Search results for: cathodes

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: E. K. Hardwick, L. B. Siwela, J. G. Falconer, M. E. Mathibela, W. Rolfe

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Lithium-ion battery (LiB) demand has increased with the advancement in technologies. The applications include electric vehicles, cell phones, laptops, and many more devices. Typical components of the cathodes include lithium, cobalt, nickel, and manganese. Recycling the spent LiBs is necessary to reduce the ecological footprint of their production and use and to have a secondary source of valuable metals. A hydrometallurgical method was investigated for the recovery of cobalt and nickel from LiB cathodes. The cathodes were leached using a chloride solution. Ion exchange was then used to recover the chloro-complexes of the metals. The aim of the research was to determine the efficiency of a chloride leach, as well as ion exchange operating capacities that can be achieved for LiB recycling, and to establish the optimal operating conditions (ideal pH, temperature, leachate and eluant, flowrate, and reagent concentrations) for the recovery of the cathode metals. It was found that the leaching of the cathodes could be hindered by the formation of refractory metal oxides of cathode components. A reducing agent was necessary to improve the leaching rate and efficiency. Leaching was achieved using various chloride-containing solutions. The chloro-complexes were absorbed by the ion exchange resin and eluted to produce concentrated cobalt, nickel, lithium, and manganese streams. Chromatographic separation of these elements was achieved. Further work is currently underway to determine the optimal operating conditions for the recovery by ion exchange.

Keywords: cobalt, ion exchange, leachate formation, lithium-ion batteries, manganese, nickel

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Authors: Ye Ling, Ruan Haihui

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Aqueous Zn-ion hybrid supercapacitors (AZHSCs) pertain to a new type of electrochemical energy storage device that has received considerable attention. They integrate the advantages of high-energy Zn-ion batteries and high-power supercapacitors to meet the demand for low-cost, long-term durability, and high safety. Nevertheless, the challenge caused by the finite ion adsorption/desorption capacity of carbon electrodes gravely limits their energy densities. This work describes titanium nitride@nitrogen-doped carbon nanocage (TiN@NCNC) composite cathodes for AZHSCs to achieve a greatly improved energy density, and the composites can be facile synthesized based on the calcination of a mixture of tetrabutyl titanate and zeolitic imidazolate framework-8 in argon atmosphere. The resulting composites are featured by the ultra-fine TiN particles dispersed uniformly on the NCNC surfaces, enhancing the Zn2+ storage capabilities. Using TiN@NCNC cathodes, the AZHSCs can operate stably with a high energy density of 154 Wh kg-¹ at a specific power of 270 W kg-¹ and achieve a remarkable capacity retention of 88.9% after 104 cycles at 5 A g-¹. At an extreme specific power of 8.7 kW kg-1, the AZHSCs can retain an energy density of 97.2 Wh kg-1. With these results, we stress that the TiN@NCNC cathodes render high-performance AZHSCs, and the facile one-pot method can easily be scaled up, which enables AZHSCs a new energy-storage component for managing intermitted renewable energy sources.

Keywords: Zn-ion hybrid supercapacitors, ion absorption/desorption reactions, titanium nitride, zeolitic imidazolate framework-8

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Authors: Pei Li, Chunyi Zhi

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Conversion-type lithium-ion batteries show great potential as high-energy-density, low-cost and sustainable alternatives to current transition-metal-based intercalation cells. Li-Cl₂/Li⁻I₂ conversion batteries, based on anionic redox reactions of Cl⁻/Cl⁰ or I⁻/I⁰, are highly attractive due to their superior voltage and capacity. However, a redox-active and reversible chlorine cathode has not been developed in organic electrolytes. And thermodynamic instability and shuttling issues of iodine cathodes have plagued the active iodine loading, capacity retention and cyclability. By reversible chemical bonds, we develop reversible chlorine redox reactions in organic electrolytes with interhalogen bonds between I and Cl for Li-I₂ batteries and develop a highly thermally stable I/I₃--bonded organic salts with iodine content up to 80% as cathode materials for the rechargeable Li-I₂ batteries. The demonstration of reversible chemical bonds enabled rechargeable Li-halogen batteries opens a new avenue to develop halogen compound cathodes.

Keywords: conversion-type, chlorine, halogen cathode, high energy density, iodine, interhalogen bond, lithium-ion batteries

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Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state Lithium metal batteries (SSLMBs) that contain polymer and ceramic solid electrolytes have received considerable attention as an alternative to substitute liquid electrolytes in lithium metal batteries (LMBs) for highly safe, excellent energy storage performance and stability under elevated temperature situations. Here, a novel fast Li-ion conducting material, LiTa₂PO₈ (LTPO), was synthesized and electrochemical performance of as-prepared powder and LTPO-incorporated composite solid polymer electrolyte (LTPO-CPE) membrane were investigated. The as-prepared LTPO powder was homogeneously dispersed in polymer matrices, and a hybrid solid electrolyte membrane was synthesized via a simple solution-casting method. The room temperature total ionic conductivity (σt) of the LTPO pellet and LTPO-CPE membrane were 0.14 and 0.57 mS cm-1, respectively. A coin battery with NCM811 cathode is cycled under 1C between 2.8 to 4.5 V at room temperature, achieving a Coulombic efficiency of 99.3% with capacity retention of 74.1% after 300 cycles. Similarly, the LFP cathode also delivered an excellent performance at 0.5C with an average Coulombic efficiency of 100% without virtually capacity loss (the maximum specific capacity is at 27th: 138 mAh g−1 and 500th: 131.3 mAh g−1). These results demonstrates the feasibility of a high Li-ion conductor LTPO as a filler, and the developed polymer/ceramic hybrid electrolyte has potential to be a high-performance electrolyte for high-voltage cathodes, which may provide a fresh platform for developing more advanced solid-state electrolytes.

Keywords: li-ion conductor, lithium-metal batteries, composite solid electrolytes, liTa2PO8, high-voltage cathode

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Authors: Jun-Lun Jiang, Bing-Sheng Yu

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Processing of flat-panel displays generates huge amount of wasted glass polishing powder, with high concentration of cerium and other elements such as lanthanum. According to the current statistics, consumption of polishing powder was approximately ten thousand tons per year in the world. Nevertheless, wasted polishing powder was usually buried or burned. If the lanthanum and cerium compounds in the wasted polishing powder could be recycled, that will greatly reduce enterprise cost and implement waste circulation. Cathodes of SOFCs are the principal consisting of rare earth elements such as lanthanum and cerium. In this study, we recycled the lanthanum and cerium from wasted glass polishing powder by acid-solution method, and synthesized La0.8Sr0.05Ca0.15Fe0.8Co0.8O3-δ and Gd0.1Ce0.9O2 (LSCCF-GDC) composite cathode material for SOFCs by glycinenitrate combustion (GNP) method. The results show that the recovery rates of lanthanum and cerium could accomplish up to 80% and 100% under 10N nitric acid solution within one hour. Comparing with the XRD data of the commercial LSCCF-GDC powder and the LSCCF-GDC product synthesized with chemicals, we find that the LSCCF-GDC was successfully synthesized with the recycled La & Ce solution by GNP method. The effect of adding ammonia to the product was also discussed, the grain size is finer and recovery rate of the product is higher without the addition of ammonia to the solution.

Keywords: glass polishing powder, acid solution, recycling, composite cathodes of solid oxide fuel, cell (SOFC), perovskite, glycine-nitrate combustion(GNP) method

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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: Olfat A. Fadali, Mohamed S. Mahmoud, Omnia H. Abdelraheem, Shimaa G. Mohammed

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The effect of electromagnetic field (EMF) on the removal of edible oil from oil-in-water emulsion by means of electrocoagulation was investigated in rectangular batch electrochemical cell with DC current. Iron (Fe) plate anodes and stainless steel cathodes were employed as electrodes. The effect of different magnetic field intensities (1.9, 3.9 and 5.2 tesla), three different positions of EMF (below, perpendicular and parallel to the electrocoagulation cell), as well as operating time; had been investigated. The application of electromagnetic field (5.2 tesla) raises percentage of oil removal from 72.4% for traditional electrocoagulation to 90.8% after 20 min.

Keywords: electrocoagulation, electromagnetic field, Oil-water emulsion, edible oil

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Authors: Zhen Qin, Yufei Peng, Jianbei Li, Jidong Long

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In order to study the activity of the coated aluminate barium-tungsten cathodes during activation, aging, poisoning and long-term use. Through a set of hot-cathode micro-area emission uniformity study device, we tested the micro-area emission performance of the cathode under different conditions. The change of activity of cathode micro-area was obtained. The influence of micro-area activity on the performance of the cathode was explained by the ageing model of barium-tungsten cathode. This helps to improve the design and process of the cathode and can point the way in finding the factors that affect life in the cathode operation.

Keywords: barium-tungsten cathode, ageing model, micro-area emission, emission uniformity

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Authors: Gabouze Nourredine, Saloua Merazga

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Due to their exceptional durability, low-cost, high-power density, and reliability, cathodes based on titanium dioxide, and more specifically spinel LTO (Li4Ti5O12), present an attractive alternative to conventional lithium cathode materials for multiple applications. The aim of this work is to synthesize and characterize the nanopowders of titanium dioxide (TiO₂) and lithium titanate (Li₄Ti5O₁₂) by the hydrothermal method and to use them as a cathode in a lithium-ion battery. The structural and morphological characterizations of the synthesized powders were performed by XRD, SEM, EDS, and FTIR-ATR. Nevertheless, the study of the electrochemical performances of the elaborated electrode materials was carried out by: cyclic voltametry (CV) and galvanostatic charge/discharge (CDG). The prepared electrode by the powder annealed at 800 °C has a good specific capacity of about 173 mAh/g and a good cyclic stability

Keywords: lithuim-ion, battery, LTO, tio2, capacity

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Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

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Authors: Boudjema Nouara, Mameri Nabil

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Bacteria have played an important role in water contamination as a consequence of organic pollution. In this study, an electrocoagulation process was adopted to remove fecal contamination and pathogenic bacteria from waste water. The effect of anode/cathodes materials as well as operating conditions for bacteria removal from water, such as current intensity and initial pH and temperature. The results indicated that the complete removal was achevied when using aluminium anode as anode at current intensity of 3A, initial pH of 7-8 and electrolysis time of 30 minutes. This process showed a bactericidal effect of 95 to 99% for the total and fecal coliforms and 99% to 100% for Eschercichia coli and fecal Streptococci. A decrease of 72% was recorded for sulphite-reducing Clostridia. Thus, this process has the potential to be one the options for treatment where high amount of bacteria in wastewater river.

Keywords: bacteria, el Harrach river, electrocoagulation, wastewater, treatment

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Authors: Po-Sun Ho, Chun-Wei Chen

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This work demonstrated a “sunlight-activated” graphene-heterostructure transparent electrode in which photogenerated charges from a light-absorbing material are transferred to graphene, resulting in the modulation of electrical properties of the graphene transparent electrode caused by a strong light–matter interaction at graphene-heterostructure interfaces. A photoactive graphene/TiOx-heterostructure transparent cathode was used to fabricate an n-graphene/p-Si Schottky junction solar cell, achieving a record-high power conversion efficiency (>10%). The photoactive graphene-heterostructure transparent electrode, which exhibits excellent tunable electrical properties under sunlight illumination, has great potential for use in the future development of graphene-based photovoltaics and optoelectronics.

Keywords: graphene, transparent electrode, graphene/Si Schottky junction, solar cells

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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: 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: Princess Stephanie P. Llanos, Rinlee Butch M. Cervera

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Lithium iron phosphate (LiFePO4) is a potential cathode material for lithium-ion batteries due to its promising characteristics. In this study, carbon-coated nanograined LiFePO4 is synthesized via wet chemistry method at a low temperature of 400 °C and investigated its performance as a cathode in Lithium battery. The X-ray diffraction pattern of the synthesized samples can be indexed to an orthorhombic LiFePO4 structure. Agglomerated particles that range from 200 nm to 300 nm are observed from scanning electron microscopy images. Transmission electron microscopy images confirm the crystalline structure of LiFePO4 and coating of amorphous carbon layer. Elemental mapping using Energy dispersive spectroscopy analysis revealed the homogeneous dispersion of Fe, P, O, and C elements. On the other hand, the electrochemical performances of the synthesized cathodes were investigated using cyclic voltammetry, galvanostatic charge/discharge tests with different C-rates, and cycling performances. Galvanostatic charge and discharge measurements revealed that the sample sintered at 400 °C for 3 hours with carbon coating demonstrated the highest capacity among the samples which reaches up to 160 mAhg⁻¹ at 0.1C rate.

Keywords: cathode, charge-discharge, electrochemical, lithium batteries

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Authors: Disha Gupta

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The aim of this research is to conduct X-ray and e-beam characterization techniques on lithium-ion battery materials for the improvement of battery performance. The key characterization techniques employed are the synchrotron X-ray Absorption Spectroscopy (XAS) combined with X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to obtain a more holistic approach to understanding material properties. This research effort provides additional battery characterization knowledge that promotes the development of new cathodes, anodes, electrolyte and separator materials for batteries, hence, leading to better and more efficient battery performance. Both ex-situ and in-situ synchrotron experiments were performed on LiFePO₄, one of the most common cathode material, from different commercial sources and their structural analysis, were conducted using Athena/Artemis software. This analysis technique was then further extended to study other cathode materials like LiMnxFe(₁₋ₓ)PO₄ and even some sulphate systems like Li₂Mn(SO₄)₂ and Li₂Co0.5Mn₀.₅ (SO₄)₂. XAS data were collected for Fe and P K-edge for LiFePO4, and Fe, Mn and P-K-edge for LiMnxFe(₁₋ₓ)PO₄ to conduct an exhaustive study of the structure. For the sulphate system, Li₂Mn(SO₄)₂, XAS data was collected at both Mn and S K-edge. Finite Difference Method for Near Edge Structure (FDMNES) simulations were also conducted for various iron, manganese and phosphate model compounds and compared with the experimental XANES data to understand mainly the pre-edge structural information of the absorbing atoms. The Fe K-edge XAS results showed a charge compensation occurring on the Fe atom for all the differently synthesized LiFePO₄ materials as well as the LiMnxFe(₁₋ₓ)PO₄ systems. However, the Mn K-edge showed a difference in results as the Mn concentration changed in the materials. For the sulphate-based system Li₂Mn(SO₄)₂, however, no change in the Mn K-edge was observed, even though electrochemical studies showed Mn redox reactions.

Keywords: li-ion batteries, electrochemistry, X-ray absorption spectroscopy, XRD

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Authors: Waqas Hassan Tanveer, Yoon Ho Lee, Taehyun Park, Wonjong Yu, Yaegeun Lee, Yusung Kim, Suk Won Cha

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Nickel-Gadolinium Doped Ceria (Ni-GDC) cermet anodic thin films were prepared on Scandia Stabilized Zirconia (ScSZ) electrolyte supports by radio frequency (RF) sputtering, with a range of different sputtering powers (50 – 200W) and background Ar gas pressures (30 – 90mTorr). The effects of varying sputtering power and pressure on the properties of Ni-GDC films were studied using Focused Ion Beam (FIB), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Energy Dispersive X-ray (EDX), and Atomic Force Microscopy (AFM) techniques. The Ni content was found to be always higher than the Ce content, at all sputtering conditions. This increased Ni content was attributed to significantly higher energy transfer efficiency of Ni ions as compared to Ce ions with Ar background sputtering gas. The solid oxide fuel cell configuration was completed by using lanthanum strontium manganite (LSM/YSZ) cathodes on the other side of ScSZ supports. Performance comparison of cells was done by Voltage-Current-Power (VIP) curves, while the resistances of various cell components were observed by nyquist plots. Initial results showed that anode films made by higher powered RF sputtering performed better than lower powered ones for a specific Ar pressure. Interestingly, however, anodes made at highest power and pressure, were not the ones that showed the maximum power output at an intermediate solid oxide fuel cell temperature of 800°C. Finally, an optimal sputtering condition was reported for high performance Ni-GDC anodes.

Keywords: intermediate temperature solid oxide fuel cells, nickel-cermet anodic thin films, nyquist plots, radio frequency sputtering

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Authors: Azri Yamina Mounia, Zitouni Dalila, Aziza Majda, Tou Insaf, Sadi Meriem

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To confront the fossil fuel crisis and the consequences of global warning, many efforts were devoted to develop alternative electricity generation and attracted numerous researchers, especially in the microbial fuel cell field, because it allows generating electric energy and degrading multiple organics compounds at the same time. However, one of the main constraints on power generation is the slow rate of oxygen reduction at the cathode electrode. This paper describes the potential of algal biomass (Chlorella vulgaris) as photosynthetic cathodes, eliminating the need for a mechanical air supply and the use of often expensive noble metal cathode catalysts, thus improving the sustainability and cost-effectiveness of the MFC system. During polarizations, MFC power density using algal biomass was 0.4mW/m², whereas the MFC with mechanic aeration showed a value of 0.2mW/m². Chlorella vulgaris was chosen due to its fastest growing. C. vulgaris grown in BG11 medium in sterilized Erlenmeyer flask. C. vulgaris was used as a bio‐cathode. Anaerobic activated sludge from the plant of Beni‐Messous WWTP(Algiers) was used in an anodic compartment. A dual‐chamber reactor MFC was used as a reactor. The reactor has been fabricated in the laboratory using plastic jars. The cylindrical and rectangular jars were used as the anode and cathode chambers, respectively. The volume of anode and cathode chambers was 0.8 and 2L, respectively. The two chambers were connected with a proton exchange membrane (PEM). The plain graphite plates (5 x 2cm) were used as electrodes for both anode and cathode. The cyclic voltammetry analysis of oxygen reduction revealed that the cathode potential was proportional to the amount of oxygen available in the cathode surface electrode. In the case of algal aeration, the peak reduction value of -2.18A/m² was two times higher than in mechanical aeration -1.85A/m². The electricity production reached 70 mA/m² and was stimulated immediately by the oxygen produced by algae up to the value of 20 mg/L.

Keywords: Chlorella vulgaris, cyclic voltammetry, microbial fuel cell, oxygen reduction

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Authors: C. D’Urso, L. Frusteri, M. Samperi, G. Leonardi

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Solid metal halides are used as active cathode ingredients in the case of Na-NiCl2 batteries that require a fused secondary electrolyte, sodium tetrachloraluminate (NaAlCl4), to facilitate the movement of the Na+ ion into the cathode. The sodium-nickel chloride (Na - NiCl2) battery has been extensively investigated as a promising system for large-scale energy storage applications. The growth of Ni and NaCl particles in the cathodes is one of the most important factors that degrade the performance of the Na-NiCl2 battery. The larger the particles of active ingredients contained in the cathode, the smaller the active surface available for the electrochemical reaction. Therefore, the growth of Ni and NaCl particles can lead to an increase in cell polarization resulting from the reduced active area. A higher current density, a higher state of charge (SOC) at the end of the charge (EOC) and a lower Ni / NaCl ratio are the main parameters that result in the rapid growth of Ni particles. In light of these problems, cathode and chemistry Nano-materials with recognized and well-documented electrochemical functions have been studied and manufactured to simultaneously improve battery performance and develop less expensive and more performing, sustainable and environmentally friendly materials. Starting from the well-known cathodic material (Na-NiCl2), the new electrolytic materials have been prepared on the replacement of nickel with iron (10-90%substitution of Nichel with Iron), to obtain a new material with potential advantages compared to current battery technologies; for example,, (1) lower cost of cathode material compared to state of the art as well as (2) choices of cheaper materials (stainless steels could be used for cell components, including cathode current collectors and cell housings). The study on the particle size of the cathode and the physicochemical characterization of the cathode was carried out in the test cell using, where possible, the GITT method (galvanostatic technique of intermittent titration). Furthermore, the impact of temperature on the different cathode compositions of the positive electrode was studied. Especially the optimum operating temperature is an important parameter of the active material.

Keywords: critical raw materials, energy storage, sodium metal halide, battery

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Authors: O. Ojeda Mena, Y. Cressault, P. Teulet, J. P. Gonnet, D. F. N. Santos, MD. Cunha, M. S. Benilov

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The assumption of plasma in local thermal equilibrium (LTE) is commonly used to perform electric arc simulations for industrial applications. This assumption allows to model the arc using a set of magneto-hydromagnetic equations that can be solved with a computational fluid dynamic code. However, the LTE description is only valid in the arc column, whereas in the regions close to the electrodes the plasma deviates from the LTE state. The importance of these near-electrode regions is non-trivial since they define the energy and current transfer between the arc and the electrodes. Therefore, any accurate modelling of the arc must include a good description of the arc-electrode phenomena. Due to the modelling complexity and computational cost of solving the near-electrode layers, a simplified description of the arc-electrode interaction was developed in a previous work to study a steady high-pressure arc discharge, where the near-electrode regions are introduced at the interface between arc and electrode as boundary conditions. The present work proposes a similar approach to simulate the arc ignition in a free-burning arc configuration following an LTE description of the plasma. To obtain the transient evolution of the arc characteristics, appropriate boundary conditions for both the near-cathode and the near-anode regions are used based on recent publications. The arc-cathode interaction is modeled using a non-linear surface heating approach considering the secondary electron emission. On the other hand, the interaction between the arc and the anode is taken into account by means of the heating voltage approach. From the numerical modelling, three main stages can be identified during the arc ignition. Initially, a glow discharge is observed, where the cold non-thermionic cathode is uniformly heated at its surface and the near-cathode voltage drop is in the order of a few hundred volts. Next, a spot with high temperature is formed at the cathode tip followed by a sudden decrease of the near-cathode voltage drop, marking the glow-to-arc discharge transition. During this stage, the LTE plasma also presents an important increase of the temperature in the region adjacent to the hot spot. Finally, the near-cathode voltage drop stabilizes at a few volts and both the electrode and plasma temperatures reach the steady solution. The results after some seconds are similar to those presented for thermionic cathodes.

Keywords: arc-electrode interaction, thermal plasmas, electric arc simulation, cold electrodes

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Authors: C. G. Mendez-Garcia, E. T. Romero-Guzman, H. Hernandez-Mendoza, C. Solis, E. Chavez-Lomeli, E. Chamizo, R. Garcia-Tenorio

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Plutonium is present in different concentrations in the environment and biological samples related to nuclear weapons testing, nuclear waste recycling and accidental discharges of nuclear plants. This radioisotope is considered the most radiotoxic substance, particularly when it enters the human body through inhalation of powders insoluble or aerosols. This is the main reason of the determination of the concentration of this radioisotope in the atmosphere. Besides that, the isotopic ratio of ²⁴⁰Pu/²³⁹Pu provides information about the origin of the source. PM₂.₅ sampling was carried out in the Metropolitan Zone of the Valley of Mexico (MZVM) from February 18th to March 17th in 2015 on quartz filter. There have been significant developments recently due to the establishment of new methods for sample preparation and accurate measurement to detect ultra trace levels as the plutonium is found in the environment. The accelerator mass spectrometry (AMS) is a technique that allows measuring levels of detection around of femtograms (10-15 g). The AMS determinations include the chemical isolation of Pu. The Pu separation involved an acidic digestion and a radiochemical purification using an anion exchange resin. Finally, the source is prepared, when Pu is pressed in the corresponding cathodes. According to the author's knowledge on these aerosols showed variations on the ²³⁵U/²³⁸U ratio of the natural value, suggesting that could be an anthropogenic source altering it. The determination of the concentration of the isotopes of Pu can be a useful tool in order the clarify this presence in the atmosphere. The first results showed a mean value of activity concentration of ²³⁹Pu of 280 nBq m⁻³ thus the ²⁴⁰Pu/²³⁹Pu was 0.025 corresponding to the weapon production source; these results corroborate that there is an anthropogenic influence that is increasing the concentration of radioactive material in PM₂.₅. According to the author's knowledge in Total Suspended Particles (TSP) have been reported activity concentrations of ²³⁹⁺²⁴⁰Pu around few tens of nBq m⁻³ and 0.17 of ²⁴⁰Pu/²³⁹Pu ratios. The preliminary results in MZVM show high activity concentrations of isotopes of Pu (40 and 700 nBq m⁻³) and low ²⁴⁰Pu/²³⁹Pu ratio than reported. These results are in the order of the activity concentrations of Pu in weapons-grade of high purity.

Keywords: aerosols, fallout, mass spectrometry, radiochemistry, tracer, ²⁴⁰Pu/²³⁹Pu ratio

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Authors: Shasha Lv, Zhengcao Li

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Due to the CMOS compatibility, silicon-based field emission (FE) devices as potential electron sources have attracted much attention. The geometrical arrangement and dimensional features of aligned silicon nanowires (SiNWs) have a determining influence on the FE properties. We discuss a multistep template replication process of Ag-assisted chemical etching combined with polystyrene (PS) spheres to fabricate highly periodic and well-aligned silicon nanowires, then their diameter, aspect ratio and density were further controlled via dry oxidation and post chemical treatment. The FE properties related to proximity and aspect ratio were systematically studied. A remarkable improvement of FE propertiy was observed with the average nanowires tip interspace increasing from 80 to 820 nm. On the basis of adjusting SiNWs dimensions and morphology, addition of a secondary material whose properties complement the SiNWs could yield a combined characteristic. Three different nanoheterostructures were fabricated to control the FE performance, they are: NiSi/Si core-shell structures, ZnO/Si nanotrees, and Graphene/SiNWs. We successfully fabricated the high-quality NiSi/Si heterostructured nanowires with excellent conformality. First, nickle nanoparticles were deposited onto SiNWs, then rapid thermal annealing process were utilized to form NiSi shell. In addition, we demonstrate a new and simple method for creating 3D nanotree-like ZnO/Si nanocomposites with a spatially branched hierarchical structure. Compared with the as-prepared SiNRs and ZnO NWs, the high-density ZnO NWs on SiNRs have exhibited predominant FE characteristics, and the FE enhancement factors were attributed to band bending effect and geometrical morphology. The FE efficiency from flat sheet structure of graphene is low. We discussed an effective approach towards full control over the diameter of uniform SiNWs to adjust the protrusions of large-scale graphene sheet deposited on SiNWs. The FE performance regarding the uniformity and dimensional control of graphene protrusions supported on SiNWs was systematically clarified. Therefore, the hybrid SiNWs/graphene structures with protrusions provide a promising class of field emission cathodes.

Keywords: field emission, silicon nanowires, heterostructures, controllable synthesis

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Authors: Saddam Husain Dhobi, Bikrant Karki

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The main objective of this paper is save money, balance ecosystem of the terrestrial organism, control global warming, and enhancing the storage capacity of the battery with requiring weight and thinness by using Cyanobacteria in the battery. To fulfill this purpose of paper we can use different methods: Analysis, Biological, Chemistry, theoretical and Physics with some engineering design. Using this different method, we can produce the special type of battery that has the long life, high storage capacity, and clean environment, save money so on and by using the byproduct of Cyanobacteria i.e. glucose. Cyanobacteria are a special type of bacteria that produces different types of extracellular glucoses and oxygen with the help of little sunlight, water, and carbon dioxide and can survive in freshwater, marine and in the land as well. In this process, O₂ is more in the comparison to plant due to rapid growth rate of Cyanobacteria. The required materials are easily available in this process to produce glucose with the help of Cyanobacteria. Since CO₂, is greenhouse gas that causes the global warming? We can utilize this gas and save our ecological balance and the byproduct (glucose) C₆H₁₂O₆ can be utilized for raw material for the battery where as O₂ escape is utilized by living organism. The glucose produce by Cyanobateria goes on Krebs's Cycle or Citric Acid Cycle, in which glucose is complete, oxidizes and all the available energy from glucose molecule has been release in the form of electron and proton as energy. If we use a suitable anodes and cathodes, we can capture these electrons and protons to produce require electricity current with the help of byproduct of Cyanobacteria. According to "Virginia Tech Bio-battery" and "Sony" 13 enzymes and the air is used to produce nearly 24 electrons from a single glucose unit. In this output power of 0.8 mW/cm, current density of 6 mA/cm, and energy storage density of 596 Ah/kg. This last figure is impressive, at roughly 10 times the energy density of the lithium-ion batteries in your mobile devices. When we use Cyanobacteria in battery, we are able to reduce Carbon dioxide, Stop global warming, and enhancing the storage capacity of battery more than 10 times that of lithium battery, saving money, balancing ecology. In this way, we can produce energy from the Cyanobacteria and use it in battery for different benefits. In addition, due to the mass, size and easy cultivation, they are better to maintain the size of battery. Hence, we can use Cyanobacteria for the battery having suitable size, enhancing the storing capacity of battery, helping the environment, portability and so on.

Keywords: anode, byproduct, cathode, cyanobacteri, glucose, storage capacity

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Authors: A. Saravanan, B. R. Huang, C. J. Yeh, K. C. Leou, I. N. Lin

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A new class of ultra-nano diamond-graphite nano-hybrid (DGH) composite materials containing nano-sized diamond needles was developed at low temperature process. Such kind of diamond- graphite nano-hybrid composite nanowires exhibit high electrical conductivity and excellent electron field emission (EFE) properties. Few earlier reports mention that addition of N2 gas to the growth plasma requires high growth temperature (800°C) to trigger the dopants to generate the conductivity in the films. High growth temperature is not familiar with the Si-based device fabrications. We have used a novel process such as bias-enhanced-grown (beg) MPECVD process to grow diamond films at low substrate temperature (450°C). We observed that the beg-N/UNCD films thus obtained possess high conductivity of σ=987 S/cm, ever reported for diamond films with excellent Electron field emission (EFE) properties. TEM investigation indicated that these films contain needle-like diamond grains about 5 nm in diameter and hundreds of nanometers in length. Each of the grains was encased in graphitic layers about tens of nano-meters in thickness. These materials properties suitable for more specific applications, such as high conductivity for electron field emitters, high robustness for microplasma cathodes and high electrochemical activity for electro-chemical sensing. Subsequently, other hand, the highly conducting DGH films were coated on vertically aligned ZnO nanorods, there is no prior nucleation or seeding process needed due to the use of BEG method. Such a composite structure provides significant enhancement in the field emission characteristics of the cold cathode was observed with ultralow turn on voltage 1.78 V/μm with high EFE current density of 3.68 mA/ cm2 (at 4.06V/μm) due to decoration of DGH material on ZnO nanorods. The DGH/ZNRs based device get stable emission for longer duration of 562min than bare ZNRs (104min) without any current degradation because the diamond coating protects the ZNRs from ion bombardment when they are used as the cathode for microplasma devices. The potential application of these materials is demonstrated by the plasma illumination measurements that ignited the plasma at the minimum voltage by 290 V. The photoresponse (Iphoto/Idark) behavior of the DGH/ZNRs based photodetectors exhibits a much higher photoresponse (1202) than bare ZNRs (229). During the process the electron transport is easy from ZNRs to DGH through graphitic layers, the EFE properties of these materials comparable to other primarily used field emitters like carbon nanotubes, graphene. The DGH/ZNRs composite also providing a possibility of their use in flat panel, microplasma and vacuum microelectronic devices.

Keywords: bias-enhanced nucleation and growth, ZnO nanorods, electrical conductivity, electron field emission, photo-detectors

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Authors: A. Volperts, G. Dobele, A. Zhurinsh, I. Kruusenberg, A. Plavniece, J. Locs

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Nowadays energy consumption constantly increases and development of effective and cheap electrochemical sources of power, such as fuel cells and electrochemical capacitors, is topical. Due to their high specific power, charge and discharge rates, working lifetime supercapacitor based energy accumulation systems are more and more extensively being used in mobile and stationary devices. Lignocellulosic materials are widely used as precursors and account for around 45% of the total raw materials used for the manufacture of activated carbon which is the most suitable material for supercapacitors. First part of our research is devoted to study of influence of main stages of wood thermochemical activation parameters on activated carbons porous structure formation. It was found that the main factors governing the properties of carbon materials are specific surface area, volume and pore size distribution, particles dispersity, ash content and oxygen containing groups content. Influence of activated carbons attributes on capacitance and working properties of supercapacitor are demonstrated. The correlation between activated carbons porous structure indices and electrochemical specifications of supercapacitors with electrodes made from these materials has been determined. It is shown that if synthesized activated carbons are used in supercapacitors then high specific capacitances can be reached – more than 380 F/g in 4.9M sulfuric acid based electrolytes and more than 170 F/g in 1 M tetraethylammonium tetrafluoroborate in acetonitrile electrolyte. Power specifications and minimal price of H₂-O₂ fuel cells are limited by the expensive platinum-based catalysts. The main direction in development of non-platinum catalysts for the oxygen reduction is the study of cheap porous carbonaceous materials which can be obtained by the pyrolysis of polymers including renewable biomass. It is known that nitrogen atoms in carbon materials to a high degree determine properties of the doped activated carbons, such as high electrochemical stability, hardness, electric resistance, etc. The lack of sufficient knowledge on the doping of the carbon materials calls for the ongoing researches of properties and structure of modified carbon matrix. In the second part of this study, highly porous activated carbons were synthesized using alkali thermochemical activation from wood, cellulose and cellulose production residues – craft lignin and sewage sludge. Activated carbon samples were doped with dicyandiamide and melamine for the application as fuel cell cathodes. Conditions of nitrogen introduction (solvent, treatment temperature) and its content in the carbonaceous material, as well as porous structure characteristics, such as specific surface and pore size distribution, were studied. It was found that efficiency of doping reaction depends on the elemental oxygen content in the activated carbon. Relationships between nitrogen content, porous structure characteristics and electrodes electrochemical properties are demonstrated.

Keywords: activated carbons, low-temperature fuel cells, nitrogen doping, porous structure, supercapacitors

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Authors: Cyril O. Ehi-Eromosele, Ajayi Kayode

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The Li-rich layered metal oxides (LLO) are the most promising candidates for promising electrodes of high energy Li-ion battery (LIB). In literature, these electrode system has either been designed as a hetero-structure of the primary components (composite) or as a core-shell structure with improved electrochemistry reported for both configurations when compared with its primary components. With the on-going efforts to improve on the electrochemical performance of the LIB, it is important to investigate comparatively the structural and electrochemical characteristics of the core-shell like and ‘composite’ forms of these materials with the same compositions and synthesis conditions which could influence future engineering of these materials. Therefore, this study concerns the structural and electrochemical properties of the ‘composite’ and core-shell like LLO cathode materials with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₂O₂ (LiNi₀.₅Mn₀.₃Co₀.₂O₂ as core and Li₂MnO₃ as the shell). The results show that the core-shell sample (–CS) gave better electrochemical performance than the ‘composite’ sample (–C). Both samples gave the same initial charge capacity of ~300 mAh/g when cycled at 10 mA/g and comparable charge capacity (246 mAh/g for the –CS sample and 240 mAh/g for the –C sample) when cycled at 200 mA/g. However, the –CS sample gave a higher initial discharge capacity at both current densities. The discharge capacity of the –CS sample was 232 mAh/g and 164 mAh/g while the –C sample is 208 mAh/g and 143 mAh/g at the current densities of 10 mA/g and 200 mA/g, respectively. Electrochemical impedance spectroscopy (EIS) results show that the –CS sample generally exhibited a smaller resistance than the –C sample both for the uncycled and after 50th cycle. Detailed structural analysis is on-going, but preliminary results show that the –CS sample had bigger unit cell volume and a higher degree of cation mixing. The thermal stability of the –CS sample was higher than the –C sample. XPS investigation also showed that the pristine –C sample gave a more reactive surface (showing formation of carbonate species to a greater degree) which could result in the greater resistance seen in the EIS result. To reinforce the results obtained for the 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₃O₂ composition, the same investigations were extended to another ‘composite’ and core-shell like LLO cathode materials also with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂. In this case, the aim was to determine the electrochemical performance of the material using a low Ni content (LiNi₀.₃Mn₀.₃Co₀.₃O₂) as the core to clarify the contributions of the core-shell configuration to the electrochemical performance of these materials. Ni-rich layered oxides show active catalytic surface leading to electrolyte oxidation resulting in poor thermal stability and cycle life. Here, the core-shell sample also gave better electrochemical performance than the ‘composite’ sample with 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂ composition. Furthermore, superior electrochemical performance was also recorded for the core-shell like spinel modified LLO (0.5Li₂MnO₃-0.45LiNi₀.₅Mn₀.₃Co₀.₂O₂-0.05LiNi₀.₅Mn₁.₅O₄) when compared to the composite system. These results show that the core-shell configuration can generally be used to improve the structural and electrochemical properties of the LLO and spinel modified LLO materials.

Keywords: lithium-ion battery, lithium rich oxide cathode, core-shell structure, composite structure

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Authors: Yohann R. J. Thomas, Sébastien Solan

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Conventional battery technology includes the assembly of electrode/separator/electrode by standard techniques such as stacking or winding, depending on the format size. In that type of batteries, coating or pasting techniques are only used for the electrode process. The processes are suited for large scale production of batteries and perfectly adapted to plenty of application requirements. Nevertheless, as the demand for both easier and cost-efficient production modes, flexible, custom-shaped and efficient small sized batteries is rising. Thin-film, printable batteries are one of the key areas for printed electronics. In the frame of European BASMATI project, we are investigating the feasibility of a new design of lithium-ion battery: interdigitated planar core design. Polymer substrate is used to produce bendable and flexible rechargeable accumulators. Direct fully printed batteries lead to interconnect the accumulator with other electronic functions for example organic solar cells (harvesting function), printed sensors (autonomous sensors) or RFID (communication function) on a common substrate to produce fully integrated, thin and flexible new devices. To fulfill those specifications, a high resolution printing process have been selected: Aerosol jet printing. In order to fit with this process parameters, we worked on nanomaterials formulation for current collectors and electrodes. In addition, an advanced printed polymer-electrolyte is developed to be implemented directly in the printing process in order to avoid the liquid electrolyte filling step and to improve safety and flexibility. Results: Three different current collectors has been studied and printed successfully. An ink of commercial copper nanoparticles has been formulated and printed, then a flash sintering was applied to the interdigitated design. A gold ink was also printed, the resulting material was partially self-sintered and did not require any high temperature post treatment. Finally, carbon nanotubes were also printed with a high resolution and well defined patterns. Different electrode materials were formulated and printed according to the interdigitated design. For cathodes, NMC and LFP were efficaciously printed. For anodes, LTO and graphite have shown to be good candidates for the fully printed battery. The electrochemical performances of those materials have been evaluated in a standard coin cell with lithium-metal counter electrode and the results are similar with those of a traditional ink formulation and process. A jellified plastic crystal solid state electrolyte has been developed and showed comparable performances to classical liquid carbonate electrolytes with two different materials. In our future developments, focus will be put on several tasks. In a first place, we will synthesize and formulate new specific nano-materials based on metal-oxyde. Then a fully printed device will be produced and its electrochemical performance will be evaluated.

Keywords: high resolution digital printing, lithium-ion battery, nanomaterials, solid-state electrolytes

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Authors: Mina Naeini, Thomas A. Adams II

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Solid Oxide Fuel Cells (SOFCs) feature high electrical efficiency and generate substantial amounts of waste heat that make them suitable for integrated community energy systems (ICEs). By harvesting and distributing the waste heat through hot water pipelines, SOFCs can meet thermal demand of the communities. Therefore, they can replace traditional gas boilers and reduce greenhouse gas (GHG) emissions. Despite these advantages of SOFCs over competing power generation units, this technology has not been successfully commercialized in large-scale to replace traditional generators in ICEs. One reason is that SOFC performance deteriorates over long-term operation, which makes it difficult to find the proper sizing of the cells for a particular ICE system. In order to find the optimal sizing and operating conditions of SOFCs in a community, a proper knowledge of degradation mechanisms and effects of operating conditions on SOFCs long-time performance is required. The simplified SOFC models that exist in the current literature usually do not provide realistic results since they usually underestimate rate of performance drop by making too many assumptions or generalizations. In addition, some of these models have been obtained from experimental data by curve-fitting methods. Although these models are valid for the range of operating conditions in which experiments were conducted, they cannot be generalized to other conditions and so have limited use for most ICEs. In the present study, a general, detailed degradation-based model is proposed that predicts the performance of conventional SOFCs over a long period of time at different operating conditions. Conventional SOFCs are composed of Yttria Stabilized Zirconia (YSZ) as electrolyte, Ni-cermet anodes, and LaSr₁₋ₓMnₓO₃ (LSM) cathodes. The following degradation processes are considered in this model: oxidation and coarsening of nickel particles in the Ni-cermet anodes, changes in the pore radius in anode, electrolyte, and anode electrical conductivity degradation, and sulfur poisoning of the anode compartment. This model helps decision makers discover the optimal sizing and operation of the cells for a stable, efficient performance with the fewest assumptions. It is suitable for a wide variety of applications. Sulfur contamination of the anode compartment is an important cause of performance drop in cells supplied with hydrocarbon-based fuel sources. H₂S, which is often added to hydrocarbon fuels as an odorant, can diminish catalytic behavior of Ni-based anodes by lowering their electrochemical activity and hydrocarbon conversion properties. Therefore, the existing models in the literature for H₂-supplied SOFCs cannot be applied to hydrocarbon-fueled SOFCs as they only account for the electrochemical activity reduction. A regression model is developed in the current work for sulfur contamination of the SOFCs fed with hydrocarbon fuel sources. The model is developed as a function of current density and H₂S concentration in the fuel. To the best of authors' knowledge, it is the first model that accounts for impact of current density on sulfur poisoning of cells supplied with hydrocarbon-based fuels. Proposed model has wide validity over a range of parameters and is consistent across multiple studies by different independent groups. Simulations using the degradation-based model illustrated that SOFCs voltage drops significantly in the first 1500 hours of operation. After that, cells exhibit a slower degradation rate. The present analysis allowed us to discover the reason for various degradation rate values reported in literature for conventional SOFCs. In fact, the reason why literature reports very different degradation rates, is that literature is inconsistent in definition of how degradation rate is calculated. In the literature, the degradation rate has been calculated as the slope of voltage versus time plot with the unit of voltage drop percentage per 1000 hours operation. Due to the nonlinear profile of voltage over time, degradation rate magnitude depends on the magnitude of time steps selected to calculate the curve's slope. To avoid this issue, instantaneous rate of performance drop is used in the present work. According to a sensitivity analysis, the current density has the highest impact on degradation rate compared to other operating factors, while temperature and hydrogen partial pressure affect SOFCs performance less. The findings demonstrated that a cell running at lower current density performs better in long-term in terms of total average energy delivered per year, even though initially it generates less power than if it had a higher current density. This is because of the dominant and devastating impact of large current densities on the long-term performance of SOFCs, as explained by the model.

Keywords: degradation rate, long-term performance, optimal operation, solid oxide fuel cells, SOFCs

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