Lithium ion rechargeable batteries: State of the art and future needs of microscopic theoretical models and simulations

This review deals with the recent developments and present status of the theoretical models for the simulation of the performance of lithium ion batteries. Preceded by a description of the main materials used for each of the components of a battery -anode, cathode and separator- and how material characteristics affect battery performance, a description of the main theoretical models describing the operation and performance of a battery are presented. The influence of the most relevant parameters of the models, such as boundary conditions, geometry and material characteristics are discussed. Finally, suggestions for future work are proposed.

Advanced lithium and lithium-ion rechargeable batteries for automotive applications

The worldwide demand for a clean and low-fuel-consuming transport promotes the development of safe, high energy and power electrochemical storage and conversion systems. Lithium-ion batteries (LIBs) are considered today the best technology for this application as demonstrated by the recent interest of automotive industry in hybrid (HEV) and electric vehicles (EV) based on LIBs. This thesis work, starting from the synthesis and characterization of electrode materials and the use of non-conventional electrolytes, demonstrates that LIBs with novel and safe electrolytes and electrode materials meet the targets of specific energy and power established by U.S.A. Department of Energy (DOE) for automotive application in HEV and EV. In chapter 2 is reported the origin of all chemicals used, the description of the instruments used for synthesis and chemical-physical characterizations, the electrodes preparation, the batteries configuration and the electrochemical characterization procedure of electrodes and batteries. Since the electrolyte is the main critical point of a battery, in particular in large- format modules, in chapter 3 we focused on the characterization of innovative and safe electrolytes based on ionic liquids (characterized by high boiling/decomposition points, thermal and electrochemical stability and appreciable conductivity) and mixtures of ionic liquid with conventional electrolyte. In chapter 4 is discussed the microwave accelerated sol–gel synthesis of the carbon- coated lithium iron phosphate (LiFePO 4 -C), an excellent cathode material for LIBs thanks to its intrinsic safety and tolerance to abusive conditions, which showed excellent electrochemical performance in terms of specific capacity and stability. In chapter 5 are presented the chemical-physical and electrochemical characterizations of graphite and titanium-based anode materials in different electrolytes. We also characterized a new anodic material, amorphous SnCo alloy, synthetized with a nanowire morphology that showed to strongly enhance the electrochemical stability of the material during galvanostatic full charge/discharge cycling. Finally, in chapter 6, are reported different types of batteries, assembled using the LiFePO 4 -C cathode material, different anode materials and electrolytes, characterized by deep galvanostatic charge/discharge cycles at different C-rates and by test procedures of the DOE protocol for evaluating pulse power capability and available energy. First, we tested a battery with the innovative cathode material LiFePO 4 -C and conventional graphite anode and carbonate-based electrolyte (EC DMC LiPF 6 1M) that demonstrated to surpass easily the target for power-assist HEV application. Given that the big concern of conventional lithium-ion batteries is the flammability of highly volatile organic carbonate- based electrolytes, we made safe batteries with electrolytes based on ionic liquid (IL). In order to use graphite anode in IL electrolyte we added to the IL 10% w/w of vinylene carbonate (VC) that produces a stable SEI (solid electrolyte interphase) and prevents the graphite exfoliation phenomenon. Then we assembled batteries with LiFePO 4 -C cathode, graphite anode and PYR 14 TFSI 0.4m LiTFSI with 10% w/w of VC that overcame the DOE targets for HEV application and were stable for over 275 cycles. We also assembled and characterized ―high safety‖ batteries with electrolytes based on pure IL, PYR 14 TFSI with 0.4m LiTFSI as lithium salt, and on mixture of this IL and standard electrolyte (PYR 14 TFSI 50% w/w and EC DMC LiPF 6 50% w/w), using titanium-based anodes (TiO 2 and Li 4 Ti 5 O 12 ) that are commonly considered safer than graphite in abusive conditions. The batteries bearing the pure ionic liquid did not satisfy the targets for HEV application, but the batteries with Li 4 Ti 5 O 12 anode and 50-50 mixture electrolyte were able to surpass the targets. We also assembled and characterized a lithium battery (with lithium metal anode) with a polymeric electrolyte based on poly-ethilenoxide (PEO 20 – LiCF 3 SO 3 +10%ZrO 2 ), which satisfied the targets for EV application and showed a very impressive cycling stability. In conclusion, we developed three lithium-ion batteries of different chemistries that demonstrated to be suitable for application in power-assist hybrid vehicles: graphite/EC DMC LiPF 6 /LiFePO 4 -C, graphite/PYR 14 TFSI 0.4m LiTFSI with 10% VC/LiFePO 4 -C and Li 4 T i5 O 12 /PYR 14 TFSI 50%-EC DMC LiPF 6 50%/LiFePO 4 -C. We also demonstrated that an all solid-state polymer lithium battery as Li/PEO 20 –LiCF 3 SO 3 +10%ZrO 2 /LiFePO 4 -C is suitable for application on electric vehicles. Furthermore we developed a promising anodic material alternative to the graphite, based on SnCo amorphous alloy.

Spent NiMH batteries-The role of selective precipitation in the recovery of valuable metals

The production of electronic equipment, such as computers and cell phones, and, consequently, batteries, has increased dramatically. One of the types of batteries whose production and consumption has increased in recent times is the nickel metal hydride (NiMH) battery. This study evaluated a hydrometallurgical method of recovery of rare earths and a simple method to obtain a solution rich in Ni-Co from spent NiMH batteries. The active materials from both electrodes were manually removed from the accumulators and leached. Several acid and basic solutions for the recovery of rare earths were evaluated. Results showed that more than 98 wt.% of the rare earths were recovered as sulfate salts by dissolution with sulfuric acid, followed by selective precipitation at pH 1.2 using sodium hydroxide. The complete process. precipitation at pH 1.2 followed by precipitation at pH 7, removed about 100 wt.% of iron and 70 wt.% of zinc from the leaching solution. Results were similar to those found in studies that used solvent extraction. This method is easy, economic, and does not pose environmental threats of solvent extraction. (C) 2009 Elsevier B.V. All rights reserved.

Numerical modeling of the failure mechanisms in Si thin film anode for Li-ion batteries

In recent times, the demand for the storage of electrical energy has grown rapidly for both static applications and the portable electronics enforcing the substantial improvement in battery systems, and Li-ion batteries have been proven to have maximum energy storage density in all rechargeable batteries. However, major breakthroughs are required to consummate the requirement of higher energy density with lower cost to penetrate new markets. Graphite anode having limited capacity has become a bottle neck in the process of developing next generation batteries and can be replaced by higher capacity metals such as Silicon. In the present study we are focusing on the mechanical behavior of the Si-thin film anode under various operating conditions. A numerical model is developed to simulate the intercalation induced stress and the failure mechanism of the complex anode structure. Effect of the various physical phenomena such as diffusion induced stress, plasticity and the crack propagation are investigated to predict better performance parameters for improved design.

Synthesis and electrochemical properties of vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films

Vanadyl phosphate and its hybrid compounds have proven to undergo electrochemical intercalation and de-intercalation of lithium ions, which enables its use as cathode material for Li ion rechargeable batteries. In this context, vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films were synthesized via the exfoliation and reconstruction approach in order to evaluate their potential use as cathode in ion lithium batteries. X-ray diffraction patterns indicate that the lamellar structure of the inorganic matrix is maintained, consistent with the topotactic process. In the scanning electron micrographs, hybrid films exhibit rough surface consisting of warped and cracked crystallites, quite different from vanadyl phosphate di-hydrate square platelets crystallites. Electrochemical evaluation using cyclic voltammetry and charge-discharge galvanostatic techniques shows small differences between the charge and the discharge curves, indicating an irreversibility of the hybrid systems. (C) 2009 Elsevier B.V. All rights reserved.

Analysis and implementation of a multi-ratio switched capacitor DC-DC converter for a supercapacitor power supply

An energy harvesting system requires an energy storing device to store the energy retrieved from the surrounding environment. This can either be a rechargeable battery or a supercapcitor. Due to the limited lifetime of rechargeable batteries, they need to be periodically replaced. Therefore, a supercapacitor, which has ideally a limitless number of charge/discharge cycles can be used to store the energy; however, a voltage regulator is required to obtain a constant output voltage as the supercapacitor discharges. This can be implemented by a Switched-Capacitor DC-DC converter which allows a complete integration in CMOS technology, although it requires several topologies in order to obtain a high efficiency. This thesis presents the complete analysis of four different topologies in order to determine expressions that allow to design and determine the optimum input voltage ranges for each topology. To better understand the parasitic effects, the implementation of the capacitors and the non-ideal effect of the switches, in 130 nm technology, were carefully studied. With these two analysis a multi-ratio SC DC-DC converter was designed with an output power of 2 mW, maximum efficiency of 77%, and a maximum output ripple, in the steady state, of 23 mV; for an input voltage swing of 2.3 V to 0.85 V. This proposed converter has four operation states that perform the conversion ratios of 1/2, 2/3, 1/1 and 3/2 and its clock frequency is automatically adjusted to produce a stable output voltage of 1 V. These features are implemented through two distinct controller circuits that use asynchronous time machines (ASM) to dynamically adjust the clock frequency and to select the active state of the converter. All the theoretical expressions as well as the behaviour of the whole system was verified using electrical simulations.

Carbon Nanotubes as Material for Supercapacitor Electrodes

Electrochemical double-layer supercapacitors have an intermediate position between rechargeable batteries, which can store high amounts of energy, and dielectric capacitors, which have high output power. Supercapacitors are widely suggested to be used in automobiles (recuperation during braking, facilitate engine starting, electric stabilization of the system), industry (forklifts, elevators), hybrid off-road machinery and also in consumer electronics. Supercapacitor electrodes require highly porous material. Typically, activated carbon is used. Specific surface area of activated carbon is approximately 1000 m2 per gram. Carbon nanotubes represent one of prospective materials. According to numerous studies this material allows to improve the properties of supercapacitors. The task of this Master‘s Thesis was to test multiwalled carbon nanotubes and become confident with the testing methods.

Kulutuselektroniikan akkujen tekniset ominaisuudet ja markkinaosuudet 2015

Työssä tutkittiin kirjallisuustyönä akkuteknologian nykytilaa ja markkinoita kulutuselektroniikan osalta. Työssä tehtiin myös katsaus potentiaalisiin tulevaisuuden akkuteknologioihin. Työssä havaittiin, että kulutuselektroniikassa ainoat suuresti käytetyt akkutyypit ovat nikkelimetallihybridi- (NiMH) ja litiumioniakut (Li-ion). Tärkeimpänä ominaisuutena kulutuselektroniikassa akuilla yleensä pidetään kapasiteettia, jossa Li-ion akut ovat selvästi parempia jopa kaksinkertaisen energiatiheyden takia. Li-ion akuilla voidaan saavuttaa myös moninkertainen käyttöikä lataussykleinä ja moninkertainen purkausvirta, riippuen käytetystä katodimateriaalista. NiMH akuilla etuna on lähinnä halvempi hinta ja parempi turvallisuus. Toisaalta myös pieni jännite voidaan laskea hyväksi puoleksi, koska NiMH akuilla voidaan korvata kertakäyttöisiä alkaliparistoja. Vuonna 2012 Li-ion akkuja myytiin kapasiteetissa mitattuna jopa kahdeksan kertaa enemmän kuin NiMH akkuja ja myyntimäärien ennustetaan myös kasvavan tulevaisuudessa. Liion akkujen myyntimääristä suurin osa oli kulutuselektroniikan käyttökohteisiin ja jopa kaksi kolmasosaa oli kannettavien tietokoneiden ja kännyköiden akkuja. Uusia akkuteknologioita ja Li-ion akkujen parannuksia on paljon kehitteillä, mutta suurimman potentiaalin ja myös suuret ongelmat kaupallistumiseen omaa litium-ilma akut. Lyhyemmällä aikavälillä potentiaalisia teknologioita ovat litium-rikki akut, sekä nykyisiin Li-ion akkuihin kehitteillä olevat anodimateriaalit kuten esim. pii ja alumiini/titaani, joiden ongelmiin on löydetty ratkaisuja nanoteknologiasta.

”Studies on Selected conducting polymers for Microwave and Electrical Applications

The electrical properties of polymers make up an inherently interdisciplinary topic, being closely associated, on the one hand, with the mechanical properties of polymers polarization and relaxation) and, on the other hand, with the semi conductive properties (conduction and break down). In addition, unlike conventional technologies, which use these properties in its various applications like antistatic coatings, rechargeable batteries, sensors, electrochromic devices, electrochemical devices etc, microwave technology extract the microwave absorbing ability of electrically conducting polymers. The conducting polymers are widely used in its potential applications like electro magnetic interference shielding, satellite communication links, beam steering radars, frequency selective surfaces etc. Considering the relevance of microwave applications of conducting polymers, the study of microwave properties of conducting polymers stands poised to become a compelling choice for synthetic chemists and condensed - matter physicists, physical chemists and material scientists, electrochemists and polymer scientists. The main aim of the present work is to study the microwave and low frequency properties of various conducting polymers, conducting semi-interpenetrating networks, conducting copolymers and to characterise it. Also this thesis collated the microwave properties of these conducting systems and exposes the various technologically important applications in the industrial, scientific, communication and defence applications.

Studies On The Electrical Properties Of Some Crystalline Organic Compounds And Conducting Polymers

Solid electrolytes for applications like chemical sensing, energy storage, and conversion have been actively investigated and developed since the early sixties. Although of immense potential, solid state protonic conductors have been ignored in comparison with the great interest that has been shown to other ionic conductors like lithium and silver ion conductors. The non-availability of good, stable protonic conductors could be partly the reason for this situation. Although organic solids are better known for their electrical insulating character, ionic conductors of organic origin constitute a recent addition to the class of ionic conductors. However, detailed studies (N1 such conductors are scarce. Also the last decade has witnessed an unprecedented boom in research on organic "conducting polymers". These newly devised materials show conductivity spanning from insulator to metallic regimes, which can be manipulated by appropriate chemical treatment. They find applications in devices ranging from rechargeable batteries to "smart windows". This thesis mainly deals with the synthesis and investigations on the electrical properties of (i) certain organbc protonic conductors derived from ethylenediamine and (ii) substituted polyanilines

Evaluation of the Power Consumption of Routing Protocols for Wireless Sensor Networks

Sensor networks are one of the fastest growing areas in broad of a packet is in transit at any one time. In GBR, each node in the network can look at itsneighbors wireless ad hoc networking (? Eld. A sensor node, typically'hop count (depth) and use this to decide which node to forward contains signal-processing circuits, micro-controllers and a the packet on to. If the nodes' power level drops below a wireless transmitter/receiver antenna. Energy saving is one certain level it will increase the depth to discourage trafiE of the critical issue for sensor networks since most sensors are equipped with non-rechargeable batteries that have limitedlifetime. Routing schemes are used to transfer data collectedby sensor nodes to base stations. In the literature many routing protocols for wireless sensor networks are suggested. In this work, four routing protocols for wireless sensor networks viz Flooding, Gossiping, GBR and LEACH have been simulated using TinyOS and their power consumption is studied using PowerTOSSIM. A realization of these protocols has beencarried out using Mica2 Motes.

Evaluation of the Power Consumption of Routing Protocols for Wireless Sensor Networks

Sensor networks are one of the fastest growing areas in broad of a packet is in transit at any one time. In GBR, each node in the network can look at itsneighbors wireless ad hoc networking (? Eld. A sensor node, typically'hop count (depth) and use this to decide which node to forward contains signal-processing circuits, micro-controllers and a the packet on to. If the nodes' power level drops below a wireless transmitter/receiver antenna. Energy saving is one certain level it will increase the depth to discourage trafiE of the critical issue forfor sensor networks since most sensors are equipped with non-rechargeable batteries that have limited lifetime.

Evaluation of the Power Consumption of Routing Protocols for Wireless Sensor Networks

Sensor networks are one of the fastest growing areas in broadwireless ad hoc networking (?Eld. A sensor node, typically'contains signal-processing circuits, micro-controllers and awireless transmitter/receiver antenna. Energy saving is oneof the critical issue for sensor networks since most sensorsare equipped with non-rechargeable batteries that have limited lifetime.In thiswork, four routing protocols for wireless sensor networks vizFlooding, Gossiping, GBR and LEACH have been simulated using Tiny OS and their power consumption is studied usingcaorwreiredTOoSuStIuMs.ingAMirceaal2izMaotitoens.of these protocols has been carried out using mica 2 motes

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.