the development of batteries based on the redox of multivalent ions is the sluggish mobility of such ions in most solids. Computational methods for efficiently predicting conductivity can accelerate the discovery of faster ion conductors. Direct first-principles calculations of conductivity are expensive and difficult to automate, which has prompted a search for other properties related to conductivity that are easier to calculate or measure. Previous studies have identified features related to the electronic charge density and phonon spectrum that are correlated with energy barriers for ion migration in monovalent conductors. Results from our first-principles simulations demonstrate that these features are not well correlated with energy barriers for multivalent ion migration. I will discuss potential reasons for this lack of correlation and propose modifications that are found to improve correlations. These findings quantify the promise of using such features to efficiently screen for better multivalent ion conductors. Figure 1
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Fernández-Saavedra, Rocío, Margarita Darder, Almudena Gómez-Avilés, Pilar Aranda, and Eduardo Ruiz-Hitzky. "Polymer-Clay Nanocomposites as Precursors of Nanostructured Carbon Materials for Electrochemical Devices: Templating Effect of Clays." Journal of Nanoscience and Nanotechnology 8, no. 4 (April 1, 2008): 1741–50. http://dx.doi.org/10.1166/jnn.2008.18238.
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The present work introduces a comparative study on the use of polymer nanocomposites containing clay minerals of different structure, such as montmorillonite and sepiolite as host solids for the templating synthesis of carbon-like materials from different organic precursors. Carbon-clay nanocomposites were obtained by polymerization of either acrylonitrile or sucrose previously inserted in the pores of the clay minerals, followed by their further thermal transformation in carbon-like compounds. Acid treatment of the resulting carbon-clay nanocomposites removes the inorganic templates giving carbon-like materials with different textural features. Polymer-clay, carbon-clay and carbon-like materials have been characterized by applying spectroscopic techniques as FTIR and in situ EIS (electrochemical impedance spectroscopy) and other structural, textural and analytical tools (chemical analysis, XRD, SEM-EDX, TEM-EDX, N2 adsorption isotherms,...). Electrochemical properties of these carbon-clay nanocomposites, as well as their templated carbonaceous materials and their use as electrode materials of different electrochemical devices such as rechargeable Li-batteries, supercapacitors and electrochemical sensors, are also discussed.
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Damasceno Borges, Daiane, Guillaume Maurin, and Douglas S. Galvão. "Design of Porous Metal-Organic Frameworks for Adsorption Driven Thermal Batteries." MRS Advances 2, no. 9 (2017): 519–24. http://dx.doi.org/10.1557/adv.2017.181.
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ABSTRACTThermal batteries based on a reversible adsorption/desorption of a working fluid (water, methanol, ammonia) rather than the conventional vapor compression is a promising alternative to exploit waste thermal energy for heat reallocation. In this context, there is an increasing interest to find novel porous solids able to adsorb a high energy density of working fluid under low relative vapor pressure condition combined with an easy ability of regeneration (desorption) at low temperature, which are the major requirements for adsorption driven heat pumps and chillers. The porous crystalline hybrid materials named Metal–Organic Frameworks (MOF) represent a great source of inspiration for sorption based-applications owing to their tunable chemical and topological features associated with a large variability of pore sizes. Recently, we have designed a new MOF named MIL-160 (MIL stands for Materials of Institut Lavoisier), isostructural to CAU-10, built from the assembly of corner sharing aluminum chains octahedra AlO4(OH)2 with the 2,5-furandicarboxylic linker substituting the pristine organic linker, 1,4-benzenedicarboxylate. This ligand replacement strategy proved to enhance both the hydrophilicity of the MOF and its amount of water adsorbed at low p/p0. This designed solid was synthesized and its chemical stability/adsorption performances verified. Here, we have extended this study by incorporating other polar heterocyclic linkers and a comparative computational study of the water adsorption performances of these novel structures has been performed. To that purpose, the cell and geometry optimizations of all hypothetical frameworks were first performed at the density functional theory level and their water adsorption isotherms were further predicted by using force-field based Grand-Canonical Monte Carlo simulations. This study reveals the ease tunable water affinity of MOF for the desired application.
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Misenan, Muhammad Syukri Mohamad, Rolf Hempelmann, Markus Gallei, and Tarik Eren. "Phosphonium-Based Polyelectrolytes: Preparation, Properties, and Usage in Lithium-Ion Batteries." Polymers 15, no. 13 (June 30, 2023): 2920. http://dx.doi.org/10.3390/polym15132920.
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Phosphorous is an essential element for the life of organisms, and phosphorus-based compounds have many uses in industry, such as flame retardancy reagents, ingredients in fertilizers, pyrotechnics, etc. Ionic liquids are salts with melting points lower than the boiling point of water. The term “polymerized ionic liquids” (PILs) refers to a class of polyelectrolytes that contain an ionic liquid (IL) species in each monomer repeating unit and are connected by a polymeric backbone to form macromolecular structures. PILs provide a new class of polymeric materials by combining some of the distinctive qualities of ILs in the polymer chain. Ionic liquids have been identified as attractive prospects for a variety of applications due to the high stability (thermal, chemical, and electrochemical) and high mobility of their ions, but their practical applicability is constrained because they lack the benefits of both liquids and solids, suffering from both leakage issues and excessive viscosity. PILs are garnering for developing non-volatile and non-flammable solid electrolytes. In this paper, we provide a brief review of phosphonium-based PILs, including their synthesis route, properties, advantages and drawbacks, and the comparison between nitrogen-based and phosphonium-based PILs. As phosphonium PILs can be used as polymer electrolytes in lithium-ion battery (LIB) applications, the conductivity and the thermo-mechanical properties are the most important features for this polymer electrolyte system. The chemical structure of phosphonium-based PILs that was reported in previous literature has been reviewed and summarized in this article. Generally, the phosphonium PILs that have more flexible backbones exhibit better conductivity values compared to the PILs that consist of a rigid backbone. At the end of this section, future directions for research regarding PILs are discussed, including the use of recyclable phosphorus from waste.
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Amiraslanova, A. J., K. N. Babanly, S. Z. Imamaliyeva, I. J. Alverdiyev, and Yu A. Yusibov. "PHASE RELATIONS IN THE Ag8SiS6–Ag8SiTe6 SYSTEM AND CHARACTERIZATION OF SOLID SOLUTIONS." Azerbaijan Chemical Journal, no. 2 (June 19, 2023): 169–77. http://dx.doi.org/10.32737/0005-2531-2023-2-169-177.
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Argyrodite family compounds and phases based on them are valuable ecologically friendly functional materials that exhibit a number of functional propreties, such as thermoelectric, photoelectric, optical, and other. On the other hand, having Cu+ and Ag+ ion conductivity, they are ionic conductors, and can be used as electrochemical sensors, electrodes, or electrolyte materials in solid-state batteries, displays, etc. In the present paper, phase relations in the Ag8SiS6–Ag8SiTe6 system were studied by differential thermal analysis and X-ray diffraction phase techniques and a T-x phase diagram was constructed. It is established that the system is quasi-binary and is characterized by the formation of a continuous series of substitutional solid solutions between Ag8SiTe6 and HT- Ag8SiS6 compounds. With the formation of solid solutions, the temperature of the polymorphic transition of the Ag8SiS6 decreases. This leads to the stabilization of the ion-conducting cubic phase in the range of compositions 30 mol. % Ag8SiTe6 at room temperature and below. The homogeneity regions based on RT-Ag8SiS6 are 10 mol. %. According to XRD data, the crystal lattice parameters of the obtained solid solutions were calculated and a their linear dependence on the composition is shown
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Naseem, Majid, Sadia Anjum, Saima Saima, Ghulam Baqar, Mahpara Jabeen, Iqra Nawaz, Muhammad Imran, Usama Aslam, and Muhammad Ibrhim. "Current Advances with Potential Role of Nanotechnology in Generation of Fuel Cells and Solar Cell Batteries." Scholars Bulletin 10, no. 04 (April 17, 2024): 136–42. http://dx.doi.org/10.36348/sb.2024.v10i04.004.
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Batteries are becoming an essential component of many different applications, such as memory backup, clocks, calculators, lighting, portable electronic devices, and photographic equipment, advancements in the electronics sector. Pure metal nanoparticles can be created either destructively or constructively using metal precursors. Because of the plasma resonance feature, it has special opto-electrical properties. Size, shape, and fact govern the metal nanoparticles replicate. Silver, gold, iron, cobalt, zinc, copper, and cadmium nanoparticles are the most prevalent metal nanoparticles. The electrical characteristics of the flower-shaped nanostructure when connected to the Pt nanoparticles are noticeably better than the typical electro-catalytic characteristics of the spherical nanoparticles. Transitional metal oxides are considered vital materials in industry because of their vast variety of magnetic, thermal, chemical, and electrical characteristics, as demonstrated by the evaluation of functional inorganic solids. The corrosive resistance of the metal at high voltages should be taken into account. Al and Ti are therefore excellent options because of the inert layer that forms on their surfaces at high potential. Building a porous metal current collector is therefore crucial to stabilizing alkali metal anodes with improved cycle and safety performance.
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Anbarasu, R., B. Kavitha, H. Aswathaman, and N. Senthil Kumar. "Studies on Polyvinyl Pyrrolidone (PVP) and Tapioca-Based Polymer Nanocomposites for Solid Polymer Electrolyte Applications in Batteries." Journal of Nanoscience and Technology 10, no. 1 (February 1, 2025): 986–89. https://doi.org/10.30799/jnst.352.25100101.
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Blending polymers has wide applications in batteries, since it possess different physical and chemical properties. In this study blending of PVP/tapioca and PVP/tapioca/polyamide have been prepared and characterized. The compatibility or miscibility of the polymers at the molecular level determines the new properties of the polymer blends. The synthesised polymer blends were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet-Visible Spectroscopy (UV-Vis) and Atomic Force Microscopy (AFM). Acoustical and excess parameters were studied for blends of PVP/tapioca and PVP/tapioca/polyamide in organic solids. By measuring ultrasonic velocity and adiabatic compressibility, the excess parameters were used to determine the nature of polymer interactions in the solvent.The topographical images are shown small particles approximately 50 nm in size, medium particles 100 nm in size, and large particles 175 nm in size were all observed. All particles exhibited a lobed-type fine structure; for the 175 nm sized particles, the lobes were 50 nm – 175 nm in size and appeared evenly distributed around the center of the particles.
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Walanda, Daud K. "KINETIC TRANSFORMATION OF SPINEL TYPE LiMnLiMn2O4 INTO TUNNEL TYPE MnO2." Indonesian Journal of Chemistry 7, no. 2 (June 20, 2010): 117–20. http://dx.doi.org/10.22146/ijc.21685.
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Lithiated phase LiMn2O4 is a potential cathode material for high-energy batteries because it can be used in conjunction with suitable carbon anode materials to produce so-called lithium ion cells. The kinetic transformation of LiMn2O4 into manganese dioxide (MnO2) in sulphuric acid has been studied. It is assumed that the conversion of LiMn2O4 into R-MnO2 is a first order autocatalytic reaction. The transformation actually proceeds through the spinel l-MnO2 as an intermediate species which is then converted into gamma phase of manganese dioxide. In this reaction LiMn2O4 whose structure spinel type, which is packing between tetrahedral coordination and octahedral coordination, is converted to form octahedral tunnel structure of manganese dioxide, which is probably regarded as a reconstructive octahedral-coordination transformation. Therefore, it is a desire to investigate the transformation of manganese oxides in solid state chemistry by analysing XRD powder patterns. Due to the reactions involving solids, concentrations of reactant and product are approached with the expression of peak areas. Keywords: high-energy battery, lithium ion cells, kinetic transformation
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Yakubovich, Olga, Nellie Khasanova, and Evgeny Antipov. "Mineral-Inspired Materials: Synthetic Phosphate Analogues for Battery Applications." Minerals 10, no. 6 (June 7, 2020): 524. http://dx.doi.org/10.3390/min10060524.
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For successful development of novel rechargeable batteries, considerable efforts should be devoted to identifying suitable cathode materials that will ensure a proper level of energy output, structural stability, and affordable cost. Among various compounds explored as electrode materials, structural analogues of minerals–natural stable inorganic solids–occupy a prominent place. The largest number of varieties of phosphate minerals occurs in rare metal granite pegmatites, and many of which contain transition metals as essential components. Transition metal phosphates are promising candidates for exploration as cathode materials due to a perfect combination of easily scalable synthesis, moderate-to-high voltage operation, thermal/chemical stability, and environmental safety. However, impurities usually presented in natural objects, and often inappropriate sample morphologies, do not permit the use of minerals as battery electrode materials. Nevertheless, the minerals of different classes, especially phosphates, are considered as prototypes for developing novel materials for battery applications. The crystal chemical peculiarities of the phosphate representatives that are most relevant in this aspect and the electrochemical characteristics of their synthetic analogues are discussed here.
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Díez, Eduardo, Cinthya Redondo, José María Gómez, Ruben Miranda, and Araceli Rodríguez. "Zeolite Adsorbents for Selective Removal of Co(II) and Li(I) from Aqueous Solutions." Water 15, no. 2 (January 9, 2023): 270. http://dx.doi.org/10.3390/w15020270.
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Cobalt and lithium are critical metals because of its shortage, difficulty of extraction and huge economic impact due to their market value. The purpose of this work is to study their selective removal from aqueous solutions in different conditions using two commercial FAU zeolites as adsorbent materials. These solids were characterized by XRD, XRF and BET analysis, to follow up of their FAU structure integrity, their Si/Al ratio, and their specific surface area evolutions through their preparation process. The kinetic study indicates that using both zeolites with a dosage of 5 g/L a 100% cobalt removal from aqueous solutions is achievable, while lithium removal is kept around 30% (separation factor of 3.33). This selectivity is important as these two metals frequently appear together in leaching solutions form, for example, ion-Li batteries. In relation to the adsorption equilibrium, cobalt adsorption presents a finite adsorption capacity while this behavior is not observed in lithium adsorption. For this reason, Langmuir model is the most adequate to represent cobalt adsorption, while lithium adsorption is better represented by Freundlich model.
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Baker, Daniel R., Mark W. Verbrugge, and Allan F. Bower. "Thermodynamics, stress, and Stefan-Maxwell diffusion in solids: application to small-strain materials used in commercial lithium-ion batteries." Journal of Solid State Electrochemistry 20, no. 1 (August 23, 2015): 163–81. http://dx.doi.org/10.1007/s10008-015-3012-7.
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Stoneham, Marshall, John Harding, and Tony Harker. "The Shell Model and Interatomic Potentials for Ceramics." MRS Bulletin 21, no. 2 (February 1996): 29–35. http://dx.doi.org/10.1557/s0883769400046273.
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In a classification of solids according to their bonding character (into metals, ceramics and glasses, polymers, and semiconductors), the ceramic class includes an enormous range of industrially important materials. From the archetypal ionic solids through oxides to silicates, and to covalently bonded materials such as SiC, they exhibit a rich variety of structures and properties. They occur as structural materials, either on their own or as composites such as SiC/Al2O3. They are important functional materials, such as fast-ion conductors as electrolytes in fuel cells (for example ZrO2/Y2O3 for hydrogen combustion) or batteries (β-alumina in the sodium-sulfur battery), ferroelectric materials such as BaTiO3 and piezoelectrics such as PZT—a solid solution of PbTiO3 and PbZrO3. The high-temperature superconductors (for example, YBa2Cu3O7) are ceramics above the superconducting transition temperature. The products of corrosion and oxidation are ionic materials, and the properties of oxide coatings are vital to the survival of high-temperature alloys in gas turbines or fuel-element claddings in nuclear reactors.To understand the behavior of ceramic materials, and to optimize their production, processing, and application, it is often necessary to model their behavior at an atomic level. In some cases this is obvious. Ionic diffusion in a solid electrolyte is a self-evidently atomic process. In other cases the need for atomistic simulation is less clear. Oxidation, for example, is a subtle blend of atomic diffusion (often along grain boundaries), metal-ceramic bonding, stress relief, and grain growth. The course of oxidation can be spectacularly affected by impurities and alloying, and this can only be understood by considering the atomicscale processes involved.
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Al-Kutubi, Hanan, Swapna Ganapathy, and Marnix Wagemaker. "Space Charges in Solid State Batteries: Friend, Foe or Fantasy?" ECS Meeting Abstracts MA2023-02, no. 8 (December 22, 2023): 3442. http://dx.doi.org/10.1149/ma2023-0283442mtgabs.
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Thermodynamics tells us that all materials have an internal energy that determines how they act and react with all matter in the universe. Furthermore, it forces all matter to strive towards equilibrium with its surroundings. For solid-state lithium-ion conductors, the chemical potential of lithium is an important parameter that determines stability and influences conductivity. However, it also implies something deeper. The chemical potential of an element in a solid is determined by the bonds that surround it as well as its concentration. Whereas the former is an intrinsic property of the material, the latter can be altered. When two solids with different chemical potentials are placed in contact, a driving force is created for atoms to migrate across the surface and establish thermodynamic equilibrium by altering their concentration. For semiconductors, in which either only a hole or electron can migrate, something interesting occurs. The migrating entity moves across but the counter-charge cannot, resulting in excess charge at the interface. The migrating partner, unable to return to its original material due to thermodynamics, is now unable to dissipate into the new material due to electrostatics. The result is a thin, charged layer across the interface. Because solid electrolytes conduct lithium cations but no anions or electrons, this ‘space-charge layer’ is also thought to occur in solid-state batteries between electrolyte and electrode. Whereas its size is thought to only be a few nanometres, its (negative) influence could be very large as it can act as barrier for lithium transport across the surface. Yet experimental evidence of its existence is rare and investigation of its behaviour even more so. The space charge between two materials is very thin and chemically almost identical to the bulk. But just like how water can carve the stone, we employ liquids to crack a solid-state problem. We find that when mixing an argyrodite solid electrolyte (Li6PS5Cl) with an ionic liquid (1-Ethyl-3-methylimidazolium bis(trifluoromethyls ulfonyl) imide or EMIN TFSI) , we observe a new chemical environment with NMR (see figure) that cannot be attributed to dissolved precursors. We see an increase in the mobility of lithium ions in the solid electrolyte itself with NMR and an increase in conductivity of the mixture with EIS. Furthermore, exchange of lithium has been confirmed between argyrodite and the mystery environment. What does this all mean? Are we observing the illusive space charge layer? Or are we just staring at an empty promise in the well-known shape of a mysterious peak in a spectrum? Figure 1
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Taghikhani, Kasra, Peter J. Weddle, William Huber, Robert M. Hoffman, Mohsen Asle Zaeem, John R. Berger, and Robert J. Kee. "Electro-Chemo-Mechanical Modeling of Composite Cathodes in All-Solid-State Li-Ion Batteries." ECS Meeting Abstracts MA2024-01, no. 38 (August 9, 2024): 2290. http://dx.doi.org/10.1149/ma2024-01382290mtgabs.
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A model-based understanding can assist and accelerate developing all-solid-state batteries (ASSB). In addition to chemo-mechanical influences within electrode particles (e.g., NMC) [1-2], a solid electrolyte (e.g., argyrodites) introduces additional interfacial interactions between electrode and electrolyte phases [3-5]. The present research derives and implements a coupled multi-physics finite-element model that captures electrochemical, transport, and structural behaviors of composite electrode structures. The models incorporate concentration-dependent and anisotropic material properties that are based on previously published combinations of experiment and density functional theory (DFT). These include stiffness and fracture toughness, porosity and crystallographic orientation, and operating conditions such as charge/discharge rates and external pressure. Figure 1 illustrates predicted stresses developed during electrode manufacturing. The relatively complex cathode microstructure is based on replicating scanning electron microscopy (SEM) images [6]. The composite electrode consists of electrode, electrolyte, and pore phases (Fig. 1a). As illustrated in Fig. 1b, the ASSB synthesis process involves applying and removing high compressive pressure, which causes plastic deformation and introduces residual stresses. Figure 1c shows residual von Mises stresses near electrode-electrolyte interfaces that can be on the order of a gigapascal. The synthesis-generated residual stresses serve as initial conditions for modeling the chemo-mechanics during battery cycling. During cell operation, spatially varying Li concentrations cause material deformation and associated stresses. Figure 1d shows predicted crack nucleation and growth during operation. Depending on the stress levels, crack nucleation and growth leads to cell degradation and capacity fade. The models predict interfacial fracture and phase separations using phase-field fracture theory. In phase-field formulation, the sharp cracks are approximated as diffuse cracks using a process-zone. High values of the phase parameter ξ (Fig. 1d) represent cracked surfaces. The structural disintegration and loss of active surface areas increase the tortuous path for Li/Li-ion transport, which eventually manifests as capacity-fade. The simulations are validated using published experimental work. The modeling approach, which combines phase-field and finite-element algorithms, is implemented using the COMSOL Multiphysics software. The models are expected to inform microstructure/manufacturing design and optimal operating conditions that improve cycling performance and limit/prevent mechanical damage. [1] K. Taghikhani, P.J. Weddle, J.R. Berger, and R.J. Kee. Modeling coupled chemo-mechanical behavior of randomly oriented NMC811 polycrystalline Li-ion battery cathodes. J. Electrochem. Soc., 168(8):080511, 2021. [2] R. Xu, Y. Yang, F. Yin, P. Liu, P. Cloetens, Y. Liu, F. Lin, and K. Zhao, Heterogeneous damage in Li-ion batteries: experimental analysis and theoretical modeling. J. Mech. Phys. Solids, 129, 160, 2019. [3] K. Taghikhani, P.J. Weddle, R.M. Hoffman, J.R. Berger, and R.J. Kee. Electro-chemo-mechanical finite-element model of single-crystal and polycrystalline NMC cathode particles embedded in an argyrodite solid electrolyte. Electrochim. Acta, 460:142585, 2023. [4] A. Bielefeld, D.A. Weber, R. Rueß, V. Glavas, and J. Janek. Influence of lithium ion kinetics, particle morphology and voids on the electrochemical performance of composite cathodes for all-solid-state batteries. J. Electrochem. Soc., 169(2):020539, 2022. [5] P. Minnmann, F. Strauss, A. Bielefeld, R. Ruess, P. Adelhelm, S. Burkhardt, S.L. Dreyer, E. Trevisanello, H. Ehrenberg, T. Brezesinski, F.H. Richter, and J. Janek. Designing cathodes and cathode active materials for solid-state batteries. Adv. Energy Mater., 12(35):2201425, 2022. [6] C. Doerrer, I. Capone, S. Narayanan, J. Liu, C.R.M. Grovenor, M. Pasta, and P.S. Grant. High energy density single-crystal NMC/Li6PS5Cl cathodes for all-solid-state lithium-metal batteries. ACS Appl. Mater. & interfaces, 13(31):37809–37815, 2021. Figure 1