Concentration Gradient Research Articles

Experimental Study on Explosion Characteristics and Consequences for Homogeneous and Inhomogeneous Methane-Air Mixtures within a Kitchen

ABSTRACT Owing to the effect of a non-uniform concentration distribution, natural gas leakage explosion accidents usually cause different degrees of damage inside residential kitchens. According to the similarity principle, a reduced-scale experiment setup of a kitchen was established. Uniform and non-uniform explosion experiments for methane-air mixtures with concentrations of 7.7%, 9.5%, and 11.2% were performed. The flame propagation behavior and pressure evolution characteristics were analyzed for homogeneous and inhomogeneous methane-air mixtures. In addition, two dimensionless coefficients, namely macroscopic and directional non-uniformity coefficients, were introduced to quantify the uneven distribution of gas concentration within the kitchen. Furthermore, the flame development process and pressure evolvement characteristics were compared between homogeneous and inhomogeneous methane-air mixtures in a fuel-lean, chemical equivalence concentration and fuel-rich state. The results show that the macroscopic non-uniformity coefficients are 0.0998, 0.0653, and 0.0571 on the fuel-lean, chemical equivalence concentration and fuel-rich conditions, respectively. It indicates that the greatest non-uniformity of methane concentration distribution within the kitchen is represented on the fuel-lean condition. The concentration gradient could obviously reduce the explosion overpressure in the fuel-lean condition, whereas it would not significantly decrease the explosion overpressure in the chemical equivalence concentration or fuel-rich condition. It means that the greater the non-uniformity coefficient is, the more significant the effect on the overpressure peak is.

Integrating cultural and natural assets in marine spatial planning: A new approach for joint management of cultural and natural assets

Effective sustainable marine management requires the integration of cultural and natural assets, a practice that is rarely attempted. This study developed and tested a new method for Marine Spatial Planning (MSP) that uses interdisciplinary knowledge of the spatial distribution of cultural and natural assets in marine ecosystems along environmental and human pressure gradients and seeks to understand their interrelationships. The study focused on Estonian marine areas in the north-eastern Baltic Sea. Environmental conditions and threats were assessed, and the extent of spatial overlap between underwater cultural heritage (UCH), natural assets and conservation measures was identified. Although nature reserves and UCH sites were generally exposed to different ranges of environmental and pressure gradients, significant overlap with UCH sites was observed for certain natural assets, as well as along gradients of current velocity, oxygen concentration, bottom sediment, and human pressure. These results highlight the value of joint archaeological and ecological analyses to identify natural assets specific to UCH regions that require protection from both a natural and cultural heritage perspective.

Multi-physics analysis of squeezing fluid flow with rotational, magnetic field, and heat transfer interactions

This research paper presents a comprehensive study on the intricate interplay of rotational, magnetic field and heat transfer effects in squeezing fluid flow, utilizing the foundational framework of Navier–Stokes equations. Fluid flow in confined geometries has significant applications in various industrial processes, including lubrication systems, microfluidics, and heat exchangers. The integration of rotational motion, magnetic fields, and heat transfer phenomena into this context holds immense potential for optimizing performance and efficiency. The study commences with the derivation and analysis of the coupled Navier–Stokes equations, incorporating the Coriolis force due to rotational motion, the Lorentz force arising from magnetic fields, and the energy equation for heat transfer. This comprehensive model accounts for the complex interactions between these physical phenomena, offering a holistic perspective on squeezing fluid flow dynamics. Numerical analysis are conducted to investigate the behavior of fluids under the influence of rotational, magnetic field, and heat transfer effects. The results reveal intricate flow patterns, including vortex formation and heat transfer enhancement. Furthermore, the impact of key parameters such as rotational speed, magnetic field strength, and temperature gradients on flow characteristics is systematically analyzed. The Dufour effect pertains to the transfer of energy resulting from a gradient in mass concentration, occurring as a correlated consequence of irreversible processes. It functions as the inverse of the Soret effect. The temperature changes due to the concentration gradient, amplifying as the Dufour number increases. The most significant temperature rise is observed at the midpoint of the fluid domain. Conversely, the Soret number behaves in a similar but opposite manner. Tables 4–10 has been created to offer a comprehensive analysis of the optimal alignment between Homotopy Analysis Method (HAM) and BVP4c. Specifically, it demonstrates a continuous decrease in skin friction for ξSo, ξRd, and ξR2, while showing an increase for ξSc, ξDo, and ξRem. Meanwhile, the skin friction remains constant for ξPr. The research centers on analyzing heat and mass transfer properties within an incompressible fluid confined between two rotating and stretching disks amidst an unpredictable flow pattern. The study employs a blend of analytical and numerical approaches to solve the governing equations, delving into the intricate fluid dynamics and the intricate processes of heat and mass transfer within this intricate system.

Long-term Monitoring of Oxygen Consumption Rates in Highly Differentiated and Polarized Retinal Pigment Epithelial Cultures.

Mitochondrial metabolism is critical for the normal function of the retinal pigment epithelium (RPE), a monolayer of cells in the retina important for photoreceptor survival. RPE mitochondrial dysfunction is a hallmark of age-related macular degeneration (AMD), the leading cause of irreversible blindness in the developed world, and proliferative vitreoretinopathy (PVR), a blinding complication of retinal detachments. RPE degenerative conditions have been well-modeled by RPE culture systems that are highly differentiated and polarized to mimic in vivo RPE. However, monitoring oxygen consumption rates (OCR), a proxy for mitochondrial function, has been difficult in such culture systems because the conditions that promote ideal RPE polarization and differentiation do not allow for easy OCR measurements. Here, we introduce a novel system, Resipher, to monitor OCR for weeks at a time in well-differentiated RPE cultures while maintaining the RPE on optimal growth substrates and physiologic culture media in a standard cell culture incubator. This system calculates OCR by measuring the oxygen concentration gradient present in the media above cells. We discuss the advantages of this system over other methods for detecting OCR and how to set up the system for measuring OCR in RPE cultures. We cover key tips and tricks for using the system, caution about interpreting the data, and guidelines for troubleshooting unexpected results. We also provide an online calculator for extrapolating the level of hypoxia, normoxia, or hyperoxia RPE cultures experience based on the oxygen gradient in the media above cells detected by the system. Finally, we review two applications of the system, measuring the metabolic state of RPE cells in a PVR model and understanding how the RPE metabolically adapts to hypoxia. We anticipate that the use of this system on highly polarized and differentiated RPE cultures will enhance our understanding of RPE mitochondrial metabolism both under physiologic and disease states.

Solvent transport behavior in polymer membranes with intrinsic microporosity for organic solvent reverse osmosis

AbstractOrganic solvent reverse osmosis (OSRO) is an emerging and promising technology for the separation of organic mixtures, which is realized by differential transport rates of organics through polymer membranes. However, the solvent transport characteristics and separation mechanism within OSRO systems remain unclear. Herein, we investigate the solvent transport behavior in polymer membranes with intrinsic microporosity by combining nonequilibrium molecular dynamics simulations with solvent permeation examinations. The results indicate that organic molecules permeate through the micropores in a clustered state driven by both pressure and concentration gradients. The selectivity of solvents is co‐determined by their sorption and diffusion in the swollen polymer membranes with a microporous character. The sorption selectivity is predominant in the overall selectivity toward polar ethyl ether/n‐butanol separation, whereas diffusion selectivity is more critical in nonpolar 1,3,5‐triisopropylbenzene/toluene separation. Generally, this work provides valuable insights into the development of next‐generation OSRO membranes for solvent separation.

Analysis of a plasma reactor performance for direct nitrogen fixation by use of three-dimensional simulations and experiments

This study utilizes state-of-the-art in-situ measurements and advanced three-dimensional simulations to investigate the operation of a microwave plasma reactor for nitrogen fixation at a high subatmospheric pressure under various power inputs. It is shown that the system should be treated as a warm plasma due to negligible differences in vibrational and rotational temperatures and that it is required to account for chemical non-equilibrium. Complex flow field and significant temperature and concentration gradients are observed, emphasizing the need for three-dimensional simulations to accurately describe the interactions between mass, heat, and momentum transport and chemical reactions in non-equilibrium conditions. The innermost plasma regions reach temperatures close to 6000 K, while wall temperatures remain low due to presence of a low-temperature swirling flow field around the hot core. Analysis reveals that the swirling flow field around the hot core provides intrinsic partial quenching in regions with large temperature gradients which counteract the return to chemical equilibrium and enrich the flow surrounding the hot core. The inner flow exhibits a recirculation zone, stagnation point, and a transition into an increasingly parabolic flow profile closer to the reactor outlet. The agreement between the numerical modeling and the measurements is strong. In-situ Raman spectroscopy measurements confirm the calculated temperature field inside the reactor. Thermocouple measurements on the reactor wall are also in good agreement with the simulation. Additionally, Fourier-transform infrared spectroscopy measurements agree very well with the simulated amount of nitrogen oxide exiting the reactor at different microwave power inputs. The understanding and modeling capabilities are expected to support the development of future reactor designs that can facilitate higher yields.

Nanocellulose aerogel prepared using discarded cotton textiles: For constructing water evaporation and self-cooling thermoelectric systems

In agricultural production, the substantial consumption of water and electricity resources is an urgent issue that needs to be addressed.In this work, we address this challenge by repurposing discarded cotton fabric and employing a unidirectional ice templating freezing technique to construct a cellulose hydrophilic aerogel featuring a biomimetic structure with unidirectional vertical channels, hereafter referred to as UVC-aerogel. This innovative material facilitates the conversion of low-grade waste heat (LGWH) into both water resources and electrical energy.The UVC aerogel exhibits remarkable evaporation performance, achieving an efficient evaporation rate of 9.18 kgm−2h−1, while demonstrating significant resistance to salt accumulation. Moreover, the evaporation effect synergistically enhances its thermoelectric power generation capacity. Through integration with a self-cooling open thermoelectric battery system, the UVC aerogel capitalizes on the concentration gradient formed within the evaporation system to augment the Seebeck coefficient (6.86 mVK−1) and power density (0.015 Wm−2K−2).This work present a green and sustainable solution to the water and electricity challenges encountered in agriculture, carrying substantial implications for both environmental conservation and agricultural advancement.

Candida albicans' inorganic phosphate transport and evolutionary adaptation to phosphate scarcity.

Phosphorus is essential in all cells' structural, metabolic and regulatory functions. For fungal cells that import inorganic phosphate (Pi) up a steep concentration gradient, surface Pi transporters are critical capacitators of growth. Fungi must deploy Pi transporters that enable optimal Pi uptake in pH and Pi concentration ranges prevalent in their environments. Single, triple and quadruple mutants were used to characterize the four Pi transporters we identified for the human fungal pathogen Candida albicans, which must adapt to alkaline conditions during invasion of the host bloodstream and deep organs. A high-affinity Pi transporter, Pho84, was most efficient across the widest pH range while another, Pho89, showed high-affinity characteristics only within one pH unit of neutral. Two low-affinity Pi transporters, Pho87 and Fgr2, were active only in acidic conditions. Only Pho84 among the Pi transporters was clearly required in previously identified Pi-related functions including Target of Rapamycin Complex 1 signaling, oxidative stress resistance and hyphal growth. We used in vitro evolution and whole genome sequencing as an unbiased forward genetic approach to probe adaptation to prolonged Pi scarcity of two quadruple mutant lineages lacking all 4 Pi transporters. Lineage-specific genomic changes corresponded to divergent success of the two lineages in fitness recovery during Pi limitation. Initial, large-scale genomic alterations like aneuploidies and loss of heterozygosity eventually resolved, as populations gained small-scale mutations. Severity of some phenotypes linked to Pi starvation, like cell wall stress hypersensitivity, decreased in parallel to evolving populations' fitness recovery in Pi scarcity, while severity of others like membrane stress responses diverged from Pi scarcity fitness. Among preliminary candidate genes for contributors to fitness recovery, those with links to TORC1 were overrepresented. Since Pi homeostasis differs substantially between fungi and humans, adaptive processes to Pi deprivation may harbor small-molecule targets that impact fungal growth, stress resistance and virulence.

Orbits, Spirals, and Trapped States: Dynamics of a Phoretic Janus Particle in a Radial Concentration Gradient.

A long-standing goal in colloidal active matter is to understand how gradients in fuel concentration influence the motion of phoretic Janus particles. Here, we present a theoretical description of the motion of a spherical phoretic Janus particle in the presence of a radial gradient of the chemical solute driving self-propulsion. Radial gradients are a geometry relevant to many scenarios in active matter systems and naturally arise due to the presence of a point source or sink of fuel. We derive an analytical solution for the Janus particle's velocity and quantify the influence of the radial concentration gradient on the particle's trajectory. Compared to a phoretic Janus particle in a linear gradient in fuel concentration, we uncover a much richer set of dynamic behaviors including circular orbits and trapped stationary states. We identify the ratio of the phoretic mobilities between the two domains of the Janus particle as a central quantity in tuning their dynamics. Our results provide a path for developing optimum protocols for tuning the dynamics of phoretic Janus particles and mixing fluid at the microscale. In addition, this work suggests a method for quantifying the surface properties of phoretic Janus particles, which have proven to be challenging to probe experimentally.

High power density charging-free thermally regenerative electrochemical flow cycle for low-temperature thermoelectric conversion

Low-temperature thermal energy widely exists in nature and is sustainable. The thermally regenerative electrochemical cycle (TREC) based on the Seebeck effect has attracted widespread attention due to its high thermoelectric efficiency and good cycle stability. However, it has a low power density and cannot sustain continuous operation for extended periods. This work proposes a continuous charging-free thermally regenerative electrochemically cycled flow battery (TREC-FB) system, which can discharge continuously at both high and low temperatures without the assistance of external power source. By adding guanidine hydrochloride (GdmCl) and inorganic salt ions (Cs+, Ca2+, Mg2+, etc.) to the K3Fe(CN)6/K4Fe(CN)6 and I2/KI electrolytes respectively, precipitates are formed in the electrolytes at low temperature and dissolve at high temperature, which creates the concentration gradient of ions. As a result, the temperature coefficient of the full cell increases from −2.24 mV/K to −3.6 mV/K, and both voltage and power density are doubled. Theoretical analysis of the temperature coefficient enhancement is conducted based on the Nernst equation, and the mechanism of the temperature coefficient enhancement is verified using UV–vis spectra. The discharging capacity and energy of the charging-free TREC-FB with high temperature coefficient reach 5 Ah/L and 1.9 kJ/L, respectively, and the thermoelectric efficiency reaches 8.9 % under sufficient heat recuperation. Two TREC-FBs at high and low temperatures are connected to carry out continuous operation experiments of the charging-free TREC-FB system. The use of charge-reinforced ion-selective membrane can effectively inhibit the migration of I− and I3− ions, achieving about 36 h of continuous operation, and the average power density achieves 0.6 W/m2.

Total atmospheric carbon detection by LIBS with multivariate physicochemical model based on transition and collision mechanism

The importance of total atmospheric carbon (TAC) has been increasingly recognized in light of the growing significance of global climate change. The concept of TAC has expanded beyond its previous focus solely on CO2 to encompass additional novel components. Here, a promising detection-analysis system for TAC quantitative detection is self-developed using LIBS and a multivariate physicochemical model based on transition and collision mechanism (MP-TC model). Spectral signals under different compositions were analyzed based on static detection. Then, a MP-TC model was developed by incorporating particle collisions and transition mechanisms. Subsequently, three dynamic monitoring were conducted analyzing the dynamic spectra obtained when CO2, CO, and CH4 were the different primary components of TAC. Interestingly, an anomalous CN transition was observed in Fuel combustion and the inhibited low vibrational transitions in symmetric molecules can be explored in CH4 gradient concentration. Additionally, each dynamic process was fitted using the MP-TC model, confirming its reliability in TAC detection and its better alignment with the observed trends.

High-Valence Ion Doped Compositionally Partitioned Li[Ni0.78Co0.10Mn0.12]O2 Cathode for Advanced Lithium-Ion Batteries

Numerous approaches have been employed to reduce the intrinsic instability of Ni-rich cathodes. Among them, the introduction of concentration gradient (CG), i.e., a strategy to protect the labile Ni-enriched compartment with a chemically protective Mn-rich shell, has proven successful in commercial applications.1 However, because the segmentation of transition metal (TM) constituents and the formation of unique geometric configurations are characteristics inherited from the CG hydroxide precursor; it is crucial to select the optimal calcination temperature and precisely control it.2 Excessive thermal energy input can result in concentration planarization because the CG of the hydroxide precursor is intrinsically susceptible to the interdiffusion of TM elements during lithiation. Moreover, the immoderate coarsening of the primary particles can eliminate the advantageous features of the CG design by producing equiaxed primary particles.2 In this study, we propose a strategy that can effectively ameliorate the deterioration of Ni-rich CG cathodes resulting from excessive thermal energy input and remarkably improve their electrochemical cycling performance. It was revealed that a trace amount of tungsten incorporation during the cathode calcination can effectively mitigate the high-temperature-induced cathode degeneration and maintain outstanding product quality over a wide range of temperatures. Thus, the proposed strategy opens new avenues for the facile synthesis of long-life Ni-rich CG cathodes. Reference s : [1] Y.-K. Sun, S.-T. Myung, B.-C. Park, J. Prakash, I. Belharouak, K. Amine, Nat. Mater. 8 (2009) 320-324.[2] G.-T. Park, H.-H. Ryu, T.-C. Noh, G.-C. Kang, Y.-K. Sun, Mater. Today 52 (2022) 9-18.

In-situ X-ray Fluorescence Analysis of In-plane Cerium-ion Distribution Under Humidity Gradients in Proton Exchange Membrane

For the wide application of polymer electrolyte fuel cells, durability of more than 50,000 hours is necessary. Chemical degradation of the perfluorosulfonic acid (PFSA) membrane electrolyte is one of the degradation factors. Hydrogen peroxide generated from crossover gas reacts with impurities, and the resulting radicals break the chemical bonds in the electrolyte membrane. To quench the radicals, cerium ions are added to the membrane electrode assembly (MEA) as a radical quencher. However, cerium ions are known to move in the in-plane direction due to the humidity gradient during fuel cell operation. In areas where cerium ions are depleted, the chemical bonds of the PFSA are attacked by radicals. Therefore, it is necessary to understand the in-plane transport phenomena of cerium ions under fuel cell operating conditionsand incorporate into the development of MEAs. In this study, we developed an operando measurement cell that can track the change of cerium ion distribution over time by X-ray fluorescence spectroscopy (XRF) using high energy X-rays under fuel cell operation while controlling the in-plane humidity gradient. The in-plane transport of cerium ions, driven by the humidity and concentration gradients, was analyzed.Two gas inlets were connected to an end plate with an X-ray transmission window to control two humidity environments on the left and right sides with in-plane direction of MEA. For MEA, Pt/C catalyst layer was coated on PFSA membranes in which a part of sulfonic acids were exchanged with cerium ions. GDL without cerium was used. Operando XRF measurements were performed at beamline BL37XU on SPring-8. The incident energy was 60 keV X-rays, and Ce-Kα fluorescence X-rays were counted. The beam size was 0.5×0.5 mm2. The cell temperature was 60°C, the different relative humidity (RH) in the in-plane direction was set to 90% and 50% using N2 gas, then the RH of the whole MEA was set to 95% to measure the relaxation behavior of cerium.Fig. 1 shows the Ce intensity variation at the vertical center of the MEA under the condition of humidity difference with in-plane direction. The x-axis corresponds to the horizontal position of the MEA, with RH 90% on the left side and RH 50% on the right side. The y-axis corresponds to the time under the humidity gradient. The darker blue indicates weaker intensity of the Ce-Kα fluorescence X-ray and the white indicates stronger Ce intensity. This suggests that cerium ions move from the high humidity side to the low humidity side with the humidity gradient as the driving force. The time scale for this movement of a few millimeters was shown to be about tens of minutes. Acknowledgments The authors would like to thank M. Toida (Toyota Motor Corporation) for providing samples and for in-depth discussions. Figure 1

Investigation of physicochemical and antibacterial properties of dill (Anethum graveolens L.) microencapsulated essential oil using fluidized bed method

The present study delves into the encapsulation of dill essential oil utilizing the fluidized bed coating methodology. The investigation focused on the impact of essential oil concentration and the application of maltodextrin and arabic gum as the primary and secondary coating agents. The dominant compounds in the dill essential oil were identified as limonene (32.32%), carvone (35.43%), and cis-dihydrocarvone (5.43%). The antimicrobial potency of the dill essential oil was evaluated, demonstrating notable inhibition against Streptococcus mutans with inhibition zone diameters ranging from 5.4 mm to 16 mm for concentrations between 250 μg/mL and 2000 μg/mL. For Streptococcus sobrinus, the inhibition zones measured from 6.6 mm to 18 mm across the same concentration gradient. An increase in maltodextrin concentration was associated with a decrease in moisture content, bulk density, and tapped density, while it improved microencapsulation efficiency and loading capacity. In contrast, a higher concentration of arabic gum increased moisture content, loading capacity, and encapsulation efficiency, but reduced bulk density and tapped density. Elevating the essential oil concentration increased all physicochemical properties of the microcapsules, except for tapped density. The optimal conditions for microencapsulation involve using a 2000 ppm concentration of dill essential oil with 75% maltodextrin and 0.1% arabic gum as carrier agents. Scanning electron microscopy images indicated that the microcapsule particles were nearly spherical with a smooth, intact surface. The release rate of phenolic compounds in a simulated saliva environment reached its maximum at 98.32% after 20 min, showcasing an efficient release profile.

Simulation of Magnetic Separation of Metal Ions in Aqueous Electrolytes

The magnetic separation of metal ions provides an alternative solution to traditional separation techniques such as pyrometallurgy, hydrometallurgy, biometallurgy or electrodialysis. Compared to traditional techniques that either use large amounts of chemicals (usually inorganic acids combined with reducing agent), produce large amounts of sludge as solid waste, consume a large amount of energy, or are difficult to separate ions of different charges [1], the magnetic separation of the metal ions can separate ions based on their magnetic susceptibility. This method is environmentally friendly [2] and consumes a small amount of energy (particularly when the system is designed using permanent magnets instead of electromagnets). The goal of this presentation is twofold. First, we derive the set of transport equations that need to be used to simulate the magnetic separation of metal ions in aqueous solutions. Then, we use these transport equations to simulate the magnetic separation process in various magnetic systems and predict the efficiency of magnetic separation of different systems.The mathematical model developed here is based on coupling the three-dimensional Navier-Stokes equations for flow transport with the drift (migration)-diffusion equations of ion transport [3] in the presence of magnetic field gradients. Both the drift-diffusion model and the Navier-Stokes equations include the magnetic force term as an additional driving force. By solving the entire system of equations self-consistently we analyze the effect of the diffusivity, concentration gradients, magnetic field gradients and fluid velocity over the capturing properties of the system. A detailed presentation of the mathematical model, underlying assumptions of the model, limiting cases, numerical implementation in three-dimensional structures, and simulations results will be presented at the meeting. In addition, we will present predictions for the magnetic separation of Li, Fe, Ni, Mn, and Co from the solution phase. Fortunately, these ions have significantly different magnetic susceptibility, which vary over more than 3 orders of magnitude, and which allows for the efficient extraction and separation of the elements from the solution and from each other.

Mechanical Failure of Core-Shell Cathode Particles: The Effects of Concentration-Dependent Material Properties and Phase Field Fracture Modelling

The use of core-shell cathode particles in lithium-ion batteries is an attractive approach to enhancing energy density whilst retaining lifetime, through reducing undesired reactions at the electrode-electrolyte interface and limiting the volume change of the electrode particles. However, mechanical failure through the fracture and debonding of the core-shell interface is a major challenge. In this work, we employ a coupled finite-element model to predict and mitigate the mechanical failure of core-shell cathode structures, taking as example a particle of NMC811 (core) coated with NMC111 (shell). In particular, we focus on two aspects:The first one involves the assumptions of material properties as inputs of the model. The material properties are often considered constant by battery modelling researchers, yet these parameters can vary significantly during charge/discharge. For example, experiments have unveiled a three-orders-of-magnitude drop in the diffusion coefficient of NMC materials during discharge [1]. Here, we incorporate material properties obtained from experimental data, including concentration-dependent diffusion coefficient obtained from GITT measurement and partial molar volume derived from in situ X-ray diffraction data. Our results indicate that when assuming a concentration-dependent partial molar volume, the maximum values of tensile hoop stress in the shell are nearly three times lower than those predicted with constant average properties, diminishing the likelihood of fracture.When accounting for concentration-dependent diffusion coefficient, large concentration gradient is observed near the outer surface of the core due to reduced lithium mobility at high states of lithiation, hindering full electrode capacity utilisation. The significant concentration gradient and capacity underutilisation align with direct observations from experiments [2]. Notably, these phenomena cannot be captured in modelling if assuming constant diffusion coefficient. These findings offer new perspectives on the performance and design of core-shell electrode particles. Safe design maps in terms of core size and shell thickness to mitigate fracture and debonding are obtained.The second focus of this work is the utilisation of phase field fracture model in predicting cracking behaviours within the core-shell particle. Phase field modelling provides a continuous representation of cracks, enabling the tracking of complex cracking patterns [3]. We predict cracking behaviors caused by volume changes during charge/discharge, as well as inaccessible capacity and newly created active surface area caused by cracking. Our multiphyics model can hopefully act as a catalyst, accelerating the development process of the core-shell structured cathode particles and shortening the time to market of advanced batteries with extended lifetime.

Assessment of Hysteresis Models for LiFePO4

The selection of the cathode material is an important task in the design phase of batteries for mobile applications. One material of increasing interest is LiFePO4 (LFP) due to its improved energy density, good thermal stability and durability. In contrast to other commonly used cathode materials, LFP features a clear phase separation between the lithium rich and the lithium poor phase, leading to a pronounced voltage plateau over wide ranges of state of charge (SOC). The level of this plateau also changes for charge and discharge operation, even at very low C-rates. This voltage hysteresis in combination with the wide plateau gives some ambiguity to the correlation between voltage and SOC, which is a challenge for battery management systems. Thus its correct description is crucial if a cell model is meant to serve as virtual twin supporting control function development and calibration. Beyond that, a highly dynamic battery development process requires models that run significantly faster than real-time and parametrization processes which allow for accurate validation and easy adaptation to modified electrodes. A simulation approach complying with these requirements is the electrochemical pseudo-two dimensional (P2D) model, though adaptions to the core model are needed to appropriately capture hysteresis-affected voltage plateau characteristics for phase-separating materials such as LFP.The goal of this study is to extend an existing P2D framework with two approaches capable of describing hysteresis effects and analyzing these extensions regarding result plausibility, computational cost and effort of parametrization. The first model of interest is based on the one-state hysteresis model proposed by Plett. This approach allows for fast simulation and accurate reproduction of the charge and discharge voltages at low C-rates but lacks deeper physical consideration of the phase-separating origin of the hysteresis and thus might lose accuracy to predict system responses on dynamic pulses. In this approach, the voltage hysteresis is not a simulation result, it is due to the input of two separate open circuit voltages for charge and discharge. The second model of interest applies variable solid diffusion (VSSD) featuring a reduced Fickian diffusion coefficient in the plateau region. Lower diffusion at a given C-rate leads to steeper concentration gradients between lithium rich and lithium poor phase. With this approach, effective phase boundaries within the representative particles can be obtained. In the limiting case, when the Fickian diffusion coefficient becomes zero or even negative at some lithium concentration, phase separation persists also when no current is applied. In this setting, the voltage hysteresis at low C-rates is an emergent phenomenon, it is not an input. The physical basis of the approach also allows to consider mechanical stresses and their impact on the voltage gap between charge and discharge. Concentration gradients cause a mismatch of volume demands and thus lead to local stresses, which in turn alter the chemical potential.Results emphasizing advantages and disadvantages of the two hysteresis models are presented. Charge and discharge simulations are performed for several C-rates and the voltage hysteresis is extrapolated to infinitely small currents. Furthermore, the effect of resting phases with zero current as in Galvanostatic Intermittent Titration Technique measurements is discussed. As hysteresis models are often tested only on charge/discharge cycles with constant currents over large SOC regions, the responses of the simulation models are also assessed in pulse tests and dynamic profiles giving a realistic picture of automotive applications. Here special focus is put on energetical aspects of the one-state model and on intra-particle concentration profiles for the VSSD model.

Interleaved Electrode Structures for Enhanced Electrolyte Mass Transport in Li-Ion Batteries : A Numerical Study

The enhancement of energy and power density in Li-ion batteries remains a focal point in battery research. When Li-ion batteries are operated at high C-rates, mass transport limitations cause large concentration gradients of Lithium ions to form in the electrolyte. The resultant concentration overpotentials and underutilization of active material effectively imply a lower capacity for higher current rates, which creates a tradeoff between energy and power density. The integration of 3D interleaved electrode structures has been proposed to augment power density while preserving energy density. This work comprehensively analyzes the capacity improvement achieved by utilizing a wavy interleaved structure using electrochemical simulations. A pseudo-3D (P3D) model based on the Doyle-Fuller-Newman framework is employed to analyze the performance of various depths and frequencies of the wavy interleaved structure. Galvanostatic simulations are performed for NMC/Graphite-SiOx and LMO/Graphite cells at different C-rates, and the resultant voltage is systematically divided into component overpotentials to delineate the contribution of activation, ohmic, and mass-transfer overpotentials in both solid electrode and electrolyte. With the same amount of active material, simulations indicate a performance improvement of 7% in capacity at high C-rates. It is observed that using a wavy structure significantly reduces electrolyte concentration heterogeneities and resulting concentration gradients when compared to a conventional flat structure. The overpotential breakdown confirms that the improvement in voltage is indeed contributed precisely by the concentration overpotential. Concentration overpotential decreases with deeper interleaved structures as well as for more spatially frequent structures.Additionally, the impact of the interleaved electrode structure on cell degradation was also assessed. Lithium plating, which is the most prominent side reaction in the anode, was modeled using a Butler-Volmer kinetic equation, with deposition occurring locally when the solid phase potential drops below that of the electrolyte potential. The interleaved structure alleviates plating significantly due to higher uniformity in Li-ion concentration. With this work, we computationally demonstrate that interleaved structure works well for extracting higher capacity with the same active material, and also aids in suppressing Lithium plating.Figure Caption : Computed Li-ion concentration profile in the solid active material of an interleaved electrode Li-ion cell as a function of location (x, y) and distance from particle center (z) Figure 1

Thermal Modeling of Li-Ion Cylindrical Cells at Scale

The electric vehicle industry has created a demand for batteries with higher power densities. The current design choice for low-weight lithium-ion battery packs for electric vehicles is to create stacks arranged in parallel or series configurations to match the power demands. The individual cells are separated and placed in a cooling duct to pull heat away from the longitudinal surface convective. The amount of cooling is dependent on the internal temperature of batteries core. The current design of the cylindrical cell is to roll the cathode, anode, and separators into a jelly roll together and attach a tab to the cathode and anode at opposite corners of the sheet. The tabs connect to the positive and negative terminals of the cell to draw current away from the cell. The tabs may act as an agent for drawing heat away from the center of the battery. Currently, commonly used cylindrical cells have a form factor of 18650, 21700, or 26650. The thermal, geometrical, and electrical properties of 18650 and 21700 cylindrical cells are studied and it is found that the 21700 cells showed additional degradation and stronger heating. Recently, companies like Tesla have produced cylindrical cells with a 4680-form factor, which is a decent way to increase the ratio of active material vs. inactive material in a cylindrical cell. However, large diameter thick cylindrical cells suffer from thermal issues. Even large format pouch cells suffer through heat trapped within the stack.Since the thermal conductivity of the anode and cathode electrodes is often near 1 W/m-K, it becomes difficult for the heat to be extracted from the center of a large-diameter cylindrical cell without forming a considerable thermal gradient. PyBaMM, an open-source mathematical modeling software written in Python programming language, has the capability to simulate different electrochemical models such as the Doyle-Fuller-Newman (DFN), Single particle model (SPM), and SPMe, and varying chemistry. The software provides easy access to the cell parameters modification and graphical user interface capabilities. The PyBaMM framework also allows to simulation lumped, isothermal, and base thermal models which are electrochemically coupled. PyBaMM uses CasADi (computer algebra systems algorithmic differentiation). The thermal gradient and heat dynamics within a porous electrode are modeled using PoreSpy and openpnm, two open-source Python libraries used to design porous networks and model physical equations such as governing heat flow, concentration gradient, and movement of water/oil through porous shale media.We have explored and combined heat dynamic models for Li-Ion cylindrical cells at both cell and electrode levels with reduced-order Doyle-Fuller-Newman electro-chemical model frameworks implemented in the PyBaMM python library. Radial temperature gradient at cell and electrode levels were both generated from simulations with a distributed parameter model as a function of electrolyte and separator thickness and thermodynamic properties. Figure 1

Density-Nematic Coupling in Isotropic Solution of DNA: Multiscale Model.

Monte Carlo simulations of isotropic solutions of double-stranded DNA (deoxyribonucleic acid) are performed using the well-established oxDNA model. By comparing the fluctuation amplitudes with theoretical predictions, the parameters of a generic macroscopic model of an isotropic linear polymer solution/melt are determined. A multiscale continuum field model is thus obtained, corresponding to the full specificity of the isotropic phase of double-stranded DNA in the usual B-form as perceived at the macroscopic level. Present research is particularly focused on the coupling between spatial concentration/density variations of the polymer and the emerging nematic orientation order of the chains. This rather unfamiliar, only recently described phenomenon, inherent to linear polymers, is outlined and interpreted. Quantitative predictions are provided for the degree of nematic order induced by concentration gradients in isotropic solutions of double-strandedDNA.