Rozprawy doktorskie na temat „Lithium gel polymer electrolyte system”

The transition from fossil fuels to renewable resources has created more demand for energy storage devices. Lithium-oxygen (Li-O2) batteries have attracted much attention due to their high theoretical energy densities. They, however, are still in their infancy and several fundamental challenges remain to be addressed. Advanced analytical techniques have revealed that all components of a Li-O2 battery undergo undesirable degradation during discharge/charge cycling, contributing to reduced cyclability. Despite many attempts to minimize the anode and cathode degradation, the electrolyte remains as the leading cause for rapid capacity fading and poor cyclability in Li-O2 batteries. In this dissertation, composite gel polymer electrolytes (cGPEs) consisting of a UV-curable polymer, tetragylme based electrolyte, and glass microfibers with a diameter of ~1 µm and an aspect ratio of >100 have been developed for their use in Li-O2 battery application. The Li-O2 batteries containing cGPEs showed superior charge/discharge cycling for 500 mAh.g-1 cycle capacity with as high as 400% increase in cycles for cGPE over gel polymer electrolytes (GPEs). Results using in-situ electrochemical impedance spectroscopy (EIS), Raman spectroscopy, and scanning electron microscopy revealed that the source of the improvement was the reduction of the rate of lithium carbonates formation on the surface of the cathode. This decrease in formation rate afforded by cGPE-containing batteries was possible due to the decrease of the rate of electrolyte decomposition. The increase in solvated to the paired Li+ ratio at the cathode, afforded by increased lithium transference number, helped lessen the probability of superoxide radicals reacting with the tetraglyme solvent. This stabilization during cycling helped prolong the cycling life of the batteries. The effect of ion complexes on the stability of liquid glyme based electrolytes with various lithium salt concentrations has also been investigated for Li-O2 batteries. Charge/discharge cycling with a cycle capacity of 500 mAh·g-1 showed an improvement as high as 300% for electrolytes containing higher lithium salt concentrations. Analysis of the Raman spectroscopy data of the electrolytes suggested that the increase in lithium salt concentration afforded the formation of cation-solvent complexes, which in turn, mitigated the tetragylme degradation.

The demand for electric vehicles is increasing rapidly as the world is preparing for a fossil fuel-free future in the automotive field. Lithium battery technologies are the most effective options to replace fossil fuels due to their higher energy densities. However, safety remains a major concern in using lithium as the anode, and the development of non-volatile, non-flammable, high conductivity electrolytes is of great importance. In this dissertation, a gel polymer electrolyte (GPE) consisting of ionic liquid, lithium salt, and a polymer has been developed for their application in lithium batteries. A comparative study between GPE and ionic liquid electrolyte (ILE) containing batteries shows a superior cyclic performance up to 5C rate and a better rate capability for 40 cycles for cells with GPE at room temperature. The improvement is attributed to GPE’s improved stability voltage window against lithium as well as higher lithium transference number. The performance of the GPE in lithium-sulfur battery system using sulfur-CNT cathodes shows superior rate capability for the GPE versus ILE for up to 1C rates. Also, GPE containing batteries had higher capacity retention versus ILE when cycled for 500 cycles vii at C/2 rate. Electrochemical impedance spectroscopy (EIS) studies reveal interfacial impedances for ILE containing batteries grew faster than in GPE batteries. The accumulation of insoluble Li2S2/Li2S on the electrodes decreases the active material thus contributes to capacity fading. SEM imaging of cycled cathodes reveals cracks on the surface of cathode recovered from ILE batteries. On the other hand, the improved electrochemical performance of GPE batteries indicates better and more stable passivation layer formation on the surface of the electrodes. Composite GPE (cGPE) containing micro glass fillers were studied to determine their electrochemical performance in Li batteries. GPE with 1 wt% micro fillers show superior rate capability for up to 7C and also cyclic stability for 300 cycles at C/2 rate. In situ, EIS also reveals a rapid increase in charge transfer resistance in GPE batteries, responsible for lowering the capacity during cycling. Improved ion transport properties due to ion-complex formations in the presence of the micro fillers, is evidenced by improved lithium transference number, ionic conduction, and ion-pair dissociation detected using Raman spectroscopy.

Dans le but d’améliorer les performances des micro-accumulateurs au lithium, de nouvelles voies de dépôt, compatibles avec des géométries texturées, sont actuellement explorées. Au cours de ce travail de thèse, un nouvel électrolyte solide déposé par voie « humide » a été développé. Ce matériau, composé d’un liquide ionique et d’un sel de lithium confinés dans une matrice solide, a été synthétisé par polymérisation in-situ d’un oligomère diméthacrylate. Afin de définir leurs caractéristiques de conduction ionique, de nouvelles méthodes, comme le suivi de la photo-polymérisation par impédance in-situ ou encore la réalisation d’un nouveau design de cellules à base de peignes interdigités, ont été développées. De plus, le transfert du lithium a été mesuré par RMN diffusionnelle. Une diminution significative de la vitesse de diffusion des ions Li+ après la photo-polymérisation a ainsi été mise en évidence. La spectroscopie Raman a permis de démontrer que celle-ci est due à la complexation des ions par les chaines de poly(oxyde d’éthylène) de la matrice solide. En outre, grâce aux observations de différentes compositions, un mécanisme de diffusion mixte des ions Li+ par migration dans le liquide et par sauts dans le solide a été identifié. Par conséquent, ces résultats nous ont permis de définir une stratégie pour améliorer la diffusion des ions Li+ : l’ajout d’un copolymère monofonctionnel a permis de diminuer la densité de réticulation de la matrice solide et ainsi d’optimiser la mobilité des chaines polymères. En effet, les performances de cyclage dans des empilements de micro-accumulateurs complets ont été améliorées. A température ambiante, ces résultats se sont révélés très proches de ceux obtenus avec l’électrolyte solide standard LiPON. En conclusion, l’analyse établie a permis de comprendre les liens entre structure et performances électrochimiques, ce qui a permis de dégager les voies d’amélioration les plus prometteuses pour ce type d’électrolytes
New deposition techniques compatible with making tridimensional geometries are currently being investigated with the aim of improving the performances of lithium microbatteries. This work focuses on the development of a new quasi-solid electrolyte deposited by a “wet process”. An ionic liquid-based membrane containing a lithium salt was prepared by the photo-induced polymerization of a dimethacrylate oligomer. New methods such as a new type of conductivity cell based on planar interdigitated electrodes to measure ionic conductivity as well as in-situ monitoring of photo-polymerization using impedance spectroscopy were used. Transport properties of lithium ion were measured by PGSE-NMR. Interestingly, a significant reduction of lithium ion mobility was observed after UV-curing while the total ionic conductivity only decreased slightly. This phenomenon is due to the formation of lithium ion complexes with ethylene oxide moieties of the solid matrix, evidenced by Raman spectroscopy measurements. Additionally, we have shown that the structures of the complexes depend on the salt concentration and a dual solid/liquid transport mechanism was suggested. Hence, in order to improve lithium ion diffusion, a co-polymer was added in an attempt to decrease the cross-linking density of the solid matrix thus improving its segmental motion. The cyclability of the all solid state micro batteries was indeed improved. Comparable performances with the standard solid electrolyte LiPON were obtained at room temperature. In summary, it was established that electrochemical performances of the solid state microbatteries depend to a certain extent on the structure of the polymer electrolyte. Therefore it is possible to find new ways in designing these types of electrolytes for further improvement

The optimisation of existing chemistries by the introduction of environmentally friendly materials and the simplification of the device production process are intriguing challenges to promote the future widespread diffusion of LIBs. Moreover, the recent development of the next-generation electronic devices promoted a new research field for the modification of the current systems into light, flexible and/or micro-sized device. The enhancement of mechanical properties through the introduction of flexible electrodes will enable LIBs to be embedded into various functional systems in a wide range of innovative products such as smart cards, displays and implantable medical devices. Moreover, the optimisation of the electrolyte by moving towards an all-solid-state configuration will offer adaptability to various designs and stressful mechanical handling, as well as enhance cell safety and reliability. During the three years of the Ph.D. course, the attention was focused on the optimisation of innovative materials for Li-ion batteries as well as the development of easily up-scalable procedures for the production of electrodes and polymer electrolytes. The basic idea was to start from eco-friendly materials to develop simple, low-cost and easily adaptable processes in order to propose innovative solutions for LIBs with a wide range of possible applications. Moreover, during my experimental activities, I considered the performances and the cycling stability of Li-ion batteries, by studying the mechanisms related to the capacity fade of lab-scale batteries and also by analysing commercial Li-ion batteries for automotive application. The results of the research work are presented in this thesis (Chapters 4-7) following an introductory section that provides the general information needed to follow the discussions (Chapters 1-3). The experimental research work presented in Chapter IV was carried out in collaboration with the Laboratory of Pulp and Paper Science and Graphic Arts (LGP2) in Grenoble (France). A well-known natural material such as cellulose was exploited for the production of innovative low-cost and easily recyclable electrodes for Li-ion batteries. A simple aqueous filtration process, based on a well-known industrialised paper-making technology, was developed and the electrodes (graphite-based anodes and LiFePO4-based cathodes) produced and partly characterized in Grenoble by Dr. Lara Jabbour were electrochemically studied in our Labs in Politecnico di Torino. In particular, cellulose fibres (FBs) were used as natural binder for the production of paper-like electrodes obtained without addition of any synthetic binder and/or solvent and showing electrochemical performance comparable to those produced with the same active materials by a standard process. In Chapter V, results are reported regarding a newly developed procedure where a methacrylic-based polymer electrolyte is directly formed in situ at the interface with the electrodes. Exploiting the versatile nature of UV-induced free-radical photo-polymerisation, novel ready-to-use multiphase electrode/electrolyte composites (MEEC) were developed in which the electrode is conformally coated by the polymer electrolyte. This “one-shot” process was successfully applied to enhance the cycling performances of two nanostructured materials conceived for microbattery application, such as Cu2O (in collaboration with CSHR@Polito IIT research institute in Torino) and V2O5 (in collaboration with Prof. Mustarelli’s group in University of Pavia), prepared in the form of thin films and proposed respectively as anode and cathode. The proposed one-shot process, thanks to the intimate interfacial contact between electrodes surface and electrolyte obtained by in situ process, induced a huge effect of stabilization thus improving the cycling stability of both the nanostructures. All along Chapter VI, the problems related to the assembling of complete Li-ion cells, starting from two well performing electrodes, are progressively discussed and valuable solutions are proposed. A strong capacity fade was initially found, thus the possible causes were studied also considering the failure mechanisms proposed in the literature. Several measures were adopted to improve the cycling stability, considering the effect of all the different cell components as well as the effects of both charging protocol and cell apparatus. Moreover, due the knowhow progressively achieved on the intimate characteristics of complete Li-ion cells and their assembly, even thanks to a three months stage at ENEA Casaccia Research Centre of Rome, the installation of a 10 m2 dry room was personally followed at our Electrochemistry Research Group Labs in Politecnico di Torino and the results obtained are presented in the same Chapter VI. These results include the realisation of an all-paper Li-ion battery with the cellulose-based electrodes and paper hand-sheets as separator. Finally, the cycling stability and the failure prediction issue was studied for a 53 Ah commercial battery. The results obtained, by means of different standard reference tests, are reported in Chapter VII. The commercial battery was also disassembled in the controlled atmosphere of an Ar-filled dry box in order to study the system structure and characterise the various components. A testing protocol was personally developed and the results obtained allowed to evaluate the commercial battery based on the performances requested for HEV and EV application. In particular, an easy measure of the internal resistance was developed, by opportunely modulating the measured parameters, and the obtained results were found to be very useful in directly predicting the cell failure which is fundamental in practical application.

Au cours de cette thèse, un nouvel électrolyte polymère gel pour la réalisation de microbatteries au lithium a été développé. Le gel a été préparé par « confinement » d’une phase de N-propyl-N-méthylpyrrolidinium bis(fluorosulfonyl)imide (P13FSI) et de LiTFSI dans un réseau semi-interpénétré (sRip) de polymère (PVdFHFP/ réseau de POE). L’électrolyte gel a tout d’abord été optimisé et étudié en termes de propriétés physicochimiques et de transport ionique en fonction de sa composition. Ensuite, des batteries Li/LiNi1/3Mn1/3Co1/3O2 ont été assemblées en utilisant l’électrolyte sRip. Les performances ont par ailleurs été comparées aux systèmes de références utilisant l’électrolyte à base de POE ou de PVdF-HFP. Outre ses propriétés améliorées par rapport au PVdF-HFP et au réseau de POE (propriétés mécaniques, confinement), l’électrolyte sRip est compatible avec le procédé de dépôt de l’électrode négative en lithium par évaporation sous vide. L’électrolyte sRip optimisé a donc été utilisé pour fabriquer une nouvelle génération de microbatteries en s’affranchissant de l’électrolyte céramique, le LiPON, afin d’abaisser la résistance interne. Les microbatteries Li/sRip gel/LiCoO2 délivrent une capacité nominale stable de 850 μAh à C sur 100 cycles à 25°C
In this thesis, a new polymer gel electrolyte was prepared and optimized for Li based microbatteries. The gel consisted of an ionic liquid based phase (P13FSI/LiTFSI) confined in a semi-interpenetrating polymers (sIPN) network (PVdF-HFP/crosslinked PEO). sIPN electrolytes were prepared and optimized according to the PVdFHFP/ crosslinked PEO ratio and the liquid phase fraction. Furthermore, the sIPN electrolyte was used as an electrolyte in Li/LiNi1/3Mn1/3Co1/3O2 battery. The performances of the battery (specific capacity, efficiency, cyclability) were determined and compared to batteries using a crosslinked PEO or PVdF-HFP based gel. Such a thin and stable sIPN electrolyte film enabled the preparation of Li based microbatteries using thermal evaporation deposition of lithium directly conducted on the sIPN electrolyte film. This assembly (Li/sIPN) was therefore used to prepare a LiCoO2/sIPN gel/Li quasi solid-state microbattery. This microbattery showed a stable nominal capacity of 850 μAh for over 100 cycles of charge and discharge under 1 C rate at 25°C

Předkládaná práce se zabývá výzkumem nových materiálů a metod přípravy gelových polymerních elektrolytů (GPE) na bázi methakrylátů, které lze zejména vzhledem k jejich mechanickým vlastnostem s výhodou využít při konstrukci elektrochromních (EC) prvků.

This master‘s thesis concerns gel polymer electrolytes formed on a methyl methacrylate base with selected types of nanoparticles. In the thesis are also analyzed the methods for measuring electrochemical properties. The practical portion deals with sample preparations of gel polymer electrolytes with different contents of alkaline salt in a solvent, creating gels with different nanoparticle content and comparing gel polymer electrolytes polymerized with heat and UV radiation. The thesis deals with the evaluation of these samples from the viewpoint of electrical conductivity and potential windows as well as thermal analysis of selected samples.

The current upsurge in demand for high energy density batteries for applications across industries ranging from small scale portable electronics, electric automobiles to storage grids, has led to research in next generation, beyond lithium -ion batteries. Alkali metals like lithium and sodium, by virtue of their high theoretical capacity (3860 mAhg-1 for Li and 1165 mAhg-1 for Na) and low electrochemical potentials, are most suitable anodes for producing high energy density batteries. The vigorous reactivity, unstable solid-electrolyte interface and dendrite formation are some of the major hurdles towards use of lithium and sodium as anodes in a conventional liquid electrolyte battery. A well designed and optimised electrolyte plays a paramount role towards safe operation of an alkali metal battery. In the present thesis, we have explored few free-standing, mechanically stable plasticised gel polymer electrolytes (GPE) for lithium and sodium metal battery which has been demonstrated to have a good ionic conductivity with very stable interfacial properties and suppressed dendrite growth. A spectroscopic investigation into the ion-conduction mechanism in a concentrated lithium gel polymer electrolyte system has also been described in detail. Along with the stable performance of alkali metal batteries with the designed GPEs, we have also ventured into few high-capacity cathodes like sulphur and oxygen using modified electrolytes.

The present thesis demonstrates and discusses polymeric ion and mixed ion-electron conductors for rechargeable batteries based on lithium viz. lithium-ion and lithium-sulphur batteries. The proposed polymer ion conductors in the thesis are discussed primarily as potential alternatives to conventional liquid and solid-crystalline electrolytes in lithium-ion batteries. These discussions are part of Chapters 2-4. On the other hand, the polymer based mixed ion-electron conductor is demonstrated as a novel electrode for lithium-Sulphur battery in Chapter 5. Possibility of application of polymer ion conductors is discussed in the context of Li-S battery in Chapter 6. A distinct correlation between the physical properties and electrochemical performance of the proposed conductors is highlighted in detail in this thesis. Systematic investigation of the ion transport mechanism in the polymeric ion conductors has been carried out using various spectroscopic techniques at different time and length scales. Such detailed investigations demonstrate the key structural and physical parameters for design of alternative polymer conductors for rechargeable batteries. Though the thesis discusses the various polymeric conductors in the context of lithium-based batteries, it is strongly felt that the design strategies are equally likely to be beneficial for different battery chemistries as well as for other electrochemical generation and storage devices. A brief discussion of the contents and highlights of the individual chapters are described below: The thesis comprises of six Chapters. Chapter 1 briefly reviews the important developments and materials of lithium-based batteries, with specific focus on Li-ion and Li-S batteries. It starts with discussions on different types of liquid, solid crystalline and solid-like electrolytes. Their materials characteristics, advantages and disadvantages are discussed in the context of secondary batteries such as lithium-ion and lithium-sulphur batteries. As prospective alternative electrolytes polymer based soft matter electrolytes are discussed in detail. Special emphasis is given to the recent developments in polymer electrolytes and their ion conduction mechanism, which are central themes to this thesis. The importance of investigation of charge transport, typically ion, on electrochemical processes is also briefly discussed in Chapter 1. A brief discussion about the characteristics, materials and non-trivialities of the electrochemical storage process in Li-S battery is also reviewed. Chapter 2A demonstrates a binary polymer physical network based gel (PN-x) electrolyte, comprising of an ionic liquid confined inside a binary polymer system for electrochemical devices such as secondary batteries. The synthesis, physical property and electrochemical performances are studied as a function of content of one of the polymers in this Chapter. A physical network of two polymers with different functional groups leads to multiple interesting consequences. The polymer physical network characteristics determine all physical properties including electrochemical property of the ionic liquid integrated PN based GPE. The conductivities of the proposed gel are nearly an order in magnitude higher than the unconfined ionic liquid electrolyte and displays good dimensional stability and electrochemical performance in a separator-free battery configuration. The ac-impedance spectroscopy, steady shear viscosity measurement, dynamic rheology are employed to study physical properties of the proposed gel polymer electrolyte. Chapter 2B discusses the detailed investigations of the ion transport mechanism of the gel polymer electrolyte, as discussed in Chapter 2A. Ion conduction mechanism is investigated in the light of ion diffusion and solvent dynamics of the entrapped ionic liquid inside the polymer. The studies reveal a heavy influence of network characteristics on the ion conduction mechanism. The influence of solvent dynamics on the ion transport is drastically altered by polymer physical network. Consequently, a drastic change in the ion mobility and nature of predominant charge carrier is observed in the polymer physical network based gel electrolyte. A clear transformation from dual ion conductivity to a predominantly anion conductivity is observed on going from single polymer to a dual polymer network. The spectroscopic tools such as pulsed field gradient nuclear magnetic resonance (PFG–NMR), Brillouin light scattering spectroscopy, ac-impedance spectroscopy, FT-Raman and FTIR spectroscopy were used to elucidate the ion transport mechanism in the Chapter. Chapter 3 demonstrates a simple design strategy of gel polymer electrolyte comprising of a lithium salt (lithium bis(trifluoromethanesulfonyl) imide, LiTFSI) solvated by two plastic crystalline solvents, one a solid (succinonitrile, abbreviated as SN) and another a (room temperature) ionic liquid (1-butyl-1-methyl-pyrrolidinium bis(trifluoromethane sulfonyl) imide, (abbreviated as IL) confined inside a linear network of poly(methyl methacrylate) (PMMA). The concentration of the IL component determines the physical properties of the unconfined electrolyte and when confined inside the polymer network in gel polymer electrolyte. Intrinsic dynamics of one plastic crystal influences the conduction mechanism of gel polymer electrolytes. The enhanced disordering in the plastic phase of succinonitrile by IL doping alters both the local ion environment and viscosity. The proposed plastic crystal electrolytes show predominantly anion conduction (tTFSI ≈ 0.5) however, lithium transference number (tLi ≈ 0.2) is nearly an order higher than the ionic liquid electrolyte (IL-LiTFSI) (tLi ≈ 0.02-0.06), discussed in Chapter 2. The gel polymer electrolyte displayed high mechanical compliability, stable Li-electrode | electrolyte interface, low rate of Al corrosion and stable cyclability. The promising electrochemical performance further justifies simple strategy of employing mixed physical state plasticizers to tune the physical properties of polymer electrolytes requisite for application in rechargeable batteries. Chapter 4A proposes a novel liquid dendrimer–based single ion conducting liquid electrolyte as potential alternative to conventional molecular liquid solvent–salt solutions and conventional solid polymer electrolytes for rechargeable batteries, sensors and actuators. The physical properties are investigated as a function of peripheral functionalities in the first generation poly(propyl ether imine) (G1-PETIM)–lithium salt complexes. The change in peripheral group simultaneously affects the effective physical properties viz. viscosity, ionic conductivity, ion diffusion coefficients, transference numbers and also the electrochemical response. The specific change from ester (–COOR) to cyano (–CN) terminated peripheral group resulted in a remarkable switch over from a high cation (tLi+ = 0.9 for –COOR) to a high anion (tPF6- = 0.8 for –CN) transference number. Chapter 4B presents an analysis of the frequency dependent ionic conductivity of single ion dendrimer conductors by using time temperature scaling principles (TTSPs) and dielectric modeling of the electrode polarization. The TTSP provides information on the salt dissociation and number density of mobile charges and hence provides direct insights into the ion conduction mechanism. Summerfield and Baranovskii–Cordes scaling laws, which are well known TTSPs, have been applied to analyze the ion conductivity. The electrode polarization, which quantifies the number density of mobile charges and ionic mobility, is studied using Macdonald-Coelho model of electrode polarization. The combination of these two theoretical investigations of the experimental data emanating from one technique i.e. ac– impedance spectroscopy, predicts independently the contributions of the effect of mobile ion charges and ionic mobility to ion conduction mechanism. In Chapter 5 focus shifts from polymer ion conductors to polymer mixed ion-electron conductor. The polymer mixed ion-electron conductor is demonstrated as a novel electrode material for Li-S battery. A simple strategy to overcome the challenges towards practical realization of a stable high performance Li–S battery is discussed. A soft mixed conducting polymeric network is utilized to configure sulphur nanoparticle. The soft matter network provides efficient and distinct pathways for lithium and electron conduction simultaneously. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li–S batteries. The S-MIEC is characterized by several methods: powder-X-ray diffraction (PXRD), thermo gravimetric analysis (TGA), fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), ac-impedance spectroscopy and dc current-voltage measurements are performed to evaluate conductivity of S-MIEC cathode. Electrochemical studies such as cyclic voltammetry, galvanostatic charge-discharge cycling, galvanostatic intermittent titration (GITT) are performed to demonstrate feasibility of S-MIEC in the Li–S battery performance. Chapter 6 provides a brief summary of the work carried out as part of this thesis and also demonstrates the future perspective of the present work. Potential of the polymer physical network based gel polymer electrolytes, which are discussed in Chapter 2A-B for lithium-ion batteries, are demonstrated in Li-S battery. The proposed polymer physical network confines higher order lithium polysulfides (typically Li2S8) dissolved in tetraethylene glycol dimethyl ether (TEGDME) based electrolyte (TEGDME-1M LiTFSI). The three dimensional polymer network is proposed to be formed by physical blending of the poly(acrylonitrile) (PAN) with the copolymer of AN and poly(ethylene glycol) methyl ether methacrylate (PEGMA), [ P(AN–co–PEGMA)]. We extend here the similar synthetic approaches as described in Chapter 2A. The approach proposed and demonstrated in this concluding Chapter is expected to mitigate some of the major issues of Li-S chemistry. The proposed Li2S8 confined gel electrolyte exhibits moderately high values of ionic conductivity, 2 × 10-3 Ω-1cm-1 and shows a stable capacity of 350 mAhg-1 over 30 days in a separator free Li-S battery.

The present thesis demonstrates and discusses polymeric ion and mixed ion-electron conductors for rechargeable batteries based on lithium viz. lithium-ion and lithium-sulphur batteries. The proposed polymer ion conductors in the thesis are discussed primarily as potential alternatives to conventional liquid and solid-crystalline electrolytes in lithium-ion batteries. These discussions are part of Chapters 2-4. On the other hand, the polymer based mixed ion-electron conductor is demonstrated as a novel electrode for lithium-Sulphur battery in Chapter 5. Possibility of application of polymer ion conductors is discussed in the context of Li-S battery in Chapter 6. A distinct correlation between the physical properties and electrochemical performance of the proposed conductors is highlighted in detail in this thesis. Systematic investigation of the ion transport mechanism in the polymeric ion conductors has been carried out using various spectroscopic techniques at different time and length scales. Such detailed investigations demonstrate the key structural and physical parameters for design of alternative polymer conductors for rechargeable batteries. Though the thesis discusses the various polymeric conductors in the context of lithium-based batteries, it is strongly felt that the design strategies are equally likely to be beneficial for different battery chemistries as well as for other electrochemical generation and storage devices. A brief discussion of the contents and highlights of the individual chapters are described below: The thesis comprises of six Chapters. Chapter 1 briefly reviews the important developments and materials of lithium-based batteries, with specific focus on Li-ion and Li-S batteries. It starts with discussions on different types of liquid, solid crystalline and solid-like electrolytes. Their materials characteristics, advantages and disadvantages are discussed in the context of secondary batteries such as lithium-ion and lithium-sulphur batteries. As prospective alternative electrolytes polymer based soft matter electrolytes are discussed in detail. Special emphasis is given to the recent developments in polymer electrolytes and their ion conduction mechanism, which are central themes to this thesis. The importance of investigation of charge transport, typically ion, on electrochemical processes is also briefly discussed in Chapter 1. A brief discussion about the characteristics, materials and non-trivialities of the electrochemical storage process in Li-S battery is also reviewed. Chapter 2A demonstrates a binary polymer physical network based gel (PN-x) electrolyte, comprising of an ionic liquid confined inside a binary polymer system for electrochemical devices such as secondary batteries. The synthesis, physical property and electrochemical performances are studied as a function of content of one of the polymers in this Chapter. A physical network of two polymers with different functional groups leads to multiple interesting consequences. The polymer physical network characteristics determine all physical properties including electrochemical property of the ionic liquid integrated PN based GPE. The conductivities of the proposed gel are nearly an order in magnitude higher than the unconfined ionic liquid electrolyte and displays good dimensional stability and electrochemical performance in a separator-free battery configuration. The ac-impedance spectroscopy, steady shear viscosity measurement, dynamic rheology are employed to study physical properties of the proposed gel polymer electrolyte. Chapter 2B discusses the detailed investigations of the ion transport mechanism of the gel polymer electrolyte, as discussed in Chapter 2A. Ion conduction mechanism is investigated in the light of ion diffusion and solvent dynamics of the entrapped ionic liquid inside the polymer. The studies reveal a heavy influence of network characteristics on the ion conduction mechanism. The influence of solvent dynamics on the ion transport is drastically altered by polymer physical network. Consequently, a drastic change in the ion mobility and nature of predominant charge carrier is observed in the polymer physical network based gel electrolyte. A clear transformation from dual ion conductivity to a predominantly anion conductivity is observed on going from single polymer to a dual polymer network. The spectroscopic tools such as pulsed field gradient nuclear magnetic resonance (PFG–NMR), Brillouin light scattering spectroscopy, ac-impedance spectroscopy, FT-Raman and FTIR spectroscopy were used to elucidate the ion transport mechanism in the Chapter. Chapter 3 demonstrates a simple design strategy of gel polymer electrolyte comprising of a lithium salt (lithium bis(trifluoromethanesulfonyl) imide, LiTFSI) solvated by two plastic crystalline solvents, one a solid (succinonitrile, abbreviated as SN) and another a (room temperature) ionic liquid (1-butyl-1-methyl-pyrrolidinium bis(trifluoromethane sulfonyl) imide, (abbreviated as IL) confined inside a linear network of poly(methyl methacrylate) (PMMA). The concentration of the IL component determines the physical properties of the unconfined electrolyte and when confined inside the polymer network in gel polymer electrolyte. Intrinsic dynamics of one plastic crystal influences the conduction mechanism of gel polymer electrolytes. The enhanced disordering in the plastic phase of succinonitrile by IL doping alters both the local ion environment and viscosity. The proposed plastic crystal electrolytes show predominantly anion conduction (tTFSI ≈ 0.5) however, lithium transference number (tLi ≈ 0.2) is nearly an order higher than the ionic liquid electrolyte (IL-LiTFSI) (tLi ≈ 0.02-0.06), discussed in Chapter 2. The gel polymer electrolyte displayed high mechanical compliability, stable Li-electrode | electrolyte interface, low rate of Al corrosion and stable cyclability. The promising electrochemical performance further justifies simple strategy of employing mixed physical state plasticizers to tune the physical properties of polymer electrolytes requisite for application in rechargeable batteries. Chapter 4A proposes a novel liquid dendrimer–based single ion conducting liquid electrolyte as potential alternative to conventional molecular liquid solvent–salt solutions and conventional solid polymer electrolytes for rechargeable batteries, sensors and actuators. The physical properties are investigated as a function of peripheral functionalities in the first generation poly(propyl ether imine) (G1-PETIM)–lithium salt complexes. The change in peripheral group simultaneously affects the effective physical properties viz. viscosity, ionic conductivity, ion diffusion coefficients, transference numbers and also the electrochemical response. The specific change from ester (–COOR) to cyano (–CN) terminated peripheral group resulted in a remarkable switch over from a high cation (tLi+ = 0.9 for –COOR) to a high anion (tPF6- = 0.8 for –CN) transference number. Chapter 4B presents an analysis of the frequency dependent ionic conductivity of single ion dendrimer conductors by using time temperature scaling principles (TTSPs) and dielectric modeling of the electrode polarization. The TTSP provides information on the salt dissociation and number density of mobile charges and hence provides direct insights into the ion conduction mechanism. Summerfield and Baranovskii–Cordes scaling laws, which are well known TTSPs, have been applied to analyze the ion conductivity. The electrode polarization, which quantifies the number density of mobile charges and ionic mobility, is studied using Macdonald-Coelho model of electrode polarization. The combination of these two theoretical investigations of the experimental data emanating from one technique i.e. ac– impedance spectroscopy, predicts independently the contributions of the effect of mobile ion charges and ionic mobility to ion conduction mechanism. In Chapter 5 focus shifts from polymer ion conductors to polymer mixed ion-electron conductor. The polymer mixed ion-electron conductor is demonstrated as a novel electrode material for Li-S battery. A simple strategy to overcome the challenges towards practical realization of a stable high performance Li–S battery is discussed. A soft mixed conducting polymeric network is utilized to configure sulphur nanoparticle. The soft matter network provides efficient and distinct pathways for lithium and electron conduction simultaneously. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li–S batteries. The S-MIEC is characterized by several methods: powder-X-ray diffraction (PXRD), thermo gravimetric analysis (TGA), fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), ac-impedance spectroscopy and dc current-voltage measurements are performed to evaluate conductivity of S-MIEC cathode. Electrochemical studies such as cyclic voltammetry, galvanostatic charge-discharge cycling, galvanostatic intermittent titration (GITT) are performed to demonstrate feasibility of S-MIEC in the Li–S battery performance. Chapter 6 provides a brief summary of the work carried out as part of this thesis and also demonstrates the future perspective of the present work. Potential of the polymer physical network based gel polymer electrolytes, which are discussed in Chapter 2A-B for lithium-ion batteries, are demonstrated in Li-S battery. The proposed polymer physical network confines higher order lithium polysulfides (typically Li2S8) dissolved in tetraethylene glycol dimethyl ether (TEGDME) based electrolyte (TEGDME-1M LiTFSI). The three dimensional polymer network is proposed to be formed by physical blending of the poly(acrylonitrile) (PAN) with the copolymer of AN and poly(ethylene glycol) methyl ether methacrylate (PEGMA), [ P(AN–co–PEGMA)]. We extend here the similar synthetic approaches as described in Chapter 2A. The approach proposed and demonstrated in this concluding Chapter is expected to mitigate some of the major issues of Li-S chemistry. The proposed Li2S8 confined gel electrolyte exhibits moderately high values of ionic conductivity, 2 × 10-3 Ω-1cm-1 and shows a stable capacity of 350 mAhg-1 over 30 days in a separator free Li-S battery.

碩士
國立成功大學
化學系
102
Gel polymer electrolytes (GPE) have been attractive for the development of plastic Li ion batteries since they combine the advantages of liquid electrolytes (high ionic conductivity) and polymers (free from leaks, good mechanical strength). Gel polymer electrolytes (GPEs) were prepared by dipping a solid polymer electrolyte in 1.0M LiPF6 in ethylene carbonate (EC)/ dimethyl carbonate (DMC)/diethyl carbonate (DEC)(1:1:1 wt% + 2wt% VC) liquid electrolyte. Compare to commercial liquid electrolyte (LE). GPE has a stable electrochemical window up to 5 V vs. Li/Li+. Higher ionic conductivity up to above 1×10-3S/cm from 10 to 90 degrees C. Better lithium ion dissociation ability and higher transfer number (0.6). The performance test are evaluated in half-cell configurations (Li/GPE/LiFePO4)with different discharge rates. The specific half-cell capacities of GPE membraneis similar to commercial separator LE (from 0.1 to 1 C). Moreover, GPE has good cycling stability at room temperature. The specific properties of the polymer electrolyte membrane allow it to act as both an ionic conductor and separator.

碩士
國立中央大學
化學研究所
92
Abstract Rechargeable lithium ionic battery, compared to other secondary batteries, has the advantages of high working potential, high specific energy, wide applied temperature and no memory effect. However, in order to make a small light-weight batteries, a solid electrolyte was needed. Solid polymer electrolytes can be categorized into three types: dry-type polymer electrolyte, gel-type polymer electrolyte, and porous-type polymer electrolyte. In this studies, two systems were studied: polyaniline derivative was blended with PEO-LiClO4 electrolyte to increase the ionic conductivity of the dry-type polymer electrolyte and PVDF-HFP was mixed with polyalkoxy block copolymer such as P123 (Mw=5750) or F108 (Mw=14600) to form porous-type polymer membranes. The porous polymer membranes were then sock in LiClO4-EC/PC solution to form porous-type electrolytes. It was found that the ionic conductivity of dry-type polymer electrolyte is too low to be commercially viable. Therefore, the study is mainly focused on the porous-type polymer electrolyte. The porous membranes were prepared by both phase inversion and evaporating methods. They were then immersed in 1 M LiClO4 –EC/PC (1:1) solution to form porous polymer electrolytes. The pore structure and density of polymer membrane varied with the ratios of P123 (or F108). Low solution leakage, high conductivity polymer electrolyte was found when 30 ~ 50 wt% of P123 was blend with PVDF-HFP. The room temperature conductivity of these hybrid porous polymer electrolytes was up to 4 × 10-3 S/cm and they can stand up to 5.0 V. They have great potential to be applied in lithium ion batteries.

University of Technology, Sydney. Faculty of Science.
It has been well established that the electrolytes and cathodes have a significant effect on the electrochemical performance of lithium oxygen batteries. In this Master project, polymers were employed as electrolyte and cathode materials due to their unique superior properties. Using different methods, we synthesized suitable gel polymer electrolytes and conducting polymer catalysts for lithium oxygen batteries. Techniques such as field emission gun scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy were used to characterize the physical properties. Electrochemical analyses including the galvanostatic discharge and charge method, the cyclic voltammetry, the linear sweep voltammetry and the impedance spectra were conducted to determine the electrochemical performance for the as-prepared materials. Gel polymer electrolytes based on low molecular weight polyethylene glycol were prepared and used as electrolyte in lithium oxygen batteries. The as-prepared polymer electrolytes showed improved stability compared with liquid electrolytes and exhibited good performance in lithium oxygen batteries. Additionally, the addition of ceramic filler SiO₂ was found to reduce the stability of polymer electrolyte towards oxygen reduction reaction although higher ionic conductivity was obtained. Polyethylene glycol based gel polymer electrolyte without SiO₂ addition exhibited excellent cycling performance and it could be used for achieving long-life lithium oxygen batteries. Poly(vinylidene fluoride-co-hexafluoropropylene) based gel polymer electrolytes were prepared by solvent casting and employed as electrolytes in lithium oxygen batteries. The stability of the gelled electrolyte with tetraethylene glycol dimethyl ether has been greatly increased than the liquid one. The as-prepared polymer electrolyte was demonstrated excellent cycling performances. This thesis also investigated the effect of different plasticizers on the performance of lithium oxygen batteries. The reason could lie on the interactions among the components when the gelled structure was set. The tetraethylene glycol dimethyl ether based gel polymer electrolyte showed the best electrochemical performance and can be used for long-life lithium oxygen batteries. Polypyrrole conducting polymers with different dopants have been synthesized and applied as the cathode catalysts in lithium oxygen batteries. Polypyrrole polymers exhibited an effective catalytic activity for oxygen reduction in lithium oxygen batteries. It was discovered that dopant significantly influenced the electrochemical performance of polypyrrole. The polypyrrole doped with Cl⁻ demonstrated higher capactity and more stable cyclability than that doped with ClO₄⁻. Polypyrrole conducting polymers also exhibited higher capacity and better cycling performance than that of carbon catalyst. Conducting polymer coated carbon nanotubes were synthesized and used as catalysts in lithium oxygen batteries. It was found that both polypyrrole and poly(3,4-ethylenedioxythiophene) coated carbon nanotubes could provide high cycling performance while polypyrrole based one exhibited higher capacities. The ratio of conducting polymer coating also affected the electrochemical performance of lithium oxygen batteries. The conducting polymer coated carbon nanotubes also showed better performance than the bare carbon nanotubes.

碩士
國立中央大學
化學研究所
91
Abstract Since 1975 Wright et al. discovered the ionic conductivity (1x10-7 S/cm) of PEO-Lithium salt, PEO-Lthium salt based solid electrolytes have under extensively studied. However, the room temperature conductivities of PEO-Li salts are usually too low (due to the semi-crystalline nature of PEO) to be applied practically in lithium batteries. Therefore, increasing the conductivity via various physical or chemical methods has become the major research efforts. To enhance the conductivity of PEO-LiClO4 system, one of the good strategies was forming polymer blend. In this thesis, we blended the precursor of conjugated polymer PAN (polyacrylonitrile) (with PAN/PEO ratios equal to 0wt%, 1wt%, 3wty%, 5wt%) into the PEO-LiClO4 system (and/or heat the blend polymer to crosslink the PAN) to increase the conductivity and film dimension stability. It was found that by adding 1wt% PAN into PEO-LiClO4(15wt%) the hybrid polymer electrolyte has the highest ionic conductivity (up to 6.8x10-4 S/cm at 50oC) and exhibit good mechanical properties. Heating the polymer blends up to 200oC can further increase their conductivity. XRD data showed that the domain size of PEO-LiClO4-PAN is smaller than that of PEO-LiClO4. DSC results also indicated that both the melting point and crystalinility of PEO-LiClO4(15wt%) decreased after adding PAN. The crystallinity of PAN- PEO-LiClO4(15wt%) decreased further after rapidly heating and cooling of the electrolyte films. SEM micrographs showed that when small amount of PAN (PAN/PEO <5wt%) was added, the electrolyte films have a smoother surface compared to pure PEO-LiClO4. The function of PAN can be regarded as a polymer support for dispersing PEO matrix and increase the dimension stability when the crystallinity of PEO decreased.

碩士
國立臺灣大學
生物產業機電工程學研究所
103
This research is dedicating to one of the most promising lithium metal battery, lithium sulfur battery. The development of this kind of lithium metal battery is facing some challenges recently, which can split to two parts. One of them is dendrite growth on the lithium metal negative electrode, which may cause some safety issue, including short-circuited and energy capacity decay. We designed a symmetric cell to in-situ observe dendrite growth when applying a constant current. In order to study the relationship between mechanical strength and dendrite growth, we fabricated the cell with different gel polymer electrolyte with different Young’s modulus. We found that when using the gel polymer electrolyte which Young’s modulus is 0.05548MPa and the current density is 0.1mA/cm2, dendrite would not grow in the first 3000 minutes. We also found that the mechanism of oxidation of lithium metal is very similar to pitting corrosion. When using the electrolyte which diffusivity is lower, the phenomena of pitting corrosion is less apparent. The other part is the dissolution of sulfur electrode. Due to its physic properties, the lithium sulfide would gradually dissolve into the electrolyte. This may cause some energy capacity decay. We add an additional layer into the cell to be a protect layer. This layer could efficiently adsorb the lithium sulfide that dissolved into the solution, reducing the decay rate of the cell. We also mixed MWCNT with carbonized lignin, and found that 50% 900℃ carbonized lignin MWCNT film could make the cell remain 1000mAh/g S capacity after 60 cycles(0.1C).

碩士
國立成功大學
化學工程學系碩博士班
101
In this study, we used PEDGE, DGEBA and D2000 by cross-linking to synthesis the copolymer –poly(ethylene oxide)-co-poly(propylene oxide) (P(EO-co-PO)). Immersing the polymer film into the organic electrolyte for 24 hours, then we got the gel polymer electrolyte (GPE). Took this GPE film to assemble batteries and test its performance. Compare the difference between GPE and the organic liquid electrolyte battery (LE) , find out the advantages of GPE. Compare to LE, the proposed GPE has higher ionic conductivity (3.8210-3 S cm-1 at 30 °C) and a wider electrochemical voltage range (5V). Besides, P(EO-co-PO) copolymer equipped better Lithium ion dissociation ability and higher transfer number (0.7). This high GPE transference number decreases electrode polarization caused by anion accumulation and suppresses the concentration gradient to facilitate lithium ion transport. That made the electrolyte-electrode surface of GPE more stable than LE with lower resistance. Therefore, the performance can be better at higher C-rate charge-discharge test and long-term stability. For battery performance test, we use LiFePO4-cathode and Graphite-anode to assemble the full-cell and compare the difference between GPE and LE. At lower C-rates, the discharge capacity is similar and the value is about 125mAh g-1. When discharge rate is higher than 10 C-rate, the performance decrease dramatically in LE full-cell, while GPE full-cell maintain the capacity even at 17C-rate. For long-term test, we conducted charge-discharge measurement at 1C-rate for 450 cycles. After 450 cycles the capacity retention maintained at ca. 77%. It’s better than the LE full-cell which kept only ca. 44%. Due to the bad performance at higher C-rates by using Graphite-anode, in this study, we also developed hydrothermal method to synthesis TiO2 nanotube. TiO2 is nontoxic, high chemical stability and low price. Moreover, the nanotube structure can help to catch the electrolyte into the tube, increase the electrolyte-electrode contact surface and decrease the distance of lithium ion diffusion. And then decrease the diffusion resistance, that resulted in a discharge capacity 70 mAh g-1 at 60C-rate.

Ionic conductivity of solid polymer electrolytes (SPEs) can be enhanced by the addition of fillers, while maintaining good chemical stability, and compatibility with popular cathode and anode materials. Additionally, polymer composite electrolytes can replace the flammable organic liquid in a lithium-ion battery design and are compatible with lithium metal. Compatibility with Li-metal is a key development towards a next-generation rechargeable Li-ion battery, as a Li-metal anode has a specific capacity an order of magnitude higher than LiC6 anodes used today in everyday devices. The addition of fillers is understood to suppress the crystalline fraction in the polymer phase, increasing the ionic conductivity, as Li-ion conduction is most mobile through the amorphous phase. A full model for a conduction mechanism has not yet constructed, as there is evidence that a semi-crystalline PEO-based electrolyte performs better than a fully amorphous electrolyte. Furthermore, it is not yet fully understood why the weight load of fillers in PCEs can range from 2.5%wt to 52.5%wt, in order to achieve high ionic conductivity (~10-4S/cm). This work seeks to investigate the conduction mechanism in the PCE through the use of doped-Li7La3Zr2O12 as a filler and analysis of the PCE microstructure. In this work, a solid-state electrolyte, doped-Li7La3Zr2O12 (LLZO) was synthesized via a sol-gel method, and characterized. The effect of doping and co-doping the Li, La and Zr sites in the LLZO garnet was investigated. A PEO-based polymer composite electrolyte (PCE) was prepared by adding bismuth doped LLZO (Li7-xLa3Zr2-xBixO12) as a filler. The bismuth molar ratio was changed in value to study the dopant role on the bulk PCE ionic conductivity, polymer phase crystallinity and microstructure. Results suggest that small variations in dopant can determine the optimal weight load of filler at which the maximum ionic conductivity is reached. By understanding the relationship between filler properties and electrochemical properties, higher performance can be achieved with minimal filler content, lowering manufacturing costs a solid-state rechargeable Li-ion battery.