Search results for: lithium rich oxide cathode

Authors: Yanhui Jia, Ning Guo, Juan Li, Yunkui Sun, Wei Yang, Tianping Zhang, Lin Ma, Wei Meng, Hai Geng

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The current statuses of lifetime test of LaB6 hollow cathode at the Lanzhou institute of physics (LIP), China, was described. 5A LaB6 hollow cathode was designed for LIPS-200 40mN Xenon ion thruster and it could be used for LHT-100 80 mN Hall thruster, too. Life test of the discharge and neutralizer modes of LHC-5 hollow cathode were stared in October 2011, and cumulative operation time reached 17,300 and 16,100 hours in April 2015, respectively. The life of cathode was designed more than 11,000 hours. Parameters of discharge and key structure dimensions were monitored in different stage of life test indicated that cathodes were health enough. The test will continue until the cathode cannot work or operation parameter is not in normally. The result of the endurance test of cathode demonstrated that the LaB6 hollow cathode is satisfied for the required of thruster in life and performance.

Keywords: LaB6, hollow cathode, thruster, lifetime test, electric propulsion

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Authors: Yongkui Cui, Fengping Wang, Hailei Zhao, Muhammad Zubair Iqbal, Ziya Wang, Yan Li, Pengpeng LV

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The novel 3D SnO cabbages self-assembled by nanosheets were successfully synthesized via template-free hydrothermal growth method under facile conditions.The XRD results manifest that the as-prepared SnO is tetragonal phase. The TEM and HRTEM results show that the cabbage nanosheets are polycrystalline structure consisted of considerable single-crystalline nanoparticles. Two typical Raman modes A1g=210 and Eg=112 cm-1 of SnO are observed by Raman spectroscopy. Moreover, galvanostatic cycling tests has been performed using the SnO cabbages as anode material of lithium ion battery and the electrochemical results suggest that the synthesized SnO cabbage structures are a promising anode material for lithium ion batteries.

Keywords: electrochemical property, hydrothermal synthesis, lithium ion battery, stannous oxide

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Authors: Nour S. Abdelrahman, Seunghyun Hong, Hassan A. Arafat, Daniel Choi, Faisal Al Marzooqi

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Abstract—The advancement of lithium extraction methods from water sources, particularly saltwater brine, is gaining prominence in the lithium recovery industry due to its cost-effectiveness. Traditional techniques like recrystallization, chemical precipitation, and solvent extraction for metal recovery from seawater or brine are energy-intensive and exhibit low efficiency. Moreover, the extensive use of organic solvents poses environmental concerns. As a result, there's a growing demand for environmentally friendly lithium recovery methods. Membrane-based separation technology has emerged as a promising alternative, offering high energy efficiency and ease of continuous operation. In our study, we explored the potential of lithium-selective sieve channels constructed from layers of 2D graphene oxide and MXene (transition metal carbides and nitrides), integrated with surface – SO₃₋ groups. The arrangement of these 2D sheets creates interplanar spacing ranging from 0.3 to 0.8 nm, which forms a barrier against multivalent ions while facilitating lithium-ion movement through nano capillaries. The introduction of the sulfonate group provides an effective pathway for Li⁺ ions, with a calculated binding energy of Li⁺ – SO³⁻ at – 0.77 eV, the lowest among monovalent species. These modified membranes demonstrated remarkably rapid transport of Li⁺ ions, efficiently distinguishing them from other monovalent and divalent species. This selectivity is achieved through a combination of size exclusion and varying binding affinities. The graphene oxide channels in these membranes showed exceptional inter-cation selectivity, with a Li⁺/Mg²⁺ selectivity ratio exceeding 104, surpassing commercial membranes. Additionally, these membranes achieved over 94% rejection of MgCl₂.

Keywords: ion permeation, lithium extraction, membrane-based separation, nanotechnology

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Authors: Atef Y. Shenouda, Anton A. Momchilov

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Graphene and CdO with different stoichiometric ratios of Cd(CH₃COO)₂ and graphene samples were prepared by hydrothermal reaction. The crystalline phases of pure CdO and 3CdO:1graphene were identified by X-ray diffraction (XRD). The particle morphology was studied with SEM. Furthermore, impedance measurements were applied. Galvanostatic measurements for the cells were carried out using potential limits between 0.01 and 3 V vs. Li/Li⁺. The current cycling intensity was 10⁻⁴ A. The specific discharge capacity of 3CdO-1G cell was about 450 Ah.Kg⁻¹ up to more than 100 cycles.

Keywords: CdO, graphene, negative electrode, lithium battery

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Authors: Soraya Hoornam, Zeinab Sanaee

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Lithium-ion batteries are widely used for providing energy for mobile electronic devices. Graphite is a traditional anode material that was used in almost all commercialized lithium-ion batteries. It gives a specific capacity of 372 mAh/g for lithium storage. But there are multiple better choices for storing lithium that propose significantly higher specific capacities. As an example, silicon-based materials can be mentioned. In this regard, SiO₂ material can offer a huge specific capacity of 1965 mAh/g. Due to this high lithium storage ability, large volume change occurs in this electrode material during insertion and extraction of lithium, which may lead to cracking and destruction of the electrode. The use of nanomaterials instead of bulk material can significantly solve this problem. In addition, if we insert lithium in the active material of the battery before its cycling, which is called pre-lithiation, a further enhancement in the performance is expected. Here, we have fabricated an anode electrode of the battery using SiO₂ nanomaterial mixed with Graphite and assembled a lithium-ion battery half-cell with this electrode. Next, a pre-lithiation was performed on the SiO₂ nanoparticle-containing electrode, and the resulting anode material was investigated. This electrode has great potential for high-performance lithium-ion batteries.

Keywords: SiO₂ nanoparticles, lithium-ion battery, pre-lithiation, anode material

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Authors: Sanaz Mosadeghsedghi, Mathew Hudder, Mohammad Ali Baghbanzadeh, Charbel Atallah, Seyedeh Laleh Dashtban Kenari, Konstantin Volchek

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Lithium has recently been extensively used in lithium-ion batteries (LIBs) for electric vehicles and portable electronic devices. The conventional evaporative approach to recover and concentrate lithium is extremely slow and may take 10-24 months to concentrate lithium from dilute sources, such as geothermal brines. To response to the increasing industrial lithium demand, alternative extraction and concentration technologies should be developed to recover lithium from brines with low concentrations. In this study, a combination of electrocoagulation (EC) and electrodialysis (ED) was evaluated for the recovery of lithium from geothermal brines. The brine samples in this study, collected in Western Canada, had lithium concentrations of 50-75 mg/L on a background of much higher (over 10,000 times) concentrations of sodium. This very high sodium-to-lithium ratio poses challenges to the conventional direct-lithium extraction processes which employ lithium-selective adsorbents. EC was used to co-precipitate lithium using a sacrificial aluminium electrode. The precipitate was then dissolved, and the leachate was treated using ED to separate and concentrate lithium from other ions. The focus of this paper is on the study of ED, including a two-step ED process that included a mono-valent selective stage to separate lithium from multi-valent cations followed by a bipolar ED stage to convert lithium chloride (LiCl) to LiOH product. Eventually, the ED cell was reconfigured using mono-valent cation exchange with the bipolar membranes to combine the two ED steps in one. Using this process at optimum conditions, over 95% of the co-existing cations were removed and the purity of lithium increased to over 90% in the final product.

Keywords: electrochemical separation, electrocoagulation, electrodialysis, lithium extraction

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Authors: Usama Mohamed, Sam Booth, Aliysn J. Nedoma

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As part of the transition to electric vehicles, there has been a recent increase in demand for battery manufacturing. Cathodes typically account for approximately 50% of the total lithium-ion battery cell cost and are a pivotal factor in determining the viability of new industrial infrastructure. Cathodes which offer lower costs whilst maintaining or increasing performance, such as nickel-rich layered cathodes, have a significant competitive advantage when scaling up the manufacturing process. This project evaluates the techno-economic value proposition of an integrated industrial scale cathode active material (CAM) production process, closing the mass and energy balances, and optimizing the operation conditions using a sensitivity analysis. This is done by developing a process model of a co-precipitation synthesis route using Aspen Plus software and validated based on experimental data. The mechanism chemistry and equilibrium conditions were established based on previous literature and HSC-Chemistry software. This is then followed by integrating the energy streams, adding waste recovery and treatment processes, as well as testing the effect of key parameters (temperature, pH, reaction time, etc.) on CAM production yield and emissions. Finally, an economic analysis estimating the fixed and variable costs (including capital expenditure, labor costs, raw materials, etc.) to calculate the cost of CAM ($/kg and $/kWh), total plant cost ($) and net present value (NPV). This work sets the foundational blueprint for future research into sustainable industrial scale processes for CAM manufacturing.

Keywords: cathodes, industrial production, nickel-rich layered cathodes, process modelling, techno-economic analysis

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Authors: A. Guemache, M. Omari

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Oxides with formula Ca1-xSrx MnO3 (0≤x≤0.2) were synthesized using co-precipitation method. The identification of the obtained phase was carried out using infrared spectroscopy and X-ray diffraction. Thermogravimetric and differential analysis was permitted to characterize different transformations of precursors which take place during one heating cycle. The study of electrochemical behavior was carried out by cyclic voltammetry and impedance spectroscopy. The obtained results show that apparent catalytic activity improved when increasing the concentration of strontium. Anodic current densities varies from 1.3 to 5.9 mA/cm2 at the rate scan of 20 mV.s-1 and a potential 0.8 V for oxides with composition x=0 to 0.2.

Keywords: oxide, co-precipitation, electrochemical properties, cathode-type

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Authors: Aravind G., Arshinder Kaur, Pushpavanam S.

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There is a strong emphasis on shifting to electric vehicles (EVs) throughout the globe for reducing the impact on global warming following the Paris climate accord. Lithium-ion batteries (LIBs) are predominantly used in EVs, and these can be a significant threat to the environment if not disposed of safely. Lithium is also a valuable resource not widely available. There are several research groups working on developing an efficient recycling process for LIBs. Two routes - pyrometallurgical and hydrometallurgical processes have been proposed for recycling LIBs. In this paper, we focus on life cycle assessment (LCA) as a tool to quantify the environmental impact of these recycling processes. We have defined the boundary of the LCA to include only the recycling phase of the end-of-life (EoL) of the battery life cycle. The analysis is done assuming ideal conditions for the hydrometallurgical and a combined hydrometallurgical and pyrometallurgical process in the inventory analysis. CML-IA method is used for quantifying the impact assessment across eleven indicators. Our results show that cathode, anode, and foil contribute significantly to the impact. The environmental impacts of both hydrometallurgical and combined recycling processes are similar across all the indicators. Further, the results of LCA are used in developing a multi-objective optimization model for the design of lithium-ion battery recycling network. Greenhouse gas emissions and cost are the two parameters minimized for the optimization study.

Keywords: life cycle assessment, lithium-ion battery recycling, multi-objective optimization, network design, reverse supply chain

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Authors: Jinliang Yuan, Jong-Sung Yu, Bengt Sundén

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A computational fluid dynamics (CFD) model is developed for rechargeable non-aqueous electrolyte lithium-air batteries with a partial opening for oxygen supply to the cathode. Multi-phase transport phenomena occurred in the battery are considered, including dissolved lithium ions and oxygen gas in the liquid electrolyte, solid-phase electron transfer in the porous functional materials and liquid-phase charge transport in the electrolyte. These transport processes are coupled with the electrochemical reactions at the active surfaces, and effects of discharge reaction-generated solid Li2O2 on the transport properties and the electrochemical reaction rate are evaluated and implemented in the model. The predicted results are discussed and analyzed in terms of the spatial and transient distribution of various parameters, such as local oxygen concentration, reaction rate, variable solid Li2O2 volume fraction and porosity, as well as the effective diffusion coefficients. It is found that the effect of the solid Li2O2 product deposited at the solid active surfaces is significant on the transport phenomena and the overall battery performance.

Keywords: Computational Fluid Dynamics (CFD), modeling, multi-phase, transport phenomena, lithium-air battery

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Authors: Yingjeng James Li, Chih Chi Hsu, Chiao-Chih Hu

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Membrane electrode assemblies MEAs for proton exchange membrane PEM water electrolyzers were prepared by employing 175um perfluorosulfonic acid PFSA membranes as the PEM, onto which iridium oxide catalyst was coated on one side as the anode and platinum catalyst was coated on the other side as the cathode. The cathode catalyst ink was prepared so that the weight ratio of the catalyst powder to ionomer was 75:25, 70:30, 65:35, 60:40, and 55:45, respectively. Whereas, the ratio of catalyst powder to ionomer of the anode catalyst ink keeps constant at 50:50. All the MEAs have a catalyst coated area of 5cm*5cm. The test cell employs a platinum plated titanium grid as anode gas diffusion media; whereas, carbon paper was employed as the cathode gas diffusion media. The measurements of the MEA gases production rate were carried out by holding the cell voltage ranging from 1.6 to 2.8 volts at room temperature. It was found that the MEA with cathode catalyst to ionomer ratio of 65:35 gives the largest hydrogen production rate which is 2.8mL/cm2*min.

Keywords: electrolyzer, membrane electrode assembly, proton exchange membrane, ionomer, hydrogen

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Authors: Sarish Rehman, Kishwar Khan, Yanglong Hou

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Among the existed myriad energy-storage technologies, lithium–sulfur batteries (LSBs) show the appealing potential for the ubiquitous growth of next-generation electrical energy storage application, owing to their unparalleled theoretical energy density of 2600 Wh/kg that is over five times larger than that of conventional lithium-ion batteries (LIBs). Despite its significant advances, its large scale implementations are plagued by multitude issues: particularly the intrinsic insulating nature of the sulfur (10-30 S/cm), mechanical degradation of the cathode due to large volume changes of sulfur up to 80 % during cycling and loss of active material (producing polysulfide shuttle effect). We design a unique structure, namely silicon/silica (Si/SiO2) crosslink with hierarchical porous carbon spheres (Si/SiO2@C), and use it as a new and efficient sulfur host to prepare Si/SiO2@C-S hybrid spheres to solve the hurdle of the polysulfides dissolution. As results of intriguing structural advantages developed hybrids spheres, it acts as efficient polysulfides reservoir for enhancing lithium sulfur battery (LSB) in the terms of capacity, rate ability and cycling stability via combined chemical and physical effects.

Keywords: high specific surface area, high power density, high content of sulfur, lithium sulfur battery

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Authors: Muhammad Husnat Khalid, Stephan Bihn, Dirk Uwe Sauer, Nisai Fuengwarodsakul

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To combat the effects of climate change, lithium-ion batteries are getting a lot of attention for energy storage. However, due to its diverse range of applications extending from small electronics equipment to energy storage systems, its output requirements, as well as limitations, vary significantly. Many efforts are underway to increase the power and energy output of the cells without any significant compromise on their size and weight. In this paper, different active materials are explored for an existing cell Kokam that initially has graphite as anode and NCO as cathode material. The Pareto front optimization tool is then utilized to pick a cell that gives the optimum results in terms of energy, power, or both. The parameter variation of the cells is done in the MATLAB application ISEA Cell and Pack Database (ICPD) created by the Institute of Power Electronics and Electrical Drives (ISEA) RWTH Aachen, University that creates the physical-chemical model of the existing cells.

Keywords: battery storage system, lithium-ion battery, active material variation, cell design optimization

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Authors: Gregory Schmidt

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Solid-state lithium batteries are broadly accepted as promising candidates for application in the next generation of EVs as they should offer safer and higher-energy-density batteries. Nonetheless, their development is impeded by many challenges, including the resistive electrode–electrolyte interface originating from the removal of the liquid electrolyte that normally permeates through the porous cathode and ensures efficient ionic conductivity through the cell. One way to tackle this challenge is by formulating composite cathodes containing solid ionic conductors in their structure, but this approach will require the conductors to exhibit chemical stability, electrochemical stability, flexibility, and adhesion and is, therefore, limited to some materials. Recently, Arkema developed a technology called buffering layer which allows the transformation of any conventional porous electrode into a catholyte. This organic layer has a very high ionic conductivity at room temperature, is compatible with all active materials, and can be processed with conventional Gigafactory equipment. Moreover, this layer helps protect the solid ionic conductor from the cathode and anode materials. During this presentation, the manufacture and the electrochemical performance of this layer for different systems of cathode and anode will be discussed.

Keywords: electrochemistry, all solid state battery, materials, interface

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Authors: Fang Li, Jiazhao Wang, Jianmin Ma

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The practical application of Li-S batteries is hampered due to poor cycling stability caused by electrolyte-dissolved lithium polysulfides. Dual functionalities such as strong chemical adsorption stability and high conductivity are highly desired for an ideal host material for a sulfur-based cathode. Polypyrrole (PPy), as a conductive polymer, was widely studied as matrixes for sulfur cathode due to its high conductivity and strong chemical interaction with soluble polysulfides. Thus, a novel cathode structure consisting of a free-standing sulfur-polypyrrole cathode and a polypyrrole coated separator was designed for flexible Li-S batteries. The PPy materials show strong interaction with dissoluble polysulfides, which could suppress the shuttle effect and improve the cycling stability. In addition, the synthesized PPy film with a rough surface acts as a current collector, which improves the adhesion of sulfur materials and restrain the volume expansion, enhancing the structural stability during the cycling process. For further enhancing the cycling stability, a PPy coated separator was also applied, which could make polysulfides into the cathode side to alleviate the shuttle effect. Moreover, the PPy layer coated on commercial separator is much lighter than other reported interlayers. A soft-packaged flexible Li-S battery has been designed and fabricated for testing the practical application of the designed cathode and separator, which could power a device consisting of 24 light-emitting diode (LED) lights. Moreover, the soft-packaged flexible battery can still show relatively stable cycling performance after repeated bending, indicating the potential application in flexible batteries. A novel vapor phase deposition method was also applied to prepare uniform polypyrrole layer coated sulfur/graphene aerogel composite. The polypyrrole layer simultaneously acts as host and adsorbent for efficient suppression of polysulfides dissolution through strong chemical interaction. The density functional theory (DFT) calculations reveal that the polypyrrole could trap lithium polysulfides through stronger bonding energy. In addition, the deflation of sulfur/graphene hydrogel during the vapor phase deposition process enhances the contact of sulfur with matrixes, resulting in high sulfur utilization and good rate capability. As a result, the synthesized polypyrrole coated sulfur/graphene aerogel composite delivers a specific discharge capacity of 1167 mAh g⁻¹ and 409.1 mAh g⁻¹ at 0.2 C and 5 C respectively. The capacity can maintain at 698 mAh g⁻¹ at 0.5 C after 500 cycles, showing an ultra-slow decay rate of 0.03% per cycle.

Keywords: polypyrrole, strong chemical interaction, long-term stability, Li-S batteries

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis

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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.

Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals

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Authors: Zhihong Luo, Guangbin Zhu, Lulu Guo, Zhujun Lyu, Kun Luo

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Cycling life has become the threshold for the prospective application of Li-O₂ batteries, and the protection of Li anode has recently regarded as the key factor to the performance. Herein, a simple low rate pre-activation (20 cycles at 0.5 Ag⁻¹ and a capacity of 200 mAh g⁻¹) was employed to effectively improve the performance and cyclability of Li-O₂ batteries. The charge/discharge cycles at 1 A g⁻¹ with a capacity of 1000 mAh g⁻¹ were maintained for up to 290 times versus 55 times for the cell without pre-activation. The ultimate battery capacity and high rate discharge property were also largely enhanced. Morphology, XRD and XPS analyses reveal that the performance improvement is in close association with the formation of the smooth and compact surface layer formed on the Li anode after low rate pre-activation, which apparently alleviated the corrosion of Li anode and the passivation of cathode during battery cycling, and the corresponding mechanism was also discussed.

Keywords: lithium oxygen battery, pre-activation, cyclability, capacity

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Authors: Nuray Ucar, Pelin Altay, Ilkay Ozsev Yuksek

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Graphene oxide fibers have recently received increasing attention due to their excellent properties such as high specific surface area, high mechanical strength, good thermal properties and high electrical conductivity. They have shown notable potential in various applications including batteries, sensors, filtration and separation and wearable electronics. Carbon nanotubes (CNTs) have unique structural, mechanical, and electrical properties and can be used together with graphene oxide fibers for several application areas such as lithium ion batteries, wearable electronics, etc. Metals salts that can be converted into metal ions and metal oxide can be also used for several application areas such as battery, purification natural gas, filtration, absorption. This study investigates the effects of CNT and metal complex compounds (MnCl₂, metal salts) on the morphological structure of graphene oxide fibers. The graphene oxide dispersion was manufactured by modified Hummers method, and continuous graphene oxide fibers were produced with wet spinning. The CNT and MnCl₂ were incorporated into the coagulation baths during wet spinning process. Produced composite continuous fibers were analyzed with SEM, SEM-EDS and AFM microscopies and as spun fiber counts were measured.

Keywords: continuous graphene oxide fiber, Hummers' method, CNT, MnCl₂

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Authors: Romeo Malik, Yashraj Tripathy, Anup Barai

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Transportation safety is a major concern for vehicle electrification on a large-scale. The failure cost of lithium-ion batteries is substantial and is significantly impacted by higher liability and replacement cost. With continuous advancement on the material front in terms of higher energy density, upgrading safety characteristics are becoming more crucial for broader integration of lithium-ion batteries. Understanding and impeding thermal runaway is the prime issue for battery safety researchers. In this study, a comprehensive comparison of thermal runaway mechanisms for two different cathode types, Li(Ni₀.₃Co₀.₃Mn₀.₃)O₂ and Li(Ni₀.₈Co₀.₁₅Al₀.₀₅)O₂ is explored. Both the chemistries were studied for different states of charge, and the various abuse scenarios that lead to thermal runaway is investigated. Abuse tests include mechanical abuse, electrical abuse, and thermal abuse. Batteries undergo thermal runaway due to a series of combustible reactions taking place internally; this is observed as multiple jets of flame reaching temperatures of the order of 1000ºC. The physicochemical characterisation was performed on cells, prior to and after abuse. Battery’s state of charge and chemistry have a significant effect on the flame temperature profiles which is otherwise quantified as heat released. Majority of the failures during transportation is due to these external short circuit. Finally, a mitigation approach is proposed to impede the thermal runaway hazard. Transporting lithium-ion batteries under low states of charge is proposed as a way forward. Batteries at low states of charge have demonstrated minimal heat release under thermal runaway reducing the risk of secondary hazards such as thermal runaway propagation.

Keywords: battery reliability, lithium-ion batteries, thermal runaway characterisation, tomography

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Authors: Yaser Maher Abdelaziz Hawa

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The Basic-ultrabasic rocks of Bou Azzer ophiolite complex in the Anti-atlas , Morrocco enclose some oxide and sulfide minerals as dissiminated traces. The oxide minerals show a wide variation in composition ranging from Cr-free. Titanomagnetite and ilmenite in the chilled margin gabbro of the upper part of the ophiolite sequence to Al-rich chromian spinel and pure magnetite enclosed in the serpentinized peridotite in the lower part of the sequence. Five mineral assemblages have been distinguished depending on the rock type of the ophiolite sequence. 1-Gersodorfite + Chalcopyrite + Al-Mg rich chromian spinel + pure magnetite, hosted by serpentinized peridotite. 2- Pyrite + Chalcopyrite, enclosed in metagabbro and overlying the ultrabasic cumulates. 3- Al-Fe rich Chromian spinel with rims of Al –rich chromian magnetite enclosed in wherlite. 4- Titanomagnetite replaced by sphene enclosed in marginal Gabbro. 5- Pyrrhotite exsolving Pentlandite + ilmenite + Ilmenite + Al- rich Chromian spinel + magnetite enclosed in fresh olivine olivine in the upper part of the ophiolite sequence.

Keywords: opaques, ophiolites, anti-atlas, morrocco

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Authors: Enhui Wang, Qingzhu Ou, Yan Tang, Xiaodong Guo

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As one of most popular polyanionic compounds in lithium-ion cathode materials, Li3V2(PO4)3 has always suffered from the low rate capability especially during 3~4.8V, which is considered to be related with the ion diffusion resistance and structural transformation during the Li+ de/intercalation. Here, as the change of cut-off voltages, cycling numbers and current densities, the process of SEI interfacial film’s formation-growing- destruction-repair on the surface of the cathode, the structural transformation during the charge and discharge, the de/intercalation kinetics reflected by the electrochemical impedance and the diffusion coefficient, have been investigated in detail. Current density, cycle numbers and cut-off voltage impacting on interfacial film and structure was studied specifically. Firstly, the matching between electrolyte and material was investigated, it turned out that the batteries with high voltage electrolyte showed the best electrochemical performance and high voltage electrolyte would be the best electrolyte. Secondly, AC impedance technology was used to study the changes of interface impedance and lithium ion diffusion coefficient, the results showed that current density, cycle numbers and cut-off voltage influenced the interfacial film together and the one who changed the interfacial properties most was the key factor. Scanning electron microscopy (SEM) analysis confirmed that the attenuation of discharge specific capacity was associated with the destruction and repair process of the SEI film. Thirdly, the X-ray diffraction was used to study the changes of structure, which was also impacted by current density, cycle numbers and cut-off voltage. The results indicated that the cell volume of Li3V2 (PO4 )3 increased as the current density increased; cycle numbers merely influenced the structure of material; the cell volume decreased first and moved back gradually after two Li-ion had been deintercalated as the charging cut-off voltage increased, and increased as the intercalation number of Li-ion increased during the discharging process. Then, the results which studied the changes of interface impedance and lithium ion diffusion coefficient turned out that the interface impedance and lithium ion diffusion coefficient increased when the cut-off voltage passed the voltage platforms and decreased when the cut-off voltage was between voltage platforms. Finally, three-electrode system was first adopted to test the activation energy of the system, the results indicated that the activation energy of the three-electrode system (22.385 KJ /mol) was much smaller than that of two-electrode system (40.064 KJ /mol).

Keywords: cut-off voltage, de/intercalation kinetics, solid electrolyte interphase film, structural transformation

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Authors: Concetta Busacca, Leone Frusteri, Orazio Di Blasi, Alessandra Di Blasi

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The large-scale extension of renewable energy led, recently, to the development of efficient and low-cost electrochemical energy storage (EES) systems such as batteries. Although lithium-ion battery (LIB) technology is relatively mature, several issues regarding safety, cyclability, and high costs must be overcome. Thanks to the availability and low cost of sodium, sodium-ion batteries (NIB) have the potential to meet the energy storage needs of the large-scale grid, becoming a valid alternative to LIB in some energy sectors, such as the stationary one. However, important challenges such as low specific energy and short cyclic life due to the large radius of Na+ must be faced to introduce this technology into the market. As an important component of SIBs, cathode materials have a significant effect on the electrochemical performance of SIBs. Recently, sodium layer transition metal oxides, phosphates, and organic compounds have been investigated as cathode materials for SIBs. In particular, phosphate-based compounds such as NaₓMPO₄ (M= Fe, Co, Mn) have been extensively studied as cathodic polyanion materials due to their long cycle stability and appropriate operating voltage. Among these, an interesting cathode material is the NaMnPO₄ based one, thanks to the stability and the high redox potential of the Mn²⁺/Mn³⁺ ion pair (3÷4 V vs. Na+/Na), which allows reaching a high energy density. This work concerns with the synthesis of a composite material based on NaMnPO₄ and carbon nanofibers (NaMnPO₄-CNF) characterized by a mixed crystalline structure between the maricite and olivine phases and a self-standing manufacture obtained by electrospinning technique. The material was tested in a Na-ion battery coin cell in half cell configuration, and showed outstanding electrocatalytic performances with a specific discharge capacity of 125 mAhg⁻¹ and 101 mAhg⁻¹ at 0.3C and 0.6C, respectively, and a retention capacity of about 80% a 0.6C after 100 cycles.

Keywords: electrospinning, self standing materials, Na ion battery, cathode materials

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Authors: Carolina A. Santos, Alexandra B. Ribeiro

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Climate change and environmental degradation are threats to humanity. Europe has been addressing these problems, namely through the Green Deal, with the use of batteries in mobility and energy fields. However, these require the use of critical raw materials, like lithium, which demand is estimated to grow 60 times in the next 30 years. Thus, it is fundamental to promote a circular economy with lithium recovery from secondary resources. These are nowadays key topics, which will be even more relevant in the future, so a new way to approach them is needed and must be encouraged. Therefore, one of our main goals is to analyse two methods of lithium retrieval from secondary sources, bioleaching, and electrodialysis, and assess them regarding their sustainability. The latest results show good efficiency of removal with both methods, even though there are some matrix interferences. Hence, further investment and research are needed in order to make this process sustainable and our society more circular.

Keywords: lithium, sustainable mining, social license to operate, bioleaching, electrodialysis

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Authors: Anna Vanderbruggen, Kai Bachmann, Martin Rudolph, Rodrigo Serna

Abstract:

Recycling of lithium-ion batteries has attracted a lot of attention in recent years and focuses primarily on valuable metals such as cobalt, nickel, and lithium. Despite the growth in graphite consumption and the fact that it is classified as a critical raw material in the European Union, USA, and Australia, there is little work focusing on graphite recycling. Thus, graphite is usually considered waste in recycling treatments, where graphite particles are concentrated in the “black mass”, a fine fraction below 1mm, which also contains the foils and the active cathode particles such as LiCoO2 or LiNiMnCoO2. To characterize the material, various analytical methods are applied, including X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Atomic Absorption Spectrometry (AAS), and SEM-based automated mineralogy. The latter consists of the combination of a scanning electron microscopy (SEM) image analysis and energy-dispersive X-ray spectroscopy (EDS). It is a powerful and well-known method for primary material characterization; however, it has not yet been applied to secondary material such as black mass, which is a challenging material to analyze due to fine alloy particles and to the lack of an existing dedicated database. The aim of this research is to characterize the black mass depending on the metals recycling process in order to understand the liberation mechanisms of the active particles from the foils and their effect on the graphite particle surfaces and to understand their impact on the subsequent graphite flotation. Three industrial processes were taken into account: purely mechanical, pyrolysis-mechanical, and mechanical-hydrometallurgy. In summary, this article explores various and common challenges for graphite and secondary material characterization.

Keywords: automated mineralogy, characterization, graphite, lithium ion battery, recycling

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Authors: P. W. Chen, C. T. Chang, Y. Peng, J. Y. Wu, D. J. Jan, Md. Manirul Ali

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In the last decade, the nature of cathode spot splitting and the current per spot depended on an oblique magnetic field was investigated. This model for cathode current splitting is developed that we have investigated with relationship the magnetic pressures produced by kinetic pressure, self-magnetic pressure, and changed with an external magnetic field. We propose a theoretical model that has been established to an external magnetic field with components normal and tangential to the cathode surface influenced on magnetic pressure strength. We mainly focus on developed to understand the current per spot influenced with the tangential magnetic field strength and normal magnetic field strength.

Keywords: cathode spot, vacuum arc discharge, oblique magnetic field, tangential magnetic field

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Authors: Xin Chen, Xinyong Li, Qidong Zhao, Dong Wang

Abstract:

A new coupling system was constructed by combining photo-electrochemical cell with electro-fenton cell (PEC-EF). The electrode material in this system was derived from MnyFe₁₋yCo Prussian-Blue-Analog (PBA). Mn₀.₄Fe₀.₆Co₀.₆₇-N@C spin-coated on carbon paper behaved as the gas diffusion cathode and Mn₀.₄Fe₀.₆Co₀.₆₇O₂.₂ spin-coated on fluorine-tin oxide glass (FTO) as anode. The two separated cells could degrade Sulfamethoxazole (SMX) simultaneously and some coupling mechanisms by PEC and EF enhancing the degradation efficiency were investigated. The continuous on-site generation of H₂O₂ at cathode through an oxygen reduction reaction (ORR) was realized over rotating ring-disk electrode (RRDE). The electron transfer number (n) of the ORR with Mn₀.₄Fe₀.₆Co₀.₆₇-N@C was 2.5 in the selected potential and pH range. The photo-electrochemical properties of Mn₀.₄Fe₀.₆Co₀.₆₇O₂.₂ were systematically studied, which displayed good response towards visible light. The photoinduced electrons at anode can transfer to cathode for further use. Efficient photo-electro-catalytic performance was observed in degrading SMX. Almost 100% SMX removal was achieved in 120 min. This work not only provided a highly effective technique for antibiotic treatment but also revealed the synergic effect between PEC and EF.

Keywords: electro-fenton, photo-electrochemical, synergic effect, sulfamethoxazole

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Authors: Wenxin Mei, Jinhua Sun, Qingsong Wang

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The volume expansion of lithium-ion batteries is mainly induced by intercalation induced stress within the negative electrode, resulting in capacity degradation and even battery failure. Stress generation due to lithium intercalation into graphite particles is investigated based on an electrochemical-mechanical model in this work. The two-dimensional model presented is fully coupled, inclusive of the impacts of intercalation-induced stress, stress-induced intercalation, to evaluate the lithium concentration, stress generation, and displacement intra and inter-particle. The results show that the distribution of lithium concentration and stress exhibits an analogous pattern, which reflects the relation between lithium diffusion and stress. The results of inter-particle stress indicate that larger Von-Mises stress is displayed where the two particles are in contact with each other, and deformation at the edge of particles is also observed, predicting fracture. Additionally, the maximum inter-particle stress at the end of lithium intercalation is nearly ten times the intraparticle stress. And the maximum inter-particle displacement is increased by 24% compared to the single-particle. Finally, the effect of graphite particle arrangement on inter-particle stress is studied. It is found that inter-particle stress with tighter arrangement exhibits lower stress. This work can provide guidance for predicting the intra and inter-particle stress to take measures to avoid cracking of electrode material.

Keywords: electrochemical-mechanical model, graphite particle, lithium concentration, lithium ion battery, stress

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Authors: Allen Yushark Fosu, Ndue Kanari, James Vaughan, Alexandre Changes

Abstract:

Spodumene is a lithium-bearing mineral of great interest due to increasing demand of lithium in emerging electric and hybrid vehicles. The conventional method of processing the mineral for the metal requires inevitable thermal transformation of α-phase to the β-phase followed by roasting with suitable reagents to produce lithium salts for downstream processes. The selection of appropriate reagent for roasting is key for the success of the process and overall lithium recovery. Several researches have been conducted to identify good reagents for the process efficiency, leading to sulfation, alkaline, chlorination, fluorination, and carbonizing as the methods of lithium recovery from the mineral.HSC Chemistry is a thermochemical software that can be used to model metallurgical process feasibility and predict possible reaction products prior to experimental investigation. The software was employed to investigate and explain the various reagent characteristics as employed in literature during spodumene roasting up to 1200°C. The simulation indicated that all used reagents for sulfation and alkaline were feasible in the direction of lithium salt production. Chlorination was only feasible when Cl2 and CaCl2 were used as chlorination agents but not NaCl nor KCl. Depending on the kind of lithium salt formed during carbonizing and fluorination, the process was either spontaneous or nonspontaneous throughout the temperature range investigated. The HSC software was further used to simulate and predict some promising reagents which may be equally good for roasting the mineral for efficient lithium extraction but have not yet been considered by researchers.

Keywords: thermochemical modelling, HSC chemistry software, lithium, spodumene, roasting

Procedia PDF Downloads 130

Authors: Shari Ann S. Botin, Ruziel Larmae T. Gimpaya, Rembrant Rockwell Gamboa, Rinlee Butch M. Cervera

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In recent years, demand for the use of solid electrolytes as alternatives to liquid electrolytes has increased due to recurring battery safety and stability issues, in addition to an increase in energy density requirement which can be made possible by using solid electrolytes. Among the solid electrolyte systems, Li7La3Zr2O12 (LLZ) is one of the most promising as it exhibits good chemical stability against Li metal and has a relatively high ionic conductivity. In this study, pure and doped LLZ were synthesized via conventional solid state reaction. The precursor chemicals (such as LiOH, La2O3, Ga2O3 and ZrO2) were ground and then calcined at 900 °C, pressed into pellets and finally sintered at 1000 °C to 1200 °C. The microstructure and ionic conductivity of the obtained samples have been investigated. Results show that for pure LLZ, sintering at lower temperature (1000 °C) produced tetragonal LLZ while sintering at higher temperatures (≥ 1150 °C) produced cubic LLZ based from the XRD results. However, doping with Ga produces an easier formation of LLZ with cubic structure at lower sintering duration. On the other hand, the lithium conductivity of the samples was investigated using electrochemical impedance spectroscopy at room temperature. Among the obtained samples, Ga-doped LLZ sintered at 1150 °C obtained the highest ionic conductivity reaching to about 1x10⁻⁴ S/cm at room temperature. In addition, fabrication and initial investigation of an all-solid state Lithium Battery using the synthesized LLZ sample with the use of commercial cathode materials have been investigated.

Keywords: doped LLZ, lithium-ion battery, pure LLZ, solid electrolytes

Procedia PDF Downloads 231