Quantitative structural analysis of the transition from LT-Li xCoO2 to HT-LixCoO2 using the rietveld method: Correlation between structure and electrochemical performance

A quantitative phase analysis was made of LixCoO2 powders obtained by two distinct chemical methodologies at different temperatures (from 400 to 700°C). A phase analysis was made using Rietveld refinements based on X-ray diffraction data, considering the Li xCoO2 powders as a multiphase system that simultaneously contained two main phases with distinct, layered and spinel-type structures. The results showed the coexistence of both structures in LixCoO 2 obtained at low temperature (400 and 500°C), although only the layered structure was detected at higher temperatures (600 and 700°C), regardless of the chemical powder process employed. The electrochemical performance, evaluated mainly by the cycling reversibility of Li xCoO2 in the form of cathode insertion electrodes, revealed that there is a close correlation between structural features and the electrochemical response, with one of the redox processes (3.3 v/3.9 v) associated only with the presence of the spinel-type structure. © 2003 Elsevier B.V. All rights reserved.

Preparação e caracterização eletroquímica de material catódico do tipo La2/3-xLi3xTiO3 para aplicações em baterias de Lítio

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

Phenothiazine based polymers for energy and data storage application

Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung von Polymeren mit redox-funktionalen Phenothiazin-Seitenketten. Phenothiazin und seine Derivate sind kleine Redoxeinheiten, deren reversibles Redoxverhalten mit electrochromen Eigenschaften verbunden ist. Das besondere an Phenothiazine ist die Bildung von stabilen Radikalkationen im oxidierten Zustand. Daher können Phenothiazine als bistabile Moleküle agieren und zwischen zwei stabilen Redoxzuständen wechseln. Dieser Schaltprozess geht gleichzeitig mit einer Farbveränderung an her.rnrnIm Rahmen dieser Arbeit wird die Synthese neuartiger Phenothiazin-Polymere mittels radikalischer Polymerisation beschrieben. Phenothiazin-Derivate wurden kovalent an aliphatischen und aromatischen Polymerketten gebunden. Dies erfolgte über zwei unterschiedlichen synthetischen Routen. Die erste Route beinhaltet den Einsatz von Vinyl-Monomeren mit Phenothiazin Funktionalität zur direkten Polymerisation. Die zweite Route verwendet Amin modifizierte Phenothiazin-Derivate zur Funktionalisierung von Polymeren mit Aktivester-Seitenketten in einer polymeranalogen Reaktion. rnrnPolymere mit redox-funktionalen Phenothiazin-Seitenketten sind aufgrund ihrer Elektron-Donor-Eigenschaften geeignete Kandidaten für die Verwendung als Kathodenmaterialien. Zur Überprüfung ihrer Eignung wurden Phenothiazin-Polymere als Elektrodenmaterialien in Lithium-Batteriezellen eingesetzt. Die verwendeten Polymere wiesen gute Kapazitätswerte von circa 50-90 Ah/kg sowie schnelle Aufladezeiten in der Batteriezelle auf. Besonders die Aufladezeiten sind 5-10 mal höher als konventionelle Lithium-Batterien. Im Hinblick auf Anzahl der Lade- und Entladezyklen, erzielten die Polymere gute Werte in den Langzeit-Stabilitätstests. Insgesamt überstehen die Polymere 500 Ladezyklen mit geringen Veränderungen der Anfangswerte bezüglich Ladezeiten und -kapazitäten. Die Langzeit-Stabilität hängt unmittelbar mit der Radikalstabilität zusammen. Eine Stabilisierung der Radikalkationen gelang durch die Verlängerung der Seitenkette am Stickstoffatom des Phenothiazins und der Polymerhauptkette. Eine derartige Alkyl-Substitution erhöht die Radikalstabilität durch verstärkte Wechselwirkung mit dem aromatischen Ring und verbessert somit die Batterieleistung hinsichtlich der Stabilität gegenüber Lade- und Entladezyklen. rnrnDes Weiteren wurde die praktische Anwendung von bistabilen Phenothiazin-Polymeren als Speichermedium für hohe Datendichten untersucht. Dazu wurden dünne Filme des Polymers auf leitfähigen Substraten elektrochemisch oxidiert. Die elektrochemische Oxidation erfolgte mittels Rasterkraftmikroskopie in Kombination mit leitfähigen Mikroskopspitzen. Mittels dieser Technik gelang es, die Oberfläche des Polymers im nanoskaligen Bereich zu oxidieren und somit die lokale Leitfähigkeit zu verändern. Damit konnten unterschiedlich große Muster lithographisch beschrieben und aufgrund der Veränderung ihrer Leitfähigkeit detektiert werden. Der Schreibprozess führte nur zu einer Veränderung der lokalen Leitfähigkeit ohne die topographische Beschaffenheit des Polymerfilms zu beeinflussen. Außerdem erwiesen sich die Muster als besonders stabil sowohl mechanisch als auch über die Zeit.rnrnZum Schluss wurden neue Synthesestrategien entwickelt um mechanisch stabile als auch redox-funktionale Oberflächen zu produzieren. Mit Hilfe der oberflächen-initiierten Atomtransfer-Radikalpolymerisation wurden gepfropfte Polymerbürsten mit redox-funktionalen Phenothiazin-Seitenketten hergestellt und mittels Röntgenmethoden und Rasterkraftmikroskopie analysiert. Eine der Synthesestrategien geht von gepfropften Aktivesterbürsten aus, die anschließend in einem nachfolgenden Schritt mit redox-funktionalen Gruppen modifiziert werden können. Diese Vorgehensweise ist besonders vielversprechend und erlaubt es unterschiedliche funktionelle Gruppen an den Aktivesterbürsten zu verankern. Damit können durch Verwendung von vernetzenden Gruppen neben den Redoxeigenschaften, die mechanische Stabilität solcher Polymerfilme optimiert werden. rn rn

Analysis and Design Considerations of an Electric Vehicle Powertrain regarding Energy Efficiency and Magnetic Field Exposure

En esta tesis se analiza el sistema de tracción de un vehículo eléctrico de batería desde el punto de vista de la eficiencia energética y de la exposición a campos magnéticos por parte de los pasajeros (radiación electromagnética). Este estudio incluye tanto el sistema de almacenamiento de energía como la máquina eléctrica, junto con la electrónica de potencia y los sistemas de control asociados a ambos. Los análisis y los resultados presentados en este texto están basados en modelos matemáticos, simulaciones por ordenador y ensayos experimentales a escala de laboratorio. La investigación llevada a cabo durante esta tesis tuvo siempre un marcado enfoque industrial, a pesar de estar desarrollada en un entorno de considerable carácter universitario. Las líneas de investigación acometidas tuvieron como destinatario final al diseñador y al fabricante del vehículo, a pesar de lo cual algunos de los resultados obtenidos son preliminares y/o excesivamente académicos para resultar de interés industrial. En el ámbito de la eficiencia energética, esta tesis estudia sistemas híbridos de almacenamiento de energía basados en una combinación de baterías de litio y supercondensadores. Este tipo de sistemas son analizados desde el punto de vista de la eficiencia mediante modelos matemáticos y simulaciones, cuantificando el impacto de ésta en otros parámetros tales como el envejecimiento de las baterías. Respecto a la máquina eléctrica, el estudio se ha centrado en máquinas síncronas de imanes permanentes. El análisis de la eficiencia considera tanto el diseño de la máquina como la estrategia de control, dejando parcialmente de lado el inversor y la técnica de modulación (que son incluidos en el estudio como fuentes adicionales de pérdidas, pero no como potenciales fuentes de optimización de la eficiencia). En este sentido, tanto la topología del inversor (trifásico, basado en IGBTs) como la técnica de modulación (control de corriente en banda de histéresis) se establecen desde el principio. El segundo aspecto estudiado en esta tesis es la exposición a campos magnéticos por parte de los pasajeros. Este tema se enfoca desde un punto de vista predictivo, y no desde un punto de vista de diagnóstico, puesto que se ha desarrollado una metodología para estimar el campo magnético generado por los dispositivos de potencia de un vehículo eléctrico. Esta metodología ha sido validada mediante ensayos de laboratorio. Otros aspectos importantes de esta contribución, además de la metodología en sí misma, son las consecuencias que se derivan de ella (por ejemplo, recomendaciones de diseño) y la comprensión del problema proporcionada por esta. Las principales contribuciones de esta tesis se listan a continuación: una recopilación de modelos de pérdidas correspondientes a la mayoría de dispositivos de potencia presentes en un vehículo eléctrico de batería, una metodología para analizar el funcionamiento de un sistema híbrido de almacenamiento de energía para aplicaciones de tracción, una explicación de cómo ponderar energéticamente los puntos de operación par-velocidad de un vehículo eléctrico (de utilidad para evaluar el rendimiento de una máquina eléctrica, por ejemplo), una propuesta de incluir un convertidor DC-DC en el sistema de tracción para minimizar las pérdidas globales del accionamiento (a pesar de las nuevas pérdidas introducidas por el propio DC-DC), una breve comparación entre dos tipos distintos de algoritmos de minimización de pérdidas para máquinas síncronas de imanes permanentes, una metodología predictiva para estimar la exposición a campos magnéticos por parte de los pasajeros de un vehículo eléctrico (debida a los equipos de potencia), y finalmente algunas conclusiones y recomendaciones de diseño respecto a dicha exposición a campos magnéticos. ABSTRACT This dissertation analyzes the powertrain of a battery electric vehicle, focusing on energy efficiency and passenger exposure to electromagnetic fields (electromagnetic radiation). This study comprises the energy storage system as well as the electric machine, along with their associated power electronics and control systems. The analysis and conclusions presented in this dissertation are based on mathematical models, computer simulations and laboratory scale tests. The research performed during this thesis was intended to be of industrial nature, despite being developed in a university. In this sense, the work described in this document was carried out thinking of both the designer and the manufacturer of the vehicle. However, some of the results obtained lack industrial readiness, and therefore they remain utterly academic. Regarding energy efficiency, hybrid energy storage systems consisting in lithium batteries, supercapacitors and up to two DC-DC power converters are considered. These kind of systems are analyzed by means of mathematical models and simulations from the energy efficiency point of view, quantifying its impact on other relevant aspects such as battery aging. Concerning the electric machine, permanent magnet synchronous machines are studied in this work. The energy efficiency analysis comprises the machine design and the control strategy, while the inverter and its modulation technique are taken into account but only as sources of further power losses, and not as potential sources for further efficiency optimization. In this sense, both the inverter topology (3-phase IGBT-based inverter) and the switching technique (hysteresis current control) are fixed from the beginning. The second aspect studied in this work is passenger exposure to magnetic fields. This topic is approached from the prediction point of view, rather than from the diagnosis point of view. In other words, a methodology to estimate the magnetic field generated by the power devices of an electric vehicle is proposed and analyzed in this dissertation. This methodology has been validated by laboratory tests. The most important aspects of this contribution, apart from the methodology itself, are the consequences (for instance, design guidelines) and the understanding of the magnetic radiation issue provided by it. The main contributions of this dissertation are listed next: a compilation of loss models for most of the power devices found in a battery electric vehicle powertrain, a simulation-based methodology to analyze hybrid energy storage performance in traction applications, an explanation of how to assign energy-based weights to different operating points in traction drives (useful when assessing electrical machine performance, for instance), a proposal to include one DC-DC converter in electric powertrains to minimize overall power losses in the system (despite the new losses added by the DC-DC), a brief comparison between two kinds of loss-minimization algorithms for permanent magnet synchronous machines in terms of adaptability and energy efficiency, a predictive methodology to estimate passenger magnetic field exposure due to power devices in an electric vehicle, and finally some useful conclusions and design guidelines concerning magnetic field exposure.

A single cation or anion dendrimer-based liquid electrolyte

We propose here a novel liquid dendrimer-based single ion conductor as a potential alternative to conventional molecular liquid solvent-salt solutions in rechargeable batteries, sensors and actuators. A specific change from ester (-COOR) to cyano (-CN) terminated peripheral groups in generation-one poly(propyl ether imine) (G1-PETIM)-lithium salt complexes results in a remarkable switchover from a high cation (tLi+ = 0.9 for -COOR) to a high anion (tPF6- = 0.8 for -CN) transference number. This observed switchover draws an interesting analogy with the concept of heterogeneous doping, applied successfully to account for similar changes in ionic conductivity arising out of dispersion of insulator particle inclusions in weak inorganic solid electrolytes. The change in peripheral group simultaneously affects the effective ionic conductivity, with the room temperature ionic conductivity of PETIM-CN (1.9 × 10-5 Ω-1 cm-1) being an order of magnitude higher than PETIM-COOR (1.9 × 10-6 Ω-1 cm-1). Notably, no significant changes are observed in the lithium mobility even following changes in viscosity due to the change in the peripheral group. Changes in the peripheral chemical functionality directly influence the anion mobility, being lower in PETIM-COOR than in PETIM-CN, which ultimately becomes the sole parameter controlling the effective transport and electrochemical properties of the dendrimer electrolytes.

Physicochemical characterization of a new family of small alkyl phosphonium imide ionic liquids

Despite their promising properties, phosphonium based ionic liquids have attracted little attention as compared to their nitrogen-based cation counterparts. This study focuses on the properties of a family of small phosphonium imide ionic liquids, as well as the effect of lithium salt addition to these. The 6 ionic liquids were either alkyl, cyclic or nitrile functionalised phoshonium cations with bis(trifluoromethanesulfonyl)imide, NTf2, or bis(fluorosulfonyl)imide (FSI) as anion. Amongst the properties investigated were ionic conductivity, viscosity, thermal behaviour, electrochemical stability and the reversibility of electrochemical lithium cycling. All ionic liquids showed very promising properties e.g. having low transition temperatures, high electrochemical stabilities, low viscosities and high conductivities. Particularly the trimethyl phosphonium ionic liquids showed some of the highest conductivities reported amongst phosphonium ionic liquids generally. The combination of electrochemical stability, high conductivity and reversible lithium cycling makes them promising systems for energy storage devices such as lithium batteries.

Effect of light-sticks and electralunie attractors on surface-longline catches of swordfish (Xiphias gladius, Linnaeus, 1959) in the southwest equatorial Atlantic

Two experimental fishing trials were carried out off the coast of Pernambuco, Brazil, in 1999 and 2001, using a small artisanal longliner. In experiment 1, six-hook baskets with three chemical light-sticks on alternating hooks had significantly higher catch rates than those with zero or with a light-stick on every hook, with most swordfish accounted for by hooks with light-sticks. Analysis of the data from experiment 2 showed no significant difference between electralume attractors, consisting of AA lithium batteries protected by a solid cover and light-sticks that produce a fluorescent light when two chemical products are mixed. Significant differences were detected in mean CPUE by size class, with most swordfish belonging to class 'b' (125-170 cm lower jaw to fork length (LJFL)). No differences, however, were found for swordfish catches in classes 'a' (< 125 cm LJFL) and V, and no evidence was found of interaction between the two factors (attractor and size class). Although there was no significant difference between the total length-frequency distributions of swordfish caught with light-sticks and electralume attractors, signibcant differences were found for fish smaller than 125 cm LJFL, with electralume catches consisting of smaller swordfish than those of gear using light-sticks. (c) 2004 Elsevier B.V. All rights reserved.

Effect of light-sticks and electralume attractors on surface-longline catches of swordfish (Xiphias gladius, Linnaeus, 1959) in the southwest equatorial Atlantic

Two experimental fishing trials were carried out off the coast of Pernambuco, Brazil, in 1999 and 2001, using a small artisanal longliner. In experiment 1, six-hook baskets with three chemical light-sticks on alternating hooks had significantly higher catch rates than those with zero or with a light-stick on every hook, with most swordfish accounted for by hooks with light-sticks. Analysis of the data from experiment 2 showed no significant difference between electralume attractors, consisting of AA lithium batteries protected by a solid cover and light-sticks that produce a fluorescent light when two chemical products are mixed. Significant differences were detected in mean CPUE by size class, with most swordfish belonging to class ‘b’ (125–170 cm lower jaw to fork length (LJFL)). No differences, however, were found for swordfish catches in classes ‘a’ (<125 cm LJFL) and ‘b’, and no evidence was found of interaction between the two factors (attractor and size class). Although there was no significant difference between the total length-frequency distributions of swordfish caught with light-sticks and electralume attractors, significant differences were found for fish smaller than 125 cm LJFL, with electralume catches consisting of smaller swordfish than those of gear using light-sticks.

Core-leaf onion-like carbon/MnO2 hybrid nano-urchins for rechargeable lithium-ion batteries

A hybrid nano-urchin structure consisting of spherical onion-like carbon and MnO2 nanosheets is synthesized by a facile and environmentally-friendly hydrothermal method. Lithium-ion batteries incorporating the hybrid nano-urchin anode exhibit reversible lithium storage with superior specific capacity, enhanced rate capability, stable cycling performance, and nearly 100% Coulombic efficiency. These results demonstrate the effectiveness of designing hybrid nano-architectures with uniform and isotropic structure, high loading of electrochemically-active materials, and good conductivity for the dramatic improvement of lithium storage.

Monoclinic β-MoO3 nanosheets produced by atmospheric microplasma : application to lithium-ion batteries

Porous high surface area thin films of nanosheet-shaped monoclinic MoO 3 were deposited onto platinized Si substrates using patch antenna-based atmospheric microplasma processing. The films were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and electrochemical analysis. The electrochemical analysis shows original redox peaks and high charge capacity, and also indicates a reversible electrochemical behaviour particularly beneficial for applications in Li-ion batteries. SEM shows that the films are highly porous and consist of nanosheets 50-100 nm thick with surface dimensions in the micrometre range. HRTEM reveals that the MoO3 nanosheets consist of the monoclinic beta phase of MoO3. These intricate nanoarchitectures made of monoclinic MoO3 nanosheets have not been studied previously in the context of applications in Li-ion batteries and show superior structural and morphological features that enable effective insertion of Li ions.

Dual-functional gum arabic binder for silicon anodes in lithium ion batteries

Si has attracted enormous research and manufacturing attention as an anode material for lithium ion batteries (LIBs) because of its high specific capacity. The lack of a low cost and effective mechanism to prevent the pulverization of Si electrodes during the lithiation/ delithiation process has been a major barrier in the mass production of Si anodes. Naturally abundant gum arabic (GA), composed of polysaccharides and glycoproteins, is applied as a dualfunction binder to address this dilemma. Firstly, the hydroxyl groups of the polysaccharide in GA are crucial in ensuring strong binding to Si. Secondly, similar to the function of fiber in fiberreinforced concrete (FRC), the long chain glycoproteins provide further mechanical tolerance to dramatic volume expansion by Si nanoparticles. The resultant Si anodes present an outstanding capacity of ca. 2000 mAh/g at a 1 C rate and 1000 mAh/g at 2 C rate, respectively, throughout 500 cycles. Excellent long-term stability is demonstrated by the maintenance of 1000 mAh/g specific capacity at 1 C rate for over 1000 cycles. This low cost, naturally abundant and environmentally benign polymer is a promising binder for LIBs in the future.

Multifunctional SA-PProDOT binder for lithium ion batteries

An environmentally benign, highly conductive, and mechanically strong binder system can overcome the dilemma of low conductivity and insufficient mechanical stability of the electrodes to achieve high performance lithium ion batteries (LIBs) at a low cost and in a sustainable way. In this work, the naturally occurring binder sodium alginate (SA) is functionalized with 3,4-propylenedioxythiophene-2,5-dicarboxylic acid (ProDOT) via a one-step esterification reaction in a cyclohexane/dodecyl benzenesulfonic acid (DBSA)/water microemulsion system, resulting in a multifunctional polymer binder, that is, SA-PProDOT. With the synergetic effects of the functional groups (e.g., carboxyl, hydroxyl, and ester groups), the resultant SA-PProDOT polymer not only maintains the outstanding binding capabilities of sodium alginate but also enhances the mechanical integrity and lithium ion diffusion coefficient in the LiFePO4 (LFP) electrode during the operation of the batteries. Because of the conjugated network of the PProDOT and the lithium doping under the battery environment, the SA-PProDOT becomes conductive and matches the conductivity needed for LiFePO4 LIBs. Without the need of conductive additives such as carbon black, the resultant batteries have achieved the theoretical specific capacity of LiFePO4 cathode (ca. 170 mAh/g) at C/10 and ca. 120 mAh/g at 1C for more than 400 cycles.

Directional synthesis of tin oxide@graphene nanocomposites via a one-step up-scalable wet-mechanochemical route for lithium ion batteries

Directional synthesis of SnO2@graphene nanocomposites via a one-step, low-cost, and up-scalable wetmechanochemical method is achieved using graphene oxide and SnCl2 as precursors. The graphene oxides are reduced to graphene while the SnCl2 is oxidized to SnO2 nanoparticles that are in situ anchored onto the graphene sheets evenly and densely, resulting in uniform SnO2@graphene nanocomposites. The prepared nanocomposites possess excellent electrochemical performance and outstanding cycling in Li-ion batteries.

Microporous bamboo biochar for lithium-sulfur batteries

Being simple, inexpensive, scalable and environmentally friendly, microporous biomass biochars have been attracting enthusiastic attention for application in lithium-sulfur (Li-S) batteries. Herein, porous bamboo biochar is activated via a KOH/annealing process that creates a microporous structure, boosts surface area and enhances electronic conductivity. The treated sample is used to encapsulate sulfur to prepare a microporous bamboo carbon-sulfur (BC-S) nanocomposite for use as the cathode for Li-S batteries for the first time. The BC-S nanocomposite with 50 wt.% sulfur content delivers a high initial capacity of 1,295 mA·h/g at a low discharge rate of 160 mA/g and high capacity retention of 550 mA·h/g after 150 cycles at a high discharge rate of 800 mA/g with excellent coulombic efficiency (⩾95%). This suggests that the BC-S nanocomposite could be a promising cathode material for Li-S batteries.