Lee, Kyu Tae; Kan, Wang H; Nazar, Linda F
Homogeneous-sized LiMPO(4) (M = Fe, Mn) nanorods and bulk particles were synthesized, and the thermodynamic characteristics of their mixtures as electrodes were analyzed to study the lithiation/delithiation mechanism for the general case of nanoparticles with a heterogeneous particle size distribution. We show that ionic transport occurs between nano and bulk particles in a cell at equilibrium, due to their electrochemical potential difference that originates from their different thermodynamic properties. This means that one phase in a single particle is preferred to two phases in a single particle during lithiation/delithiation of LiMPO(4) from the viewpoint of thermodynamics if the electrode is composed of differing particle sizes. PMID:19366201
Jena, Ajit Kumar; Nanda, B. R. K.; Condensed Matter Theory; Computation Team
Through density functional calculations we have investigated the electronic and magnetic properties of LiMPO4, where M is a 3d transition metal element. We find that contrary to many transition metal oxides, in these Olivine phosphates the band gap is originated due to crystal field anisotropy as well as weak O-p - M-d covalent interaction. Both of them are attributed to the presence of PO43- polyanion. The anisotropic crystal field, in the absence of covalent interactions, creates atomically localized non-degenerate M-d states and therefore the gap is a natural outcome. Onsite repulsion, due to strong correlation effect, further enhances the gap. These localized d states favor high-spin configuration which leads to antiferromagnetic ordering due to Hund's coupling. Experimentally observed low Neel temperature of this family of compounds is explained from the DFT obtained spin exchange interaction parameters. Work supported by Nissan Research Program.
Zhou, Yanping; Yang, Dan; Zeng, Yi; Zhou, Yan; Ng, Wun Jern; Yan, Qingyu; Fong, Eileen
In this work, a novel waste-to-resource strategy to convert waste bacteria into a useful class of cathode materials, lithium metal phosphate (LiMPO4; M = Fe, Mn), is presented. Escherichia coli (E. coli) bacteria used for removing phosphorus contamination from wastewater are harvested and used as precursors for the synthesis of LiMPO4. After annealing, LiFePO4 and LiMnPO4 nanoparticles with dimensions around 20 nm are obtained. These particles are found to be enveloped in a carbon layer with a thickness around 3-5 nm, generated through the decomposition of the organic matter from the bacterial cell cytoplasm. The battery performance for the LiFePO4 is evaluated. A high discharge capacity of 140 mAh g(-1) at 0.1 C with a flat plateau located at around 3.5 V is obtained. In addition, the synthesized particles display excellent stability and rate capabilities. Even under a high C rate of 10 C, a stable discharge capacity of 75.4 mAh g(-1) can still be achieved. PMID:24930375
Vadivel Murugan, A; Muraliganth, T; Ferreira, P J; Manthiram, A
We demonstrate an efficient and rapid microwave irradiated solvothermal method to prepare nanostructured lithium metal phosphates LiMPO(4) (M = Mn, Fe, Co, and Ni) within a short reaction time (5-15 min) at temperatures as low as 300 degrees C without requiring any post annealing at elevated temperatures. The highly viscous, high-boiling tetraethyleneglycol used as the solvent not only provides a reducing atmosphere to prevent the oxidation of M(2+) to M(3+) but also inhibits the agglomeration of the nanoparticles formed. The enhanced reaction rates facilitated by the dielectric volumetric heating of the microwave absorbing reactants led to the formation of highly crystalline, phase-pure LiMPO(4) powders. The samples are characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy (TEM), and electrochemical measurements in lithium cells. High-resolution TEM studies reveal the formation of single-crystalline LiMPO(4) with nano-thumblike shapes. The dimensionally modulated nano-thumblike shapes with the lithium diffusion direction (b axis) along the shorter dimension are particularly beneficial to achieve high-power capability in lithium ion cells. Subsequent networking of the single-crystalline LiMPO(4) nano-thumps with multiwalled carbon nanotubes by a simple solution-based mixing at ambient temperatures to overcome the electronic conductivity limitations offers excellent electrochemical performance in lithium ion cells. PMID:19125669
Sugiyama, Jun; Nozaki, Hiroshi; Harada, Masashi; Kamazawa, Kazuya; Ikedo, Yutaka; Miyake, Yasuhiro; Ofer, Oren; Månsson, Martin; Ansaldo, Eduardo J.; Chow, Kim H.; Kobayashi, Genki; Kanno, Ryoji
In order to study the diffusive nature of lithium transition-metal phospho-olivines, we measured muon-spin relaxation (μ+SR) spectra for the polycrystalline LiMPO4 samples with M=Mn, Fe, Co, or Ni in the temperature range between 50 and 500 K. The μ+SR spectra under zero applied field are strongly affected by the magnetic moments of the 3d electrons in the M2+ ions so that, for LiMnPO4, it was difficult to detect the relaxation change caused by the diffusion due to the large Mn2+(S=5/2) moments. However, diffusive behavior was clearly observed via the relaxation due to nuclear dipolar fields above ˜150 K for LiFePO4, LiCoPO4, and LiNiPO4 as S decreased from 2 to 1. From the temperature dependence of the nuclear field fluctuation rate, self-diffusion coefficients of Li+ ions (DLi) at 300 K and its activation energy (Ea) were estimated, respectively, as ˜3.6(2)×10-10 cm2/s and Ea=0.10(2) eV for LiFePO4, ˜1.6(1)×10-10 cm2/s and Ea=0.10(1) eV for LiCoPO4, and ˜2.7(4)×10-10 cm2/s and Ea=0.17(2) eV for LiNiPO4, assuming that the diffusing Li+ ions jump between the regular site and interstitial sites.
Vijayan, Lakshmi; Cheruku, Rajesh; Govindaraj, G.
Olivine structured material shows specific capacities up to 170mAh/g and can be charged in a very short time. LiMPO4, (M=transition metal ion) does not consists of heavy metal and have no memory loss like Ni-Cd, Ni-metal hydride solutions. Benefit of LiMPO4 is its flexibility for the cell design and battery applications. Li based LiCoPO4 of Orthophosphate family is synthesized by template free sucrose assisted hydrothermal method. Olivine structured compounds possess orthorhombic crystal structure with Pnma, pmnb space group having four formula units. The material is characterized through different techniques like XRD, FTIR, SEM, VSM and electrical characterization is done through impedance spectroscopy and the results are reported.
Laveda, Josefa Vidal; Chandhok, Vibhuti; Murray, Claire A; Paterson, Gary W; Corr, Serena A
Microwave or ultrasonic treatment of metal alkoxides presents a fast, low cost route to both anode and cathode nanomaterials for Li-ion battery applications. Here, we demonstrate the formation of LiMPO4 (M = Fe, Mn) and Mn3O4 nanostructures via this simple route which exhibit excellent electrochemical performances. This approach opens up a new avenue for the targeted design of nanostructured materials, where co-location of the desired metals in a single starting material shortens reaction times and temperatures since there is a decrease in diffusional energy requirements usually needed for these reactions to proceed. PMID:26486274
Rempel, E. L.; Chian, A. C.-L.; Macau, E. E. N.; Rosa, R. R.
Dados medidos no vento solar rápido proveniente dos buracos coronais revelam que os plasmas no meio interplanetário são dominados por flutuações Alfvênicas, caracterizadas por uma alta correlação entre as variações do campo magnético e da velocidade do plasma. As flutuações exibem muitas características esperadas em turbulência magneto-hidrodinâmica totalmente desenvolvida, tais como intermitência e espectros contínuos. Contudo, os mecanismos responsáveis pela evolução de turbulência Alfvênica intermitente não são completamente compreendidos. Neste trabalho a teoria de caos é usada para explicar como sistemas Alfvênicos, modelados pela equação Schrödinger não-linear derivativa e pela equação Kuramoto-Sivashinsky, podem se tornar fortemente caóticos à medida em que parâmetros do plasma são variados. Pequenas perturbações no parâmetro de dissipação podem fazer com que o sistema mude bruscamente de um regime periódico, ou fracamente caótico, para um regime fortemente caótico. As séries temporais das flutuações do campo magnético nos regimes fortemente caóticos exibem comportamento intermitente, em que fases laminares ou fracamente caóticas são interrompidas por fortes estouros caóticos. É mostrado que o regime fortemente caótico é atingido quando as soluções periódicas ou fracamente caóticas globalmente estáveis interagem com soluções do sistema que são fortemente caóticas, mas globalmente instáveis. Estas soluções globalmente instáveis são conjuntos caóticos não-atrativos conhecidos como selas caóticas, e são responsáveis pelos fortes estouros nos regimes intermitentes. Selas caóticas têm sido detectadas experimentalmente em uma grande variedade de sistemas, sendo provável que elas desempenhem um papel importante na turbulência intermitente observada em plasmas espaciais.
Oliveira, P. T. S.; Leite, M.; Mattos, T.; Wendland, E.; Nearing, M. A.
Since 2014, several cities of southeastern Brazil have grappled with their worst drought in nearly 80 years. To improve water availability in this region, the Brazilian government has studied the possibility of increasing groundwater use, mainly in the Guarani Aquifer System (GAS), the largest (~1.2 million km2) transnational boundary groundwater reservoir in South America. Approximately one half of the outcrop areas of the GAS are located in the Cerrado biome, the main agricultural expansion region in Brazil. Large areas of Cerrado vegetation have been converted into farmland in recent years; however, little attention has been paid to the consequences of this land cover and land use change on groundwater recharge. In this study we assessed groundwater recharge in different physiognomies of the Cerrado located in an outcrop area of the GAS. Water table fluctuations were measured from October 2011 through August 2013, by 64 monitoring wells distributed on five physiognomies of the undisturbed Cerrado. We used 20 (2.2±0.3 m), 20 (4.3±1.4 m), 14 (4.7±1.9 m), 9 (6.2±0.7 m), and 1 (42 m) monitoring wells (and average depth of wells) for "campo limpo" (cerrado grassland), "campo sujo" (shrub cerrado), "campo cerrado" (shrub cerrado), "cerrado sensu stricto" (wooded cerrado), and "cerrado sensu stricto denso" (cerrado woodland), respectively. Recharge was computed for each well using the Water Table Fluctuation method. The measured precipitation for hydrological years 2011-12 and 2012-13 were 1247 mm and 1194 mm, respectively. We found values of average annual recharge of 363 mm, 354 mm, 324 mm, and 315 mm for "campo limpo", "campo sujo","campo cerrado", and "cerrado sensu stricto", respectively. We did not find changes in the water table level in the one well located in the "cerrado sensu stricto denso". The water table in this well was 35 m deep; therefore, the amount of water that eventually reached the saturated zone was not enough to cause a rapid change in the
Major, K.; Veilleux, J.; Brisard, G.
Lithium-ion batteries have high energy efficiency and good cycling life and are considered as one of the best energy storage device for hybrid and/or electrical vehicle. Still, several problems must be solved prior to a broad adoption by the automotive industry: energy density, safety, and costs. To enhance both energy density and safety, the current study aims at depositing binder-free cathode materials using inductively coupled thermal plasma. In a first step, lithium iron phosphate (LiFePO4) powders are synthesized in an inductively coupled thermal plasma reactor and dispersed in a conventional polyvinylidene fluoride (PVDF) binder. Then, binder-free LiFePO4 coatings are directly deposited onto nickel current collectors by solution precursor plasma spraying (SPPS). The morphology, microstructure, and composition of the synthesized LiFePO4 powders and coatings are fully characterized by electronic microscopy, x-ray diffraction, and x-ray photoelectron spectroscopy (XPS). Quantifying Li with XPS requires the substitution of iron with manganese in the SPPS precursors (LiMPO4, where M = Fe or Mn). The plasma-derived cathodes (with and without PVDF binder) are assembled in button cells and tested. Under optimized plasma conditions, cyclic voltammetry shows that the electrochemical reversibility of plasma-derived cathodes is improved over that of conventional sol-gel-derived LiFePO4 cathodes.
Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong
Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.
Briceno, D.; Eberhard, W.; Vilardi, J.; Cayol, J.-P.; Shelly, T.
This study documents differences in the courtship behavior of wild strains of Ceratitis capitata (Wiedemann) from Madeira (Portugal), Hawaii (U.S.A.), Costa Rica, and Patagonia (Argentina). Some traits showed large variations and others substantial overlaps. The angle at which the male faced toward the female at the moment of transition from continuous wing vibration and intermittent buzzing changed very little during the course of courtship in all strains, but males from Madeira tended to face more directly toward the female than other males. Females tended to look more, and more directly, toward the males as courtship progressed in all strains. The distance between male and female tended to decrease as courtship proceeded in all strains, but the distances at which males initiated continuous vibration, intermittent buzzing, and jumped onto the female were relatively less variable between strains, except for the strain from Costa Rica. Flies of Madeira courted for longer and the male moved his head and buzzed his wings longer than the other strains. (author) [Spanish] Este estudio documenta diferencias en el comportamiento de cortejo de cepas silvestres de Ceratitis capitata (Wied.) provenientes de Madeira (Portugal), Hawaii (Estados Unidos de Norte America), Costa Rica y Patagonia (Argentina). Algunas caracteristicas mostraron grandes variaciones y traslape substancial. Los angulos a los cuales los machos miraron hacia las hembras cambiaron muy poco en el momento de la transicion de la vibracion continua al zumbido intermitente durante el curso del cortejo en todo las cepas, pero los machos de Madeira tendieron a enfrentar mas directamente a la hembra que otros machos. Los angulos de las hembras disminuyeron claramente durante el cortejo en todas las cepas. La distancia entre el macho y la hembra tendio a disminuir conforme el cortejo continuaba en todas las cepas, pero las distancias a las cuales los machos iniciaron la vibracion continua, el zumbido intermitente
Asari, Yusuke; Suwa, Yuji; Hamada, Tomoyuki
Formation and diffusion of a vacancy-polaron complex in olivine-type cathode-active materials, namely, LiMPO4 (M = Fe, Mn), were theoretically investigated by using the first-principles density functional theory within a framework of GGA + U method. It is shown that a lithium vacancy and a corresponding hole-polaron form the complex at the fully lithiated limit owing to lattice distortion and Coulomb interaction between them. It is also shown that the formation energy of the complex in LiMnPO4 is 0.19 eV higher than that in LiFePO4, since a hole polaron in LiMnPO4 is not sufficiently relaxed. As a result, the nucleation rate of MnPO4 phase in LiMnPO4 is 10-3 times slower than that in LiFePO4 and represents the main difference between the kinetics in the initial stage of charging of the two olivine materials. It was also found that the activation energy of the complex diffusion is limited by vacancy hopping in LiMnPO4, while it is determined by both vacancy hopping and polaron hopping in LiFePO4. The activation energy in LiMnPO4, 0.38 eV, is comparable with that in LiFePO4, 0.42 eV. The calculated potential energy profile, showed that the minimum energy path of the diffusing lithium in LiMnPO4 has the same winding shape as that in LiFePO4.
Meng, Ying Shirley; Arroyo-de Dompablo, M Elena
To meet the increasing demands of energy storage, particularly for transportation applications such as plug-in hybrid electric vehicles, researchers will need to develop improved lithium-ion battery electrode materials that exhibit high energy density, high power, better safety, and longer cycle life. The acceleration of materials discovery, synthesis, and optimization will benefit from the combination of both experimental and computational methods. First principles (ab Initio) computational methods have been widely used in materials science and can play an important role in accelerating the development and optimization of new energy storage materials. These methods can prescreen previously unknown compounds and can explain complex phenomena observed with these compounds. Intercalation compounds, where Li(+) ions insert into the host structure without causing significant rearrangement of the original structure, have served as the workhorse for lithium ion rechargeable battery electrodes. Intercalation compounds will also facilitate the development of new battery chemistries such as sodium-ion batteries. During the electrochemical discharge reaction process, the intercalating species travel from the negative to the positive electrode, driving the transition metal ion in the positive electrode to a lower oxidation state, which delivers useful current. Many materials properties change as a function of the intercalating species concentrations (at different state of charge). Therefore, researchers will need to understand and control these dynamic changes to optimize the electrochemical performance of the cell. In this Account, we focus on first-principles computational investigations toward understanding, controlling, and improving the intrinsic properties of five well known high energy density Li intercalation electrode materials: layered oxides (LiMO2), spinel oxides (LiM2O4), olivine phosphates (LiMPO4), silicates-Li2MSiO4, and the tavorite-LiM(XO4)F (M = 3d
Julian, Guilherme Silva; Oliveira, Renato Watanabe de; Tufik, Sergio; Chagas, Jair Ribeiro
Obstructive sleep apnea (OSA) has been associated with oxidative stress and various cardiovascular consequences, such as increased cardiovascular disease risk. Quantitative real-time PCR is frequently employed to assess changes in gene expression in experimental models. In this study, we analyzed the effects of chronic intermittent hypoxia (an experimental model of OSA) on housekeeping gene expression in the left cardiac ventricle of rats. Analyses via four different approaches-use of the geNorm, BestKeeper, and NormFinder algorithms; and 2-ΔCt (threshold cycle) data analysis-produced similar results: all genes were found to be suitable for use, glyceraldehyde-3-phosphate dehydrogenase and 18S being classified as the most and the least stable, respectively. The use of more than one housekeeping gene is strongly advised. RESUMO A apneia obstrutiva do sono (AOS) tem sido associada ao estresse oxidativo e a várias consequências cardiovasculares, tais como risco aumentado de doença cardiovascular. A PCR quantitativa em tempo real é frequentemente empregada para avaliar alterações na expressão gênica em modelos experimentais. Neste estudo, analisamos os efeitos da hipóxia intermitente crônica (um modelo experimental de AOS) na expressão de genes de referência no ventrículo cardíaco esquerdo de ratos. Análises a partir de quatro abordagens - uso dos algoritmos geNorm, BestKeeper e NormFinder e análise de dados 2-ΔCt (ciclo limiar) - produziram resultados semelhantes: todos os genes mostraram-se adequados para uso, sendo que gliceraldeído-3-fosfato desidrogenase e 18S foram classificados como o mais e o menos estável, respectivamente. A utilização de mais de um gene de referência é altamente recomendada. PMID:27383935
Martínez García, Rosa María
El embarazo representa un desafío desde el punto de vista nutricional, debido a que las necesidades de nutrientes están aumentadas y una alteración en su ingesta puede afectar la salud materno-fetal. Estados deficitarios en micronutrientes están relacionados con preeclampsia, retraso del crecimiento intrauterino, aborto y anomalías congénitas. Actualmente, la dieta de muchas madres gestantes es insuficiente en micronutrientes, siendo necesaria su suplementación. Se recomienda la suplementación con ácido fólico en dosis de 400 μg/día, y de 5 mg en embarazadas de riesgo, debiendo comenzar al menos 1 mes antes de la concepción y durante las primeras 12 semanas de gestación, y prolongarla durante todo el embarazo en madres con riesgo nutricional. Es importante vigilar la dosis adecuada de ácido fólico para prevenir los posibles efectos adversos derivados de su acumulación plasmática no metabolizada. Un elevado porcentaje de gestantes presenta anemia ferropénica, estando recomendado el uso intermitente de suplementos con hierro (menor alteración gastrointestinal y estrés oxidativo); no recomendándose en madres no anémicas (con hemoglobina > 13,5 g/L). Dado que la absorción de calcio está aumentada hasta un 40% en gestación, no se recomienda su suplementación en madres con ingestas adecuadas (3 lácteos/día), debiéndose reservar su uso a madres con ingestas insuficientes y/o que tengan alto riesgo de preeclampsia. Respecto al iodo, existen posicionamientos contradictorios por parte de distintos grupos de trabajo, estableciéndose la suplementación con yoduro potásico en mujeres que no alcanzan las ingestas recomendadas con su dieta (3 raciones de leche y derivados lácteos + 2 g de sal yodada). Dado que la vitamina A y D pueden ser tóxicas para la madre y el feto, no está recomendada su suplementación excepto en casos de deficiencia. Aunque la administración de suplementos con varios micronutrientes puede repercutir favorablemente en el
Caproni, A.; de Gouveia dal Pino, E. M.; Abraham, Z.; Raga, A. C.
Observações com técnicas de interferometria com longa linha de base têm mostrado a existência de um jato relativístico com componentes superluminais na região central de 3C 120. Estas componentes são ejetadas em distintas direções no plano do céu e com diferentes velocidades aparentes. Estas características foram interpretadas em trabalhos anteriores como efeitos da precessão do jato relativístico. Neste trabalho, realizamos simulações tri-dimensionais do jato de 3C 120 utilizando os parâmetros de precessão determinados em trabalhos anteriores e variando as características iniciais do jato e meio ambiente, tais como densidade numérica e temperatura. Todas as simulações foram feitas com o código hidrodinâmico YGUAZÚ-A, assumindo-se um jato adiabático descrito por uma equação de estado relativística. Pelo fato de estarmos utilizando um código hidrodinâmico, nós assumimos que a intensidade do campo magnético e a distribuição de partículas, necessários para se calcular a emissão sincrotron, são proporcionais à pressão hidrodinâmica. Comparação entre dois cenários distintos, nos quais o material do jato é ejetado com velocidade constante (jato contínuo) e com velocidade modulada por um padrão sinusoidal no tempo (jato intermitente), é apresentada e discutida. Para jatos que apresentam fenômenos de precessão e intermitência, com amplitude de variação na velocidade de injeção maior que dez por cento da velocidade média de injeção, a hipótese balística, controlada pela intermitencia, é mais provável. Por outro lado, para jatos com precessão mas sem intermitência (ou com amplitude de variabilidade em velocidade mais baixa que no caso anterior), o efeito da precessão na morfologia do jato não é desprezível. Portanto, de um modo geral, ambos efeitos (precessão e movimentos balísticos) devem estar concorrendo para afetar a morfologia dos jatos superluminais.
Bustamante, M.; Potter, C.; Corbeels, M.; Scopel, E.
Tropical savannas cover 22.5 x 106 km2, an area nearly 30% larger than the area of tropical forests. Although the average carbon \\(C\\) content of savanna vegetation is only about 25% as great as tropical forest vegetation (29 vs. 120 Mg C ha-1), land use changes in tropical savannas are even more rapid than changes in tropical forests. The Brazilian savanna, locally known as Cerrado, covers about 2 x 106 km2 and is the largest savanna formation in South America. Its area is comparable to the Miombo savanna of Southern Africa. Biomass in the Cerrado varies from 1.9 Mg C ha-1 \\(grassy campo limpo\\) to 30.5 Mg C ha-1 \\(woody cerradão\\). Cerrado vegetation can be highly productive; annual net ecosystem exchange fluxes as high as 2.5 Mg C ha-1 yr-1 have been measured although lower values are more common. Assuming approximately 40 years of land use conversion and an average net biomass change \\(29 Mg C ha-1\\), this would lead to an average loss of C from the Cerrado of nearly 0.1 Pg C y-1. These values can be higher if belowground biomass is included as in Cerrado the ratio of belowground to aboveground biomass reaches values as high as 7.7. Fire is a principle factor controlling vegetation dynamics in the Cerrado \\(especially the ratio of grass to woody biomass\\). Frequent fires kill trees and shrubs favoring grasses favoring more open vegetation types. Inversely fire suppression favors woody growth. Advances in agricultural productivity have made the Cerrado the leading region of Brazil for beef cattle production and soybean production. It is estimated that between 40% and 55% of the region has been converted to pasture and other agricultural uses with peak rates in the early 1970's. Increasing international demand of biofuels represents a new aspect of land use in the region. Soil organic matter stocks exceed biomass stocks and data on soil C storage with conversion of native savanna into pasture indicated that well-managed, cultivated pastures may provide
Hashambhoy, Ayesha Maria
The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization
) la dimension limitée du conduit karstique, (2) l'écoulement en charge, (3) le débordement dans un autre bassin, (4) le débordement du réseau s'écoulant vers la source principale par des sources temporaires dans le même bassin, (5) le stockage d'eau dans la zone surmontant l'aquifère karstique ou la zone épikarstique du bassin, et (6) des facteurs tels que le climat, le sol et le couvert végétal, l'altitude et la géologie du bassin d'alimentation. Le phénomène de capacité limitée du débit maximal des sources karstiques n'est pas pris en compte dans la modélisation des processus de précipitation-ruissellement, ce qui est probablement une des principales raisons de l'actuelle médiocre qualité de la modélisation hydrologique du karst. Resumen. Se presenta un análisis de las condiciones que limitan la descarga de algunos manantiales kársticos. Un elevado número de los manantiales estudiados muestra que, bajo condiciones de precipitación extremadamente intensa, hay un valor máximo para la descarga de los manantiales principales de la cuenca, independientemente del tamaño de ésta y del volumen de precipitación. La modelación de la descarga de manantiales kársticos no es fácil de generalizar y esquematizar debido a la existencia de numerosas características que son inherentes a los sistemas kársticos de flujo. A partir del estudio detallado de los datos publicados sobre cuatro manantiales kársticos, se identificó las posibles causas de la existencia de un caudal máximo de descarga: (1) el tamaño limitado del conducto kárstico, (2) el caudal surgente, (3) la descarga a otras cuencas, (4) el desbordamiento del sistema de flujo principal hacia manantiales intermitentes dentro de la misma cuenca, (5) el almacenamiento de agua en la zona superior del acuífero kárstico o zona epikárstica de la cuenca, y (6) factores tales como el clima, suelo y cubierta vegetal, y la altitud y geología de la zona de captación. La limitación de la