An effective three-dimensional ordered mesoporous CuCo2O4 as electrocatalyst for Li-O2 batteries

Three-dimensional ordered mesoporous (3DOM) CuCo₂O₄ materials have been synthesized via a hard template and used as bifunctional electrocatalysts for rechargeable Li-O₂ batteries. The characterization of the catalyst by X-ray diffractometry and transmission electron microscopy confirms the formation of a single-phase, 3-dimensional, ordered mesoporous CuCo₂O₄ structure. The as-prepared CuCo₂O₄ nanoparticles possess a high specific surface area of 97.1 m² g^{- 1} and a spinel crystalline structure. Cyclic voltammetry demonstrates that mesoporous CuCo₂O₄ catalyst enhances the kinetics for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER). The Li-O₂ battery utilizing 3DOM CuCo₂O₄ shows a higher specific capacity of 7456 mAh g^{- 1} than that with pure Ketjen black (KB). Moreover, the CuCo₂O₄-based electrode enables much enhanced cyclability with a 610 mV smaller discharge-recharge voltage gap than that of the carbon-only cathode at a current rate of 100 mA g^{- 1}. Such excellent catalytic performance of CuCo₂O₄ could be associated with its larger surface area and 3D ordered mesoporous structure. The excellent electrochemical performances coupled with its facile and cost-effective way will render the 3D mesoporous CuCo₂O₄ nanostructures as attractive electrode materials for promising application in Li-O₂ batteries.

Synthèse de titanates de lithium nanostructurés par plasma inductif pour les batteries lithium-ion

Le marché des accumulateurs lithium-ion est en expansion. Cette croissance repose partiellement sur la multiplication des niches d’utilisation et l’amélioration constante de leurs performances. En raison de leur durabilité exceptionnelle, de leur faible coût, de leur haute densité de puissance et de leur fiabilité, les anodes basées sur les titanates de lithium, et plus particulièrement le spinelle Li4Ti5O12, présentent une alternative d’intérêt aux matériaux classiques d’anodes en carbone pour de multiples applications. Leur utilisation sous forme de nanomatériaux permet d’augmenter significativement la puissance disponible par unité de poids. Ces nanomatériaux ne sont typiquement pas contraints dans une direction particulière (nanofils, nanoplaquettes), car ces formes impliquent une tension de surface plus importante et requièrent donc généralement un mécanisme de synthèse dédié. Or, ces nanostructures permettent des réductions supplémentaires dans les dimensions caractéristiques de diffusion et de conduction, maximisant ainsi la puissance disponible, tout en affectant les propriétés habituellement intrinsèques des matériaux. Par ailleurs, les réacteurs continus reposant sur la technologie du plasma thermique inductif constituent une voie de synthèse démontrée afin de générer des volumes importants de matériaux nanostructurés. Il s’avère donc pertinent d’évaluer leur potentiel dans la production de titanates de lithium nanostructurés. La pureté des titanates de lithium est difficile à jauger. Les techniques de quantification habituelles reposent sur la fluorescence ou la diffraction en rayons X, auxquelles le lithium élémentaire se prête peu ou pas. Afin de quantifier les nombreuses phases (Li4Ti5O12, Li2Ti3O7, Li2TiO3, TiO2, Li2CO3) identifiées dans les échantillons produits par plasma, un raffinement de Rietveld fut développé et validé. La présence de γ-Li2TiO3 fut identifiée, et la calorimétrie en balayage différentiel fut explorée comme outil permettant d’identifier et de quantifier la présence de β-Li2TiO3. Différentes proportions entre les phases produites et différents types de morphologies furent observés en fonction des conditions d’opération du plasma. Ainsi, des conditions de trempe réductrice et d’ensemencement en Li4Ti5O12 nanométrique semblent favoriser l’émergence de nanomorphologies en nanofils (associés à Li4Ti5O12) et en nanoplaquette (associées à Li2TiO3). De plus, l’ensemencement et les recuits augmentèrent significativement le rendement en la phase spinelle Li4Ti5O12 recherchée. Les recuits sur les poudres synthétisées par plasma indiquèrent que la décomposition du Li2Ti3O7 produit du Li4Ti5O12, du Li2TiO3 et du TiO2 (rutile). Afin d’approfondir l’investigation de ces réactions de décomposition, les paramètres cristallins du Li2Ti3O7 et du γ-Li2TiO3 furent définis à haute température. Des mesures continues en diffraction en rayon X à haute température furent réalisées lors de recuits de poudres synthétisées par plasma, ainsi que sur des mélanges de TiO2 anatase et de Li2CO3. Celles-ci indiquent la production d’un intermédiaire Li2Ti3O7 à partir de l’anatase et du carbonate, sa décomposition en Li4Ti5O12 et TiO2 (rutile) sur toute la plage de température étudiée, et en Li2TiO3 et TiO2 (rutile) à des températures inférieures à 700°C.

Vaness: DNS for nomadic users in vehicular networks

Vehicular networks, also known as VANETs, are an ad-hoc network formed by vehicles and road-side units. Nowadays they have been attracting big interest both from researchers as from the automotive industry. With the upcoming of automotive specific operating systems and self-driving cars, the use of applications on vehicles and the integration with common mobile devices is becoming a big part of VANETs. Although many advances have been made on this field, there is still a big discrepancy between the communication layer services provided by VANETs and the user level services, namely those accessible through mobile applications on other networks and technologies. Users and developers are accustomed to user-to-user or user-tobusiness communication without explicit concerns related with the available communication transport layer. Such is not possible in VANETs since people may use more than one vehicle. However, to send a message to a specific user in these networks, there is a need to know the ID of the vehicle where the user is, meaning that there is a lack of services that map each individual user to VANETs endpoint (vehicle identification). This dissertation work proposes VANESS, a naming service as a resource to support user-to-user communication within a heterogeneous scenario comprising typical ISP scenario and VANETs focused on mobile devices. The proposed system is able to map the user to an end point either locally (i.e. there is not internet connection at all), online (i.e. system is not in a vehicular network but has direct internet connection) and using a gateway (i.e. the system is in a vehicular network where some of the nodes have internet access and will act as a gateway). VANESS was fully implemented on android OS with results proving his viability, and partially on iOS showing its multiplatform capabilities.

Collection of waste batteries in Portugal and Brazil

Selected papers from the 3rd Edition of the International Conference on Wastes: Solutions, Treatments and Opportunities

Forwarding and security in vehicular networks

The growing research in vehicular network solutions provided the rise of interaction in these highly dynamic environments in the market. The developed architectures do not usually focus, however, in security aspects. Common security strategies designed for the Internet require IP. Since nodes' addresses in a vehicular network are too dynamic, such solutions would require cumbersome negotiations, which would make them unsuitable to these environments. The objective of this dissertation is to develop, and test a scalable, lightweight, layer 3 security protocol for vehicular networks, in which nodes of the network are able to set up long-term security associations with a Home Network, avoiding session renegotiations due to lack of connectivity and reduce the protocol stacking. This protocol allows to provide security independent of the nodes (vehicles) position, of its addressing and of the established path to access the Internet, allowing the mobility of vehicles and of its active sessions seamlessly without communication failures.

Mobility in vehicular networks with multiple access points to the infrastructure

Nowadays there is a huge evolution in the technological world and in the wireless networks. The electronic devices have more capabilities and resources over the years, which makes the users more and more demanding. The necessity of being connected to the global world leads to the arising of wireless access points in the cities to provide internet access to the people in order to keep the constant interaction with the world. Vehicular networks arise to support safety related applications and to improve the traffic flow in the roads; however, nowadays they are also used to provide entertainment to the users present in the vehicles. The best way to increase the utilization of the vehicular networks is to give to the users what they want: a constant connection to the internet. Despite of all the advances in the vehicular networks, there were several issues to be solved. The presence of dedicated infrastructure to vehicular networks is not wide yet, which leads to the need of using the available Wi-Fi hotspots and the cellular networks as access networks. In order to make all the management of the mobility process and to keep the user’s connection and session active, a mobility protocol is needed. Taking into account the huge number of access points present at the range of a vehicle for example in a city, it will be beneficial to take advantage of all available resources in order to improve all the vehicular network, either to the users and to the operators. The concept of multihoming allows to take advantage of all available resources with multiple simultaneous connections. This dissertation has as objectives the integration of a mobility protocol, the Network-Proxy Mobile IPv6 protocol, with a host-multihoming per packet solution in order to increase the performance of the network by using more resources simultaneously, the support of multi-hop communications, either in IPv6 or IPv4, the capability of providing internet access to the users of the network, and the integration of the developed protocol in the vehicular environment, with the WAVE, Wi-Fi and cellular technologies. The performed tests focused on the multihoming features implemented on this dissertation, and on the IPv4 network access for the normal users. The obtained results show that the multihoming addition to the mobility protocol improves the network performance and provides a better resource management. Also, the results show the correct operation of the developed protocol in a vehicular environment.

NETCODE: an XOR-based warning dissemination scheme for vehicular wireless networks

The next generation of vehicles will be equipped with automated Accident Warning Systems (AWSs) capable of warning neighbouring vehicles about hazards that might lead to accidents. The key enabling technology for these systems is the Vehicular Ad-hoc Networks (VANET) but the dynamics of such networks make the crucial timely delivery of warning messages challenging. While most previously attempted implementations have used broadcast-based data dissemination schemes, these do not cope well as data traffic load or network density increases. This problem of sending warning messages in a timely manner is addressed by employing a network coding technique in this thesis. The proposed NETwork COded DissEmination (NETCODE) is a VANET-based AWS responsible for generating and sending warnings to the vehicles on the road. NETCODE offers an XOR-based data dissemination scheme that sends multiple warning in a single transmission and therefore, reduces the total number of transmissions required to send the same number of warnings that broadcast schemes send. Hence, it reduces contention and collisions in the network improving the delivery time of the warnings. The first part of this research (Chapters 3 and 4) asserts that in order to build a warning system, it is needful to ascertain the system requirements, information to be exchanged, and protocols best suited for communication between vehicles. Therefore, a study of these factors along with a review of existing proposals identifying their strength and weakness is carried out. Then an analysis of existing broadcast-based warning is conducted which concludes that although this is the most straightforward scheme, loading can result an effective collapse, resulting in unacceptably long transmission delays. The second part of this research (Chapter 5) proposes the NETCODE design, including the main contribution of this thesis, a pair of encoding and decoding algorithms that makes the use of an XOR-based technique to reduce transmission overheads and thus allows warnings to get delivered in time. The final part of this research (Chapters 6--8) evaluates the performance of the proposed scheme as to how it reduces the number of transmissions in the network in response to growing data traffic load and network density and investigates its capacity to detect potential accidents. The evaluations use a custom-built simulator to model real-world scenarios such as city areas, junctions, roundabouts, motorways and so on. The study shows that the reduction in the number of transmissions helps reduce competition in the network significantly and this allows vehicles to deliver warning messages more rapidly to their neighbours. It also examines the relative performance of NETCODE when handling both sudden event-driven and longer-term periodic messages in diverse scenarios under stress caused by increasing numbers of vehicles and transmissions per vehicle. This work confirms the thesis' primary contention that XOR-based network coding provides a potential solution on which a more efficient AWS data dissemination scheme can be built.

Valoración económica de la reducción del ruido por tráfico vehicular: una aplicación para Medellín (Colombia)

El objetivo de este trabajo es la determinación de los beneficios económicos que obtendrían los hogares de zonas residenciales en la ciudad de Medellín (Colombia) por la reducción del ruido por tráfico vehicular. Para tal propósito se utilizó el método de valoración contingente en combinación con información de percepción de calidad acústica de los hogares. Este enfoque permitió estimar la disponibilidad a pagar esperada por la reducción de un decibel en los niveles de ruido a los cuales están expuestos los hogares. Los resultados demuestran que si  se aplica para la ciudad un programa, política o proyecto que logre una reducción generalizada de 5 decibeles en el ruido por tráfico vehicular los beneficios económicos agregados ascienden a 397 millones de pesos colombianos al año. El estudio concluye que estos resultados generan conocimiento importante para hacer más efectiva la toma de decisiones en el marco de políticas regionales con respecto a la gestión de la reducción del ruido por tráfico vehicular. 

Effects of synthetic conditions on the structural, stability and ion conducting properties of Li0.30(La0.50Ln0.50)0.567TiO3 (Ln= La, Pr, Nd) solid electrolytes for rechargeable lithium batteries

The structure, thermal stability, morphology and ion conductivity of titanium perovskites with the general formula Li3xLn2/3−xTiO3 (Ln = rare earth element; 3x= 0.30) are studied in the context of their possible use as solid electrolyte materials for lithium ion batteries. Materials are prepared by a glycine-nitrate method using different sintering treatments, with a cation-disorder-induced structural transition from tetragonal to cubic symmetry, detected as quenching temperature increases. SEM images show that the average grain size increases with increasing sintering temperature and time. Slightly higher bulk conductivity values have been observed for quenched samples sintered at high temperature. Bulk conductivity decreases with the lanthanide ion size. A slight conductivity enhancement, always limited by grain boundaries, is observed for longer sintering times. TDX measurements of the electrolyte/cathode mixtures also show a good stability of the electrolytes in the temperature range of 30-1100ºC.

Congestión vehicular en Medellín: una posible solución desde la Economía

Según la teoría económica el mecanismo de precios es una herramienta adecuada para solucionar el problema de congestión vehicular. El objetivo de este artículo es diagnosticar el grado de congestión vehicular de la ciudad de Medellín (Colombia) y proponer alternativas que den solución a dicho problema desde la óptica de la teoría económica. A diferencia de otros estudios, esta investigación analizó la relación entre el gasto de las familias en transporte y la elección de transporte (público o privado) a través la metodología de elasticidades. Se encontró evidencia a favor de la hipótesis de los precios como mecanismos para desincentivar el uso del automóvil privado, pues a medida que aumenta el nivel de gasto en transporte (asociado a un supuesto peaje urbano), la probabilidad de usar transporte privado disminuye, mientras que la probabilidad de utilizar transporte público aumenta.

Exposición a monóxido de carbono en trabajadores de control vehicular-Cuenca: estudio exploratorio

El presente estudio exploratorio evalúa la exposición al monóxido de carbono (CO), expresado en porcentaje de carboxihemoglobina (%COHb), entre los trabajadores de los centros de control vehicular (CRV) DANTON-Cuenca. Todos los trabajadores (n=55) de los CRVs de Capulispamba y Mayancela participaron en este estudio. El %COHb se determinó a partir de muestras de sangre tomadas al inicio y final de un día laboral de febrero, abril y julio de 2013. Los resultados muestran que el %COHb se incrementó del inicio al final de la jornada laboral en ambos CRVs tanto en el grupo de trabajadores que fuman y no fumadores (P<0.001). Entre los no fumadores (N=42), el %COHb al final de la jornada sobrepasó el valor límite biológico (VLB) para COHb (3.5%) únicamente en el CRV de Mayancela (4.12%, P<0.05). Entre los fumadores (N=13), los promedios de %COHb al final de la jornada sobrepasaron los VLB en ambos CRVs. Se concluye, que los trabajadores de los CRVs de Mayancela y aquellos que fuman presentan %COHb mayores al VLB.

Sketch showing the positions of the redoubts and batteries of the lines of the U.S. Forces in front of Petersburg /

Shows fortifications and names of some residents.

DEVELOPMENT OF LI+ AND NA+ CONDUCTING CERAMICS AND CERAMIC STRUCTURES FOR USE IN SOLID STATE BATTERIES

A solid state lithium metal battery based on a lithium garnet material was developed, constructed and tested. Specifically, a porous-dense-porous trilayer structure was fabricated by tape casting, a roll-to-roll technique conducive to high volume manufacturing. The high density and thin center layer (< 20 μm) effectively blocks dendrites even over hundreds of cycles. The microstructured porous layers, serving as electrode supports, are demonstrated to increase the interfacial surface area available to the electrodes and increase cathode loading. Reproducibility of flat, well sintered ceramics was achieved with consistent powderbed lattice parameter and ball milling of powderbed. Together, the resistance of the LLCZN trilayer was measured at an average of 7.6 ohm-cm2 in a symmetric lithium cell, significantly lower than any other reported literature results. Building on these results, a full cell with a lithium metal anode, LLCZN trilayer electrolyte, and LiCoO2 cathode was cycled 100 cycles without decay and an average ASR of 117 ohm-cm2. After cycling, the cell was held at open circuit for 24 hours without any voltage fade, demonstrating the absence of a dendrite or short-circuit of any type. Cost calculations guided the optimization of a trilayer structure predicted that resulting cells will be highly competitive in the marketplace as intrinsically safe lithium batteries with energy densities greater than 300 Wh/kg and 1000 Wh/L for under $100/kWh. Also in the pursuit of solid state batteries, an improved Na+ superionic conductor (NASICON) composition, Na3Zr2Si2PO12, was developed with a conductivity of 1.9x10-3 S/cm. New super-lithiated lithium garnet compositions, Li7.06La3Zr1.94Y0.06O12 and Li7.16La3Zr1.84Y0.16O12, were developed and studied revealing insights about the mechanisms of conductivity in lithium garnets.