Дисертації з теми "Electrolyte hybride"
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Monin, Guillaume. "Stabilisation chimique des électrolytes polymères pour pile à combustible." Phd thesis, Université de Grenoble, 2012. http://tel.archives-ouvertes.fr/tel-00728176.
Chometon, Ronan. "Exploring the role of polymers in scaling up the manufacturing of solid-state batteries." Electronic Thesis or Diss., Sorbonne université, 2024. http://www.theses.fr/2024SORUS046.
The imperative transition toward renewable energy sources and the ongoing electrification of transportation position battery technologies at the forefront of this transformation. While the lithium-ion technology is already well-established, the quest for higher energy density has drawn significant attention to the emerging solid-state batteries (SSBs). Their working principle is based on ion and electron transfers through solid-solid contacts, which are complex to master and sustain, giving rise to most of the challenges associated with their realisation. Especially, the capability to scale up SSBs' fabrication process is critical for future implementation and calls for a shift from pellet-type to sheet-type assembly. Thus, this doctoral research delved into the role of polymers in facilitating this transition by exploring two strategies differing on the binder's ability to conduct lithium ions. In the first approach, we capitalised on the polymer electrolyte PEO:LiTFSI favourable mechanical properties to prepare self-standing films of hybrid solid electrolyte with a high content of Li6PS5Cl, using a dry process. However, the instability between the organic and inorganic phases resulted in a resistive interphase that prevents a shared conduction mechanism within the hybrid. After that, we pursued a simpler approach to fabricate self-standing SSBs by employing a conventional non-conductive binder, PVDF-HFP, and using a slurry-based tape casting process. The thorough optimisation of the formulation and preparation of the electrodes and solid-state separators gave promising results, closely approaching the electrochemical performance of binder-free reference SSBs, even under low operating pressure. The reliability of our fabrication process thus paves the way for assembling self-standing solid-state full cells, integrating high energy density anodes such as lithium metal
Issa, Sébastien. "Synthèse et caractérisation d'électrolytes solides hybrides pour les batteries au lithium métal." Electronic Thesis or Diss., Aix-Marseille, 2022. http://www.theses.fr/2022AIXM0046.
The problems caused by the intensive extraction and use of fossil fuels have forced humanity to turn to the development of renewable energies and electric vehicles. However, these technologies need to be coupled with efficient energy storage means to exploit their potential. Lithium metal anode systems are particularly interesting because they have a high energy density. However, this technology suffers from the formation of dendrites that can trigger short circuits causing the device to explode. Thus, many efforts have been devoted to the development of POE-based solid polymer electrolytes (SPEs) that provide a barrier that blocks dendritic growth while preserving ionic conduction properties. However, the ionic conductivity of POE-based SPEs decreases strongly with temperature. Currently, the best SPEs in the literature would require operation at 60 °C, which means that some of the energy in the battery will be diverted from its use to maintain this temperature. Thus, the main objective of this thesis work is to design an SPE that allows the operation of lithium metal battery technology at room temperature. These SPEs must exhibit high ionic conductivity at room temperature (≈ 10-4 S.cm-1) and mechanical properties that allow the inhibition of the dendritic growth phenomenon. For this, the objectives of the project are focused on the development of new nanocomposite and hybrid SPEs
Leclercq, Florent. "Étude d'électrolytes hybrides solides destinés aux batteries lithium." Electronic Thesis or Diss., Paris Sciences et Lettres (ComUE), 2019. http://www.theses.fr/2019PSLET068.
This work focuses on the comparison of two processes for the elaboration of a solid hybrid electrolyte made of a mix of two polymers (PEO and PVDF-HFP), a lithium salt (LiTFSI), and of a silica network made in situ via a sol-gel method and functionalized with imidazolium groups. At first, the influence of the different components on the physicochemical and electrochemical properties of electrolytes made by dry casting is studied. Conductivities of 10⁻⁴ S/cm at 80 °C allow us to cycle LiFePO₄/Li batteries at a C/10 rate at the same temperature. A skeleton of hybrid PVDF-HFP/silica (functionalized or not) nanofibers is synthesized by electrospinning and its porosity is filled with a PEO/LiTFSI mix. The particular architecture of this type of electrolyte enables the decoupling of conduction and mechanical properties. Conductivities of 5.10-4 S/cm at 80 °C allow the cycling of LiFePO₄/Li batteries at a C/2 rate at the same temperature. The same electrospun hybrid membranes are evaluated as separators for hybrid water-in-salt electrolytes. Thanks to their excellent wetting and retention properties, LiMn₂O₄/TiO₂ batteries are cycled at a 10C rate with a low quantity of electrolyte
Chamaani, Amir. "Hybrid Polymer Electrolyte for Lithium-Oxygen Battery Application." FIU Digital Commons, 2017. https://digitalcommons.fiu.edu/etd/3562.
Lundgren, Henrik. "Thermal Aspects and Electrolyte Mass Transport in Lithium-ion Batteries." Doctoral thesis, KTH, Tillämpad elektrokemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-166857.
Temperatur är en av de viktigaste parametrarna gällande ett litiumjonbatteris prestanda, säkerhet och åldring och har länkats till de främsta barriärerna för en storskalig kommersiell framgång för elbilar. Syftet med den här avhandlingen är att belysa vikten av temperatureffekter, samt att bidra med ingenjörsverktyg att studera dessa. Masstransporten för elektrolyten LiPF6 i EC:DEC karakteriserades fullständigt i temperaturintervallet 10 till 40 °C för LiPF6-koncentrationer på 0.5 till 1.5 M. Alla masstransport-egenskaper fanns variera kraftigt med temperaturen. Den superkoncentrerade elektrolyten med LiTFSI i ACN karakteriserades även den fullständigt vid 25 °C. Dess egenskaper och interaktioner fanns vara väldigt annorlunda jämfört med LiPF6 i EC:DEC. Fördelen med att använda utvärderingsmetoden elektrolytmasstransportresistivitet (EMTR) jämfört med att endast mäta konduktivitet illustrerades för flertalet system, däribland organiska vätskor, jonvätskor, fasta polymerer, gellade polymerer, och elektrolyter med flamskyddsadditiv. Flamskyddsadditivet TPP utvärderades med en hybridbils-lastcykel och fanns vara olämplig för högeffektsapplikationer, som hybridbilar. Ett kommersiellt storformatsbatteri med ett temperatur-kontrollsystem karakteriserades med b.de experiment och en kopplad termisk och elektrokemisk modell under en lastcykel utvecklad för plug-inhybridbilar. Olika strategier för kontroll av temperaturen utvärderades, men fanns bara ha liten inverkan på batteriets temperatur då begränsningarna för värmetransport ligger i elektrodrullen, och inte i batteriets metalliska ytterhölje.
QC 20150522
Swedish Hybrid Vehicle Center
Romer, Frederik. "Multinuclear NMR of hybrid proton electrolyte membranes in metal oxide frameworks." Thesis, University of Warwick, 2017. http://wrap.warwick.ac.uk/89874/.
Seck, Serigne. "Elaboration de matériaux hybrides organiques / inorganiques par extrusion réactive : Application en pile à combustible." Thesis, Lyon, INSA, 2013. http://www.theses.fr/2013ISAL0027.
Fuel cells technologies are electrochemical energy conversion devices and have a real potential to revolutionize the way to produce energy, offering cleaner, more-efficient alternatives to combustion of gasoline and other fossil fuels. In that way, the Proton Exchange Membrane Fuel Cells (PEMFC) are probably the most studied. Those fuel cells are mainly based on perfluorosulfonic acid membranes, such as Nafion®. However, Nafion® membranes, present some limitations such as dehydration at high temperatures or at low relative humidity rate leading to a decrease of proton conductivity and thus poor PEMFC performance. Consequently, PEMFC require significant improvements prior to be largely used in the automobile field. Research efforts have been oriented on the development of new materials for the PEMFC membrane as it is the main limitative component for high temperature fuel cell. In the present contribution, we wish to report the validation of a new concept of hybrid materials for the realization of proton exchange membranes. The originality of this hybrid concept is based on the contribution of both phases’ specific properties. We investigated the preparation of hybrid materials based on an inert polymer matrix (low cost) providing the mechanical stability embedding inorganic phase providing the necessary properties of proton-conduction and water retention. Hybrid nanocomposite membranes were synthesized using evaporation and recasting technique from solution containing dispersion of inorganic particles in the adequate polymer. Scanning electron microscopy (SEM) images for membrane morphology and proton conductivity results using impedance measurements from hybrid membranes will be presented. The performance of the membrane-electrode assembly (MEA) using the hybrid membrane was also evaluated by a fuel cell test. Finally, we wish to present a promising way of research based on Sol-Gel approach to generate a proton-conducting inorganic phase into the polymer matrix
Boaretto, Nicola. "Inorganic-organic hybrid polymer electrolytes for secondary lithium metal batteries." Doctoral thesis, Università degli studi di Padova, 2016. http://hdl.handle.net/11577/3424435.
Gli elettroliti polimerici costituiscono un’importante classe di materiali a conduzione ionica, che trova applicazione essenzialmente in dispositivi di stoccaggio elettrochimici, quali batterie al litio o celle a combustibile. Nel campo delle batterie al litio, l’interesse per questi materiali deriva principalmente dalla loro non infiammabilità, che li distingue dagli elettroliti liquidi attualmente utilizzati. In aggiunta, gli elettroliti polimerici mostrano una maggiore compatibilità nei confronti del litio metallico. L’utilizzo di questo come materiale anodico permette una riduzione della massa della cella e quindi un aumento dell’energia specifica della stessa. Questo studio descrive la sintesi e la caratterizzazione di elettroliti polimerici ibridi a base polisilossanica/polieterea. La sintesi include una reazione d’idrolisi/co-condensazione tra alcossisilani funzionalizzati e la reticolazione di gruppi terminali vinilici o epossidici. La struttura, le proprietà termomeccaniche, elettrochimiche e di trasporto sono caratterizzate tramite varie tecniche analitiche. Infine, i materiali più promettenti sono testati in celle con anodi in litio metallico. Lo studio descrive, infine, un tentativo di migliorare la ciclabilità delle celle litio/polimero tramite pre-passivazione degli elettrodi in litio. I materiali sintetizzati sono caratterizzati da buona conducibilità ionica (fino a 8∙10-5 S•cm-1 a temperatura ambiente) e da buona stabilità termomeccanica ed elettrochimica. L’analisi degli spettri elettrici (BES) rivela che la mobilità ionica è massimizzata a) in assenza di interazioni inter-ioniche a corto raggio e b) in assenza di ordine nei domini polieterei. Se queste due condizioni sono soddisfatte, la migrazione ionica a lungo raggio è modulata dal moto segmentale delle catene polieteree. Test in cella a 60 °C dimostrano che questi materiali possono essere utilizzati come elettroliti polimerici in celle con anodo in litio metallico, seppur con una moderata perdita di capacità. Questa è in parte attribuita a problemi di contatto e di stabilità elettrochimica tra l’elettrolita e l’anodo. La pre-passivazione degli elettrodi in litio metallico protegge l’elettrolita dal deterioramento e permette di migliorare le prestazioni in cella.
Meyer, Mathieu. "Membranes électrolytes à porteurs de charge Li+." Thesis, Montpellier 2, 2014. http://www.theses.fr/2014MON20119/document.
The topical demand in all-solid lithium-ion batteries suitable for portable consumer electronicdevices has triggered extensive research on more and more sophisticated polymer electrolytemembranes (PEM).This PhD work deals with the synthesis and the mechanical, thermal andstructural characterization of new nanocomposite PEM arising from the sol-gel cross-linking ofPEO chains end-capped with alkoxysilane groups. Thus, the polysilsesquioxane nano-domainsformed by hydrolysis-condensation reactions form a high density of cross-links and play the roleof nanocharges, giving rise to mechanical resistance, which allows incorporating high amounts ofplasticizer. Moreover, sol-gel process allows the functionalization of these nanodomains withlithium sulfonate or perfluorosulfonate groups, which supply Li+ charge carriers homogeneouslydispersed throughout the membrane. In addition the immobilization of the anions via covalentbonds prevents them from contributing to the overall conductivity, thus ensuring a single-ionconduction, which is a compulsory condition to prevent the further formation of lithium dendriteson charge-discharge cycles. The ionic conductivity study of the membranes, in the dry state orafter swelling in propylene carbonate, was done. It led to discuss the dynamics of lithium cation inthe nanocomposite membranes and the possible ways to improve their conductionperformances
Chaker, Juliano. "Corrélations structure/propriétés de conduction ionique dans des matériaux hybrides siloxane-poly(oxydepropylène) dopés par des sels de sodium et de potassium." Paris 11, 2004. http://www.theses.fr/2004PA112190.
Siloxane-poly(oxi propylene) (PPO) or Siloxane-poly(oxi propylene) hybrid materials prepared by the sol-gel route show increasing scientific and technological interest due to its particular structure in which the polymer chains are grafted to the inorganic nanoparticules. When doped within alkaline salts these hybrids present ionic conductivity similar to that of ionic conductive polymers (10-4 S/cm), and both their mechanical and optical properties are improved. However, the nature of the mobile species, are responsible for there conductivity (free ions, ion-pairs, aggregates) is not well established. So that the knowledge of the nature and the local structure around the mobile ions is the challenger to improve the ionic properties. The but of this work was to establish the correlations between the local structure around the charge carriers (coordination shell, solvation sphere) and the macroscopic conductivity. To reach this objective the local structure was probed by X ray absorption (XANES and EXAFS), Raman and NMR spectroscopy and the results related to that obtained from conductivity measurements
Meera, P. "Nafion based hybrid polymer electrolytes and nanocomposites: design and electrochemical investigations." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2009. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/2726.
DE, BONIS CATIA. "Hybrid polymer electrolytes for proton exchange membrane fuel cells: synthesis and applications." Doctoral thesis, Università degli Studi di Roma "Tor Vergata", 2009. http://hdl.handle.net/2108/1129.
Proton exchange membrane fuel cells (PEMFCs) are promising power sources emerging among alternative energy conversion systems, because they can operate at relatively low temperature and offer numerous benefits, such as high efficiency, high power density and low polluting emissions. The present dissertation deals with the development of new proton conducting membranes having good conductivity, chemical and thermal stability, low methanol permeability and low cost. The main strategy used in this work was the preparation of sulfonated and silylated polyetheretherketone (PEEK) and polyphenylsulfone (PPSU) as membrane materials, because this synthetic approach represents a powerful tool to modulate the proton conductivity and hydrolytic stability of the electrolyte by the dosage of sulfonic acid groups and inorganic moieties covalently bound to the aromatic chains. Several types of proton exchange membranes were studied. Sulfonated and silylated PEEK and/or PPSU were used to prepare systems where two components resulted crosslinked by physical interactions or covalent bonds, obtaining the synergic effect of polymers having different conductivity and mechanical properties. • Sulfonated and silylated polyetheretherketone PhSi0.1S0.9PEEK (degree of sulfonation DS=0.9, and degree of silylation DSi=0.1) was synthesized via (i) sulfonation of PEEK, (ii) conversion of sulfonated polyetheretherketone (S0.9PEEK) into sulfonyl chlorinated derivative (PEEKSO2Cl), (iii) lithiation of PEEKSO2Cl and subsequent addition of PhSiCl3, followed by hydrolysis. The solubility of PEEKSO2Cl in organic solvent allows the silylation reaction to be carried out in homogeneous conditions. The structural characterization of the products by 1H and 13C NMR and ATR/FTIR spectroscopies highlighted the success of the synthetic pathway. The thermogravimetric analysis of PEEK derivatives indicated that the presence of the inorganic moieties stabilizes the aromatic matrix of the sulfonated polyetheretherketone. Blends of PhSi0.1S0.9PEEK and S0.5PEEK (DS=0.5) were prepared using different weight ratios of the two polymers. The membranes were characterized by water uptake measurements and electrochemical impedance spectroscopy (EIS). The results converge to indicate that the developed materials are promising electrolytes for PEMFC application. • Silylated and sulfonated polyphenylsulfone PhSi0.2S2PPSU (DS=2.0 and DSi=0.2) was synthesized via (i) lithiation of PPSU and subsequent addition of PhSiCl3, followed by hydrolysis, (ii) sulfonation by reaction with concentrated sulphuric acid. The chemical structure of polymers was investigated by 1H and 13C NMR, and ATR/FTIR, verifying the success of the developed synthetic route. Blends of PhSi0.2S2PPSU and S0.5PEEK were prepared, obtaining electrolytes with higher hydrolytic stability and increased proton conductivity with respect to those of pure S0.5PEEK membrane. Blend membranes showed also better performance in DMFC, where a reduced methanol permeability and adequately high power density values were observed, at temperature values as high as 100°C. All these features identify the prepared blend membranes as promising electrolytes for DMFC operating at intermediate temperatures. • Two silylated and sulfonated PPSU derivatives: Si0.2S2PPSU (DS=2.0 and DSi=0.2) and Si0.03S0.05PPSU (DS=0.05 and DSi=0.03) were synthesized following two different routes. In the first one, PPSU was silylated by reaction with SiCl4, then sulfonated by reaction with concentrated sulphuric acid, and Si0.2S2PPSU was obtained. In the second route, the use of the mild sulfonating agent ClSO3Si(CH3)3 allowed a careful control of the degree of sulfonation, and PPSU with a lower DS was obtained. Subsequent silylation by reaction with SiCl4 led to the final product Si0.03S0.05PPSU. An organic-inorganic hybrid polymer HSiSPPSU was synthesized by non-hydrolytic sol–gel reaction of Si0.2S2PPSU and Si0.03S0.05PPSU. The condensation between the silanol groups of the two polymers led to the formation of Si-O-Si bonds, as highlighted by analysis of ATR/FTIR spectra. The electrochemical characterization of HSiSPPSU membranes by EIS showed adequately high conductivity values to make the hybrid polymer a suitable candidate for application in PEMFCs operating at T > 100°C. The strategies followed in this work seems to be an effective way to overcome some drawbacks related to conventional polymer membranes currently used, demonstrating the relevant role played by synthesis in the preparation of electrolytes for PEMFCs.
Gu, Bin. "Power Converter and Control Design for High-Efficiency Electrolyte-Free Microinverters." Diss., Virginia Tech, 2014. http://hdl.handle.net/10919/25236.
Ph. D.
Maouacine, Koceila. "Matériaux hybrides poreux silice/polymère comme électrolytes pour batterie lithium-ion tout solide." Electronic Thesis or Diss., Aix-Marseille, 2023. http://www.theses.fr/2023AIXM0024.
The design of lithium-ion batteries using a solid electrolyte is currently one of the most studied ways to overcome safety problem of these devices. In this thesis work, we propose a new approach to develop a porous silica/polymer hybrid electrolyte, containing a higher weight fraction of mesoporous silica than polymer. Two morphologies of silica hybrid materials were studied: as compressed powders (pellets) and as thin films. In the first part of the work, a hybrid silica powder was synthesized and then calcined to liberate the porosity. The mesoporous silica was then functionalized with different polymers of PEG of low molecular weight then by a simple solution impregnation. The hybrid powders were shaped as pellets, presenting inter- and intra-particle porosity. It was shown that the hybrid pellets present promising ionic conductivity properties when the inter- and intraparticle porosities are filled with the PEG-LiTFSI complex for PEG of low molar mass (300-600 g/mol). In the second part, mesoporous silica films were deposited on a glassy carbon electrode using a rotating disc electrode (RDE). After the characterization of these films from a textural properties and a microstructure point of view, they were functionalized by the PEG-LiTFSI complex via an impregnation process and the preliminary study of their ionic conductivity was performed
Zamanillo, López Isabel. "Membranes hybrides pour pile à combustible." Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAI120/document.
Fuel cell is a promising solution for clean production of hydrogen based energy. However to achieve a large-scale deployment of this technology, issues remain to be addressed. One of the remaining problems concerns the heart of the cell (polymer membrane sandwiched between two electrodes). We can stress the fact that it is impossible to improve the catalyst efficiency and the cell performance by a simple increase of the operating temperature (100-120 °C). Indeed the reference membrane (Nafion) exhibit a step decrease of its thermomechanical properties beyond 80 °C, whereas alternative membranes (with a better thermomechanical stability) are victims of a much faster chemical aging resulting into unexpected failure of the device.Our main objective is to develop novel hybrid membranes consisting of a commercial ionomer matrix in which we will introduce precursors capable to form a sol-gel phase. It will result on membrane composed of two interpenetrating phases, an ion conductive non-crosslinked polymer phase and a crosslinked inorganic phase providing chemical and thermomechanical stabilization. The control of the chemistry of this sol-gel phase, its morphology and its location in the membrane, which will improve the membrane properties, are essential to consider the development of these membranes for fuel cells.A careful analysis of the hydrothermal treatment effect on the microstructure of sPEEK membranes has been performed. Thanks to this analyse we can relate the microstructure with the functional properties of the polymer. The sol-gel process enables the growth of the sol-gel phase without disturbance of the initial nanostructured membrane. This strategy makes possible to control the distribution and morphology of the inorganic phase.The elaboration process of hybrid membrane has been studied. We presented the influence of elaboration parameters regarding the best conditions to prepare an optimized hybrid membrane. The physical and chemical properties of the inorganic phase were evaluated by many techniques (SANS, IR, DMA, etc.). The influence of the chemical structure (cross-linking degree) of the sol-gel network andthe impact of the sol-gel content and its distribution (morphology) into the host membrane on their functional properties is presented. We observed the great influence of cross-linking degree and of the amount of sol-gel present in the membrane which determines the functional properties of the membrane
Goh, Wei Chiun. "Hybrid hydrogen energy stored in stand-alone power system." Thesis, Curtin University, 2008. http://hdl.handle.net/20.500.11937/578.
Yahata, Yoshikazu. "Extended Design of Concentrated-Polymer-Brush-Decorated Hybrid Nanoparticles and Their Use for Phase-Separation Control." Kyoto University, 2018. http://hdl.handle.net/2433/232486.
Kroll, Douglas M. "Using polymer electrolyte membrane fuel cells in a hybrid surface ship propulsion plant to increase fuel efficiency." Thesis, Cambridge Massachusetts Institute of Technology, 2010. http://hdl.handle.net/10945/4941.
Approved for public release; distribution is unlimited
An increasingly mobile US Navy surface fleet and oil price uncertainty contrast with the Navy's desire to lower the amount of money spent purchasing fuel. Operational restrictions limiting fuel use are temporary and cannot be dependably relied upon. Long term technical research toward improving fuel efficiency is ongoing and includes advanced gas turbines and integrated electric propulsion plants, but these will not be implemented fleet wide in the near future. The focus of this research is to determine if a hybrid fuel cell and gas turbine propulsion plant outweigh the potential ship design disadvantages of physically implementing the system. Based on the potential fuel savings available, the impact on surface ship architecture will be determined by modeling the hybrid fuel cell powered ship and conducting a side by side comparison to one traditionally powered. Another concern that this solution addresses is the trend in the commercial shipping industry of designing more cleanly running propulsion plants.
Kroll, Douglas M. (Douglas Michael). "Using polymer electrolyte membrane fuel cells in a hybrid surface ship propulsion plant to increase fuel efficiency." Thesis, Massachusetts Institute of Technology, 2010. http://hdl.handle.net/1721.1/61909.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 59).
An increasingly mobile US Navy surface fleet and oil price uncertainty contrast with the Navy's desire to lower the amount of money spent purchasing fuel. Operational restrictions limiting fuel use are temporary and cannot be dependably relied upon. Long term technical research toward improving fuel efficiency is ongoing and includes advanced gas turbines and integrated electric propulsion plants, but these will not be implemented fleet wide in the near future. The focus of this research is to determine if a hybrid fuel cell and gas turbine propulsion plant outweigh the potential ship design disadvantages of physically implementing the system. Based on the potential fuel savings available, the impact on surface ship architecture will be determined by modeling the hybrid fuel cell powered ship and conducting a side by side comparison to one traditionally powered. Another concern that this solution addresses is the trend in the commercial shipping industry of designing more cleanly running propulsion plants.
Douglas M. Kroll.
S.M.in Engineering and Management
Nav.E.
Gazey, Ross Neville. "Sizing hybrid green hydrogen energy generation and storage systems (HGHES) to enable an increase in renewable penetration for stabilising the grid." Thesis, Robert Gordon University, 2014. http://hdl.handle.net/10059/947.
Weldekidan, Ephrem Terefe. "Design of lithium ion conducting porous hybrid materials for the development of solid Li-battery electrolytes." Thesis, Aix-Marseille, 2019. http://www.theses.fr/2019AIXM0707.
In this work, porous polymer-silica hybrid materials as a powder and thin film are synthesized and characterized. The preliminary study of their Li+ ionic conductivity properties are carried out as well. Here, the polymer electrolyte is embedded in silica matrix - polymer-in-ceramic approach. The hybrid powders are synthesized through sol-gel using conventional triblock (Pluronic, P123) and laboratory made bifunctional diblock amphiphilic copolymers as structure directing agents (SDA). In the first case, post-synthetic modification is used to functionalize the pore surface of silica with PEO. The second allowed to direct functionalization the pore surface with hydrophilic block (PEO) through extraction of hydrophobic block. Particle-free mesoporous silica films with hexagonally ordered and vertically oriented mesochannels are synthesized on electrode surface via electro-assisted self-assembly method under hydrodynamic condition. The resulting films are mesoporous (a diameter of 3 nm) and fully accessible. A film with thickness of 660 nm was grown in 200 s, and functionalized with PEO and then lithium salt through solution impregnation method. The ionic conductivity properties of hybrids were performed after shaping the powder as a pellet or with the hybrid film directly formed on the electrode surface. The results showed that the Li+ conductivity brought to the materials. The pellets have 40 % interparticle porosity and filling this with polymer electrolyte has positive effect on optimizing conductivity of the pellets (2.0 x 10-7 Scm-1 for 35 % filling and 6.8 x 10-7 Scm-1 for 100% filling at 25 °C)
Lancel, Gilles. "Synthèse et caractérisation de membranes hybrides pour la conduction des ions lithium, et application dans les batteries lithium-air à électrolyte aqueux." Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066011/document.
Aqueous lithium-air batteries could be a revolution in energy storage, but the main limitation is the use of a thick glass-ceramic lithium ionic conductor to isolate the metallic lithium from the aqueous electrolyte. This makes the system more fragile, limits its cyclability and increases ohmic resistance. The aim of this work is to replace the glass-ceramic by a hybrid membrane made by electrospinning, which combines water tightness, flexibility and lithium-ions conductivity. The ionic conductivity is provided by a nanostructured solid electrolyte ceramic: both Li1,4Al0,4Ti1,6(PO4)3 (LATP) and Li0,33La0,57TiO3 (LLTO) were studied. The water tightness is ensured by a fluorinated polymer. Different powders synthesis methods are reported and compared in terms of purity, microstructure, specific surface area and electrochemical properties. Especially, the LATP microwave-assisted synthesis is reported for the first time. Sub-micrometric LATP particles were obtained in times as short as 2 min. The fabrication of hybrid membranes from suspension is then reported. In a second approach, the coupling between sol-gel chemistry and electrospinning made possible the fabrication of a self-standing lithium-conducting network, made of interconnected crystalline nanofibers. After an impregnation step, a flexible, lithium-conducting and watertight hybrid membrane is obtained. A mechanical reinforcement is observed, which is attributed to the inorganic nanofibers. This approach is exposed for both LATP and LLTO solid electrolytes. This work opens new prospects in lithium-air, lithium-sulfur and lithium-ion batteries
Wickramaarachchi, Kethaki. "Synthesis of electrolytic manganese dioxide (EMD) and biomass waste-derived carbon for hybrid capacitors." Thesis, Wickramaarachchi, Kethaki (2022) Synthesis of electrolytic manganese dioxide (EMD) and biomass waste-derived carbon for hybrid capacitors. PhD thesis, Murdoch University, 2022. https://researchrepository.murdoch.edu.au/id/eprint/66472/.
Martín, Dalmas Joël. "Modélisation multi-échelle du transport du lithium dans des électrolytes Li-ion solides et hybrides et leurs interfaces." Electronic Thesis or Diss., Université Grenoble Alpes, 2023. http://www.theses.fr/2023GRALY098.
Hybrid Solid Electrolytes (HSEs) offer a promising alternative to conventional liquid electrolytes in the field of Li-ion batteries. These HSEs incorporate ceramic fillers, typically in nanoparticle form, into polymeric electrolytes. This integration aims to address the primary challenge encountered by Solid Polymeric Electrolytes (SPEs): their lower conductivity when compared to alternatives such as liquid or ceramic electrolytes. However, it remains uncertain whether the addition of ceramic fillers to pure SPEs yields a positive impact. The literature presents two distinct sets of findings. The first, stemming from early experimental research conducted two decades ago, advocates a significant improvement in SPE conductivity through the incorporation of passive ceramic fillers such as silica or alumina across various concentrations and temperatures. Conversely, an opposing perspective has emerged, highlighting outcomes that demonstrate an adverse effect of ceramics on the ionic mobility within SPEs, particularly when the polymer is in its amorphous phase.The ongoing debate in this field calls for a needed clarification. In this thesis, we seek to provide answers to a critical question: Does the inclusion of ceramic nanoparticles in Solid Polymeric Electrolytes enhance or impede ion mobility? To address this inquiry, we employ molecular dynamics simulation techniques to analyze two hybrid systems comprised of Polyethylene Oxide (PEO) as the polymer, LiTFSI as the lithium salt, and either silica or alumina as the ceramic components. Our approach involves classical molecular dynamics simulations using the OPLS-AA force field, enabling us to explore the dynamic behaviors and interactions of these materials over extended time scales, typically spanning tenths of nanoseconds. The force field parameters are examinated from various literature sources, each having undergone individual validation through comparisons with experimental data.We carried out an analysis of their structural properties, closely examining their correlation with the dynamic behavior of ions. This analysis provides a detailed account of the shifts in the system's dynamics.Our results demonstrate a high precision in replicating the temperature-dependent behavior observed in experimental studies of pure SPEs. Moreover, our simulations reproduce the solvation mechanisms of the salt on PEO, serving as a robust validation of our findings for pure SPEs.Our findings concerning the use of silica nanoparticles reveal a substantial reduction in conductivity upon their addition, regardless of the ionic concentration. Most of this reduction can be accounted for by the diffusion equation, resulting from the fact that the space occupied by the nanoparticles is made inactive and unable to sustain ionic diffusion, interupting the movement of the ions. We identify two distinct concentration regimes: one above and one below a threshold concentration of 2 mol/L, which coincides with the point of maximum conductivity. These regimes exhibit contrasting ionic distributions and coordination properties among species. In the low-concentration regime, lithium ions are predominantly coupled to oxygen atoms within the PEO, leading to its saturation at 2 mol/L. In the second regime, the surplus of lithium ions interacts with TFSI anions, influencing interactions among other ions in the system.The absence of conductivity enhancement observed in our simulations aligns with recent experimental measurements, contrary to earlier reports on hybrid ceramic/polyethylene-oxide electrolytes. Similar outcomes are evident in our results for alumina nanoparticles. In the specific case of alumina nanoparticles, we explored the utilization of a new set of force field parameters, resulting in significant alterations in the internal organization of the electrolyte. Despite these variations, our simulations consistently indicate a reduction in conductivity upon the addition of alumina nanoparticles
Gu, Yu. "A PVDF-BASED HYBRID ELECTROLYTE INCORPORATING LATP AND Al2O3 FILLERS WITH ENHANCED IONIC CONDUCTIVITY AND THERMAL STABILITY FOR LI-ION BATTERIES." Case Western Reserve University School of Graduate Studies / OhioLINK, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=case1618903524872759.
Klett, Matilda. "Electrochemical Studies of Aging in Lithium-Ion Batteries." Doctoral thesis, KTH, Tillämpad elektrokemi, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-145057.
QC 20140512
Sundaresan, Meenakshi. "A thermal model to evaluate sub-freezing startup for a direct hydrogen hybrid fuel cell vehicle polymer electrolyte fuel cell stack and system /." For electronic version search Digital dissertations database. Restricted to UC campuses. Access is free to UC campus dissertations, 2004. http://uclibs.org/PID/11984.
Zhou, Tao. "Commande et supervision énergétique d’un générateur hybride actif éolien incluant du stockage sous forme d’hydrogène et des super-condensateurs pour l’intégration dans le système électrique d’un micro réseau." Thesis, Ecole centrale de Lille, 2009. http://www.theses.fr/2009ECLI0010/document.
A hybrid power system is studied in this thesis for the distributed generation based on renewable energy resources and energy storage systems in microgrid applications. It consists of a wind generator as primary energy source, super-capacitors as fast-dynamic storage system, fuel cells and electrolyzers as long-term storage system in hydrogen. They are all connected to a common DC bus and an inverter is used for the connection of the whole system to the grid. In this thesis, we have presented the system modeling, the control design including the power balancing and energy management strategies. This hybrid power system can finally supply controllable smooth powers as most conventional power plants. The performances have been tested in numerical simulations and also on an experimental test bench. As result, it is able to provide ancillary services to the microgrid. The main scientific contributions of this thesis are: the use and the adaptation of the graphical tools for the modeling of complex systems and their design; the design and the experimental implementation of real-time emulators in order to reduce the time and the cost of an experimental platform; the proposition and the validation of two power balancing strategies for the DC-bus voltage regulation and the grid power control and finally the proposition of energy management strategies for the active wind generator to ensure the energy availability
Lancel, Gilles. "Synthèse et caractérisation de membranes hybrides pour la conduction des ions lithium, et application dans les batteries lithium-air à électrolyte aqueux." Electronic Thesis or Diss., Paris 6, 2016. http://www.theses.fr/2016PA066011.
Aqueous lithium-air batteries could be a revolution in energy storage, but the main limitation is the use of a thick glass-ceramic lithium ionic conductor to isolate the metallic lithium from the aqueous electrolyte. This makes the system more fragile, limits its cyclability and increases ohmic resistance. The aim of this work is to replace the glass-ceramic by a hybrid membrane made by electrospinning, which combines water tightness, flexibility and lithium-ions conductivity. The ionic conductivity is provided by a nanostructured solid electrolyte ceramic: both Li1,4Al0,4Ti1,6(PO4)3 (LATP) and Li0,33La0,57TiO3 (LLTO) were studied. The water tightness is ensured by a fluorinated polymer. Different powders synthesis methods are reported and compared in terms of purity, microstructure, specific surface area and electrochemical properties. Especially, the LATP microwave-assisted synthesis is reported for the first time. Sub-micrometric LATP particles were obtained in times as short as 2 min. The fabrication of hybrid membranes from suspension is then reported. In a second approach, the coupling between sol-gel chemistry and electrospinning made possible the fabrication of a self-standing lithium-conducting network, made of interconnected crystalline nanofibers. After an impregnation step, a flexible, lithium-conducting and watertight hybrid membrane is obtained. A mechanical reinforcement is observed, which is attributed to the inorganic nanofibers. This approach is exposed for both LATP and LLTO solid electrolytes. This work opens new prospects in lithium-air, lithium-sulfur and lithium-ion batteries
Nyman, Andreas. "An Experimental and Theoretical Study of the Mass Transport in Lithium-Ion Battery Electrolytes." Doctoral thesis, KTH, Tillämpad elektrokemi, 2011. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-29121.
Litiumjonbatterier är speciellt lämpliga som ackumulatorer i högeffektsapplikationer som elhybridfordon. Det är idag allmänt accepterat att en av processerna som begränsar effekttätheten för litiumjonbatterier är masstransporten i elektrolyten. Trots detta är det fortfarande svårt att få tag på data som fullständigt beskriver masstransporten i de vanligaste elektrolyterna. I det här arbetet har masstransportkarakteriseringar gjorts för två tekniskt viktiga elektrolyter: (1) en vätskeelektrolyt som består av LiPF6 upplöst i etylenkarbonat (EC) och etylmetylkarbonat (EMC), och (2) en gel elektrolyt som består av LiPF6 upplöst i EC, propylenkarbonat (PC) och poly(vinylidene fluoride‐hexafluoro propylene) (P(VdFHFP)). Masstransporten i elektrolyterna karakteriserades genom att kombinera ett antal karakteriseringsexperiment. Maxwell‐Stefans ekvation användes som utgångspunkt i karakteriseringarna. Modeller av transporten formulerades från ekvationen och de effektiva transportegenskaperna identifierades. En matematisk analys gjordes först av karakteriseringstekniken, så att det kunde fastslås för vilka förhållanden experimenten skulle utföras. Värderna av transportegenskaperna erhölls genom att optimera modellerna till det experimentella beteendet. För att ge karakteriseringsresultaten en begriplig tolkning och för att kunna mäta prestandan av elektrolyter, infördes konceptet normaliserad potentialgradient. Resultatet från karakteriseringen av vätskeelektrolyten användes i en model av en LiNi0.8Co0.15Al0.05O2 | LiPF6 EC:EMC (3:7) | MAG‐10 cell. Modellen utvecklades för att analysera masstransporten i cellen under ett hybridpulstest (HPPC). Analysen gjordes med en metod där polarisationen delades upp i delar som var och en var kopplad till en process i batteriet. Den optimala sammansättningen med avseende på masstransporten låg i regionen 0.5–1.2 mol/dm3 LiPF6 för vätskeelektrolyten och 5‐7 vikt% LiPF6 för gelelektrolyten. Mindre mängd polymer i gelelektrolyten gav en snabbare masstransport. Det konstaterades också att masstransporten i vätskeelektrolyten bidrog med en av de största delarna till polarisationen i HPPC testen.
QC 20110128
Baumann, Lars. "Improved system models for building-integrated hybrid renewable energy systems with advanced storage : a combined experimental and simulation approach." Thesis, De Montfort University, 2015. http://hdl.handle.net/2086/11103.
Gailly, Frédéric. "Alimentation électrique d'un site isolé à partir d'un générateur photovoltaïque associé à un tandem électrolyseur/pile à combustible (batterie H2/O2)." Phd thesis, Toulouse, INPT, 2011. http://oatao.univ-toulouse.fr/11527/1/Gailly_Frederic.pdf.
Tabanjat, Abdulkader. "Modélisation, commande et supervision d'un système multi-sources connecté au réseau avec stockage tampon de l'énergie électrique via le vecteur hydrogène." Thesis, Belfort-Montbéliard, 2015. http://www.theses.fr/2015BELF0266/document.
The limited reserves of fossil fuel and the pollution gases produced pave the way to promising alternativeRenewable Energy Sources (RESs) such as Solar Energy Sources (SESs) and Wind Energy Sources (WESs).SESs and WESs are freely available and environmentally friendly. However, RESs are intermittent in nature.Therefore, the smoothing of power fluctuations by storing the energy during periods of oversupply and restore it tothe grid when demand becomes necessary. Accordingly, Energy Storage Systems (ESSs) can be appropriatelyused for this purpose.Using several energy sources for constructing HPSs alongside with ESS will require an energy managementstrategy to achieve minimum HPS cost and optimal balance between energy generation and energy consumption.This energy management method is a mechanism to achieve an ideal energy production and to conveniently satisfythe load demand at relatively high efficiency.In this thesis, a Hybrid Power System (HPS) including Renewable Energy Sources (RESs) such as main sourcescombined with Gas Micro-Turbine (GMT) and hydrogen storage system such as Back-up Sources (BKUSs) hasbeen presented. The aim of this hybridization is to build a reliable system, which is able to supply the load andhaving the ability to store the excess energy in hydrogen form and reuse it later when demanded. Consequently, thestored energy at the end of each cycle will be zero and a minimum generated power cost is achieved. In addition,partial shading problem of Photovoltaic (PV) panels is comprehensively studied and a new solution based on simpleswitches and Fuzzy Logic Control (FLC) integrated into dSPACE electronic card is created. Consequently, a realtime PV panels reconfiguration and disconnecting shaded ones is performed and minimum power losses isachieved. Then, the PV panels are connected to a Proton Exchange Membrane Electrolyser (PEM ELS). Theemitted temperature by the PV panels is transferred to the endothermic element PEM ELS. Consequently, anefficiency enhancement of the hybrid system PVPEM ELS is realized
Hibino, Takashi, Atsuko Tomita, Mitsuru Sano, Toshio Kamiya, Masahiro Nagao, and Pilwon Heo. "Sn0.9In0.1P2O7-Based Organic/Inorganic Composite Membranes : Application to Intermediate-Temperature Fuel Cells." The Electrochemical Society, 2007. http://hdl.handle.net/2237/18430.
Ndipingwi, Miranda Mengwi. "Graphol and vanadia-linkedzink-doped lithium manganese silicate nanoarchitectonic platforms for supercapatteries." University of Western cape, 2020. http://hdl.handle.net/11394/7236.
Energy storage technologies are rapidly being developed due to the increased awareness of global warming and growing reliance of society on renewable energy sources. Among various electrochemical energy storage technologies, high power supercapacitors and lithium ion batteries with excellent energy density stand out in terms of their flexibility and scalability. However, supercapacitors are handicapped by low energy density and batteries lag behind in power. Supercapatteries have emerged as hybrid devices which synergize the merits of supercapacitors and batteries with the likelihood of becoming the ultimate power sources for multi-function electronic equipment and electric/hybrid vehicles in the future. But the need for new and advanced electrodes is key to enhancing the performance of supercapatteries. Leading-edge technologies in material design such as nanoarchitectonics become very relevant in this regard. This work involves the preparation of vanadium pentoxide (V2O5), pristine and zinc doped lithium manganese silicate (Li2MnSiO4) nanoarchitectures as well as their composites with hydroxylated graphene (G-ol) and carbon nanotubes (CNT).
2023-12-01
Barakat, Mahmoud. "Development of models for inegrating renewables and energy storage components in smart grid applications." Thesis, Normandie, 2018. http://www.theses.fr/2018NORMC217/document.
This thesis presents a unique model of the SGAM (Smart Grid Architecture Model) with considering the state of the art of the different research directions of the smart grid and. The hybrid marine-hydrogen active power generation system has been modeled to represent the component layer of the SGAM. The system integrates the MW scale PEM electrolyzer and fuel cell systems as the main energy balance components. The LiFePO4 battery is used to cover the fast dynamics of the electrical energy. Moreover, the thesis analyzes the centralized and the decentralized energy management system. The MAS (Multi-Agent Systems) represents the paradigm of the decentralized system. The JADE platform is used to develop the MAS due to its general domain of application, open source and free license software, interface with MATLAB and the computability with the FIPA (Foundation of Intelligent Physical Agent) standards. The JADE based energy management system balances the energy between the generation (marine-current energy conversion system) and the demand side (residential load profile) during the stand-alone and the grid-connected modes of operation. The proposed model of the SGAM can be considered as a pilot case study that enables the detailed analysis and the applications of the different smart grid research directions
Sayah, Simon. "Impact de la formulation d'électrolytes sur les performances d'une électrode négative nanocomposite silicium-étain pour batteries Li-ion." Thesis, Tours, 2017. http://www.theses.fr/2017TOUR4025/document.
This study focuses on new electrolytes and additives in order to improve the cyclability of a Si0.32Ni0.14Sn0.17Al0.04C0.35 negative composite electrode (Si-Sn) and to obtain a stable electrolyte|electrolyte interface. Indeed, like most silicon-based materials, this high-capacity Si-Sn composite (over 600 mA.hg-1) currently suffers from a short cycle life due to volume expansion during charge-discharge processes leading to the degradation of the SEI. To improve the quality of the interface, two kinds of electrolytes were evaluated: (i) mixtures of alkyl carbonates EC/PC/3DMC in which a lithium salt (LiPF6, LiTFSI, LiFSI or LiDFOB) and additives like SEI builder (vinylene carbonate (VC) or fluoroethylene carbonate (FEC)) were added, (ii) ionic liquids (IL) based on quaternary ammonium (N1114+), imidazolium (EMI+) or pyrrolidinium (PYR+) cation, associated with delocalized charge anions such as bis(trifluoromethanesulfonyl)imide (TFSI-) or bis(fluorosulfonyl)imide (FSI-). The Walden diagram confirms the efficient dissociation of LiFSI and LiPF6 in EC/PC/3DM ensuring ionic conductivities as high as 12 mS.cm-1. Although possessing limited transport properties in such a ternary mixture compared to other salts, LiDFOB forms, without additional additives, an high quality SEI allowing the composite to provide the best performances in half cells (560 mA.hg-1 and 98.4% coulombic efficiency). The use of additive is however necessary to reach the objectives fixed by the ANR research project in terms of coulombic efficiency (>99.5%). In this case, the addition of 2%VC+10%FEC to the ternary mixture is the most interesting composition with LiPF6 as lithium salt. So, the Si-Sn nanocomposite material reaches 550 mA.h.g-1 during 100 cycles at C/5 with 99.8% efficiency. In IL, the best performances are achieved in [EMI][FSI]/LiFSI (1 mol.L-1). The performances of the Si-Sn composite reaches 635 mA.h.g-1 for 100 cycles at C/5 with coulombic efficiency close to 100%, without additives. This electrolyte formulation generates a stable SEI which the mainly mineral composition, is predominantly derived from the reduction products of FSI-
Lo, Cheng Hsing, and 羅正欣. "Experimental investigations on PVA/PEO hybrid polymer electrolytes." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/11099861979646423606.
長庚大學
化工與材料工程研究所
91
The alkaline polymer electrolyte membranes containing polyethylene oxide (PEO), polyvinyl alcohol (PVA) and using water as the solvent and potassium hydroxide (KOH) as the salt have been investigated in the present study. These polymer electrolyte membranes were characterized by A.C. impedance spectroscopic techniques. The ionic conductivity of the polymer electrolyte membranes increased with increasing PEO/PVA ratio. Ionic conductivity of these polymer membranes increases from 6.8×10-6 S/cm to 1.12×10-2 S/cm at room temperature when the ratio of PEO:PVA varied from 10:0 to 2:8. Temperature dependence of the conductivity was found to be in agreement with Arrhenius type with activation energy in the range of 2-9 kJ mole-1, depending on the electrolyte compositions. The characterizations of electrolyte properties were carried out on the PEO/PVA hybrid polymer membranes using DSC, SEM, POM, a.c impedance spectroscopic techniques and electrochemical spectroscopic techniques. It was found that the polymer electrolyte membranes exhibited high ionic conductivity, good mechanical property and excellent electrochemical stability.
Cardoso, Marita Alves. "Luminescent organic-inorganic hybrid electrolytes for smart building glazing." Doctoral thesis, 2021. http://hdl.handle.net/10773/31524.
Existe uma necessidade global de melhorar a eficiência energética nos edifícios com vista a uma nova geração de edifícios denominados edifícios de balanço energético nulo (ZEBs). Uma das estratégias propostas inclui o desenvolvimento de janelas inteligentes baseadas em dispositivos eletrocrómicos (ECDs) acoplados a camadas luminescentes e concentradores solares luminescentes (LSCs). Novos materiais baseados em complexos de iões lantanídeos com elevado rendimento quântico de emissão incorporados em matrizes hospedeiras apropriadas, preparadas pelo método sol-gel, abrem um leque de oportunidades para o desenvolvimento de novos dispositivos com notável desempenho eletro-ótico para janelas de ZEBs. Nesta tese, novos eletrólitos baseados em híbridos orgânicos-inorgânicos dopados com um líquido iónico luminescente permitiram a produção de ECDs com elevada transparência nas regiões espetrais do visível e NIR e, possibilitando o ajuste fino da passagem de luz solar e da energia solar, permitindo operação em três modos (brilhante quente, semi-brilhante quente, e frio escuro). O ECD oferece uma série de recursos extraordinários, em particular alta eficiência e modulação ótica, boa estabilidade, grande eficiência de coloração, excelente memória ótica e capacidade de auto-regeneração após stress mecânico. Além disso, novas ionossílicas funcionalizadas na superfície dopadas com iões lantanídeos (Ln3+ = Nd3+, Eu3+, Tb3+,Yb3+) foram produzidas, caracterizadas e incorporadas em poli(metil metacrilato) produzindo filmes transparentes com auto-absorção desprezável com potencial aplicação em LDS e LSC. Foi observado um aumento absoluto significativo na eficiência quântica externa da célula PV (EQE ~ 32% entre 300-360 nm em relação à célula PV base) demostrando a aplicabilidade dos materiais desenvolvidos para ZEBs.
Programa Doutoral em Ciência e Engenharia de Materiais
Angjeli, Kristina, Carlo Versace, Isabella Nicotera, and Roberto Bartolino. "Hybrid nanostructured fillers for polymer electrolytes in the PEM Fuel Cells." Thesis, 2012. http://hdl.handle.net/10955/1150.
The present thesis is focused on the development of novel nancomposite membranes, prepared by the incorporation of two-dimensional inorganic layered structures such as (i) smectite clays (synthetic and natural), (ii) graphene oxide (GO), and (iii) layered double hydroxides (LDHs) with different compositions into the polymer matrix of Nafion, for use as electrolytes in Proton Exchange Membrane fuel cells. The characteristics of the membranes were studied mainly, in terms of transport properties by NMR spectroscopy, in order to study the water dynamics inside the electrolyte membranes. For this purpose the Pulse-Field-Gradient Spin-Echo NMR (PFGSENMR) method was employed to obtain a direct measurement of water self-diffusion coefficients on the water-swelled membranes in a wide temperature range (25-140 °C). This technique together with the 1H-NMR spectral analysis and NMR spin-lattice relaxation times (T1) conducted under variable temperature. Furthermore, both pristine materials (fillers and Nafion) as well as the resulted nanocomposite membranes were characterized by a combination of X-ray diffraction, FTIR spectroscopy, thermal analysis (DTA/TGA), Raman spectroscopies and scanning electronic microscopy (SEM).
Università della Calabria
Chou, Chih-Yu, and 周致羽. "Glyme solvents based on Mg(BH4)2 as electrolyte for magnesium hybrid batteries." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/f4gtn8.
國立中央大學
化學工程與材料工程學系
104
Magnesium is an attractive anode material for secondary batteries because of low cost, low pollution, abundance, high energy density and high safety. However, there are two major obstacle in developing ideal magnesium ion batteries (MIBs). The first one is the formation of passivation layer on the surface due to the high chemical activity of magnesium. This result in restrictions on selecting suitable electrolytes. The other one is the strong coulombic interaction between Mg2+ and the intercalation host, which makes the ion diffusion sluggish, creating a barrier for the development of the cathode materials for MIBs. In this study, MoS2 is chosen as the active material which Mg2+ ion cannot intercalate/deintercalate into the host structure in the presence of APC electrolyte. After adding the lithium salt (LiCl) in the APC electrolyte, the Mg//MoS2 cell starts storing energy and its electrochemical behavior is very similar to MoS2 in lithium-ion battery system. The electrochemical performances significantly increase with the increase of lithium-ion concentration. At low concentration (0.1 M), the cell delivers reversible capacity of 45 mAh/g (at 25 mA/g), whereas at high concentration (0.7 M) the cell delivers superior capacity of 166 mAh/g. Similarly, the cell with high concentration of Li salt showed excellent high rate retention of 64% at 1000 mA/g, whereas the cell with low concentration of Li salt showed poor retention of 31%. The ion mobility is believed to play important role in electrochemical performance. After showing the remarkable benefits of dual-salts electrolyte, it is worth expanding this concept to other electrolytes, which have the nature of high safety and environmental friendliness. Therefore, we introduce Mg(BH4)2 salt and Glyme-based solvents as electrolyte. The present study indicate that substrates, temperature, concentration, solvent and the additive effects the reversibility of Magnesium deposition and dissolution. The study showed addition of LiBH4 and NaBH4 can improve the electrochemical performance of MIBs to a greater extent. To investigate the properties of different dual-salts Mg(BH4)2 (MBH) electrolyte, MoS2/Graphene composite is chosen as the active material. Among them, MBH-diglyme electrolyte delivered highest capacity, whereas MBH-triglyme and MBH-tetraglyme electrolytes showed slightly decreased capacity owing to their high viscosity. Despite the electrochemical performance between MBH and APC electrolyte are similar, MBH electrolyte is expected to replace APC electrolyte for practical application. This study reports the possibility of Na/Mg hybrid battery based on intercalated cathode material for the first time. Compared to lithium-ion and Li/Mg hybrid battery, the high rate retention of Na/Mg hybrid battery is much higher (up to 76%) but the capacity at low current density needs to be further improved. These results provide insight for further development of Na/Mg hybrid battery.
Pan, Yu-chi, and 潘育麒. "Structural characterization and dynamic properties of star-like organic-inorganic hybrid electrolytes." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/69131505390397753054.
國立中央大學
化學研究所
96
A sol-gel synthetic route for preparing poly(oxyalkylene) block copolymers has been developed by using 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride, cc) as the coupling core. The coupling reaction involves the selective substitutions of oligo(oxyalkylene)-amines at 0?C, 25?C and 130?C. Afterwards, (3-glycidyloxypropyl)-trimethoxysilane (GLYMO) reacts with the NH2 end groups of oligo(oxyalkylene)amines (Jeffamine-ED serious), and then the Si-OCH3 will condensation with other GLYMO. The effects of several variables on ionic conductivity were investigated, such as length of PEO chain, percentage of EO/PO segment, extent of cross-linking, and salt concentration (LiClO4). Characterization was made by solid-state NMR, Differential scanning calorimetry (DSC), AC-Impedance and IR spectroscopy. The optimal lithium conductivity for the copolymer electrolytes thus obtained reaches 4.3 x 10-5 S/cm at 30?C.
Lu, Shao Hao, and 呂紹豪. "Application of flexible composite lithium ion conducting membranes in hybrid electrolyte lithium air batteries." Thesis, 2019. http://ndltd.ncl.edu.tw/cgi-bin/gs32/gsweb.cgi/login?o=dnclcdr&s=id=%22107CGU05063035%22.&searchmode=basic.
Lo, Chieh, and 羅傑. "Studies on LixSnOS Superionic Conductor and its Hybrid Electrolyte for Solid State Lithium Ion Battery." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/2z8wch.
國立臺灣科技大學
材料科學與工程系
106
In recent years, commercially available lithium ion batteries have been mainly produced using organic electrolytes, but the problem of heat and explosion caused by improper use of batteries still continuously occurs. In addition, considering the miniaturization, flexibility and high energy density, the development of flexible all-solid-state lithium batteries is of importance. At present, there are two types of solid electrolyte materials: (1) Inorganic ceramic solid electrolyte and (2) Polymer solid electrolyte thin film. Although inorganic ceramic solid electrolyte membrane can provide the required lithium ion conductivity, there is a problem of rigidity, which cannot be applied to the flexible electronics; the polymer solid electrolyte membrane materials are all conductive macromolecules and can transfer conjugated electrons, but its lithium ion conductivity is not ideal. At present, in terms of research, Li10GeP2S12 and its derivatives Li10MP2X12 (M= Ge; Sn; Si, X=S; Se) and others have shown the good lithium ion conductivity of 10-2 S/cm at room temperature. Unfortunately, this type of sulfides is extremely sensitive to moisture. This study combines the advantages of high Li ion conductivity of sulfides and high chemical stability of oxides to prepare Li-Sn bimetal oxysulfide at different Li:Sn molar ratios to form the Li ion conductor of Li3x[LixSn1-x(O,S)2]. The experimental parameters include the different Li:Sn molar ratios for LixSnOS powders at x= 1, 1.5, 1.8, 2, and 2.2, the different processing temperatures at 500 oC, 550oC, and 600oC, and the different numbers of compensation disks for sulfurization at 0S, 0.5S, 1S, and 1.5S. The best solid electrolyte is the Li2SnOS-550-1S with Li ion conductivity of 1.92×10-4 S/cm, in which Li2SnOS-550-1S means the LixSnOS mixed powder has a Li:Sn molar ratio of 2:1 and is fired at 550 oC under one compensation disk. Solid-state lithium ion conductive powder of Li2SnOS-550-1S in the amount of 10, 20, 30, 40, and 50 wt.% was mixed with the modified PVDF-HFP electrolyte provided by the Institute of Nuclear Energy Research of Taiwan to form the inorganic/organic hybrid electrolytes. The hybrid electrolyte and its Li-ion battery device were evaluated for their properties. It was observed that the Li-ion conductivity of Li2SnOS-550/ PVDF-HFP hybrid films decreased with the increase in the amount of Li2SnOS-550, but the hybrid Li-ion battery with the sandwich structure of LiCoO2 /hybrid solid electrolyte/Li demonstrated improved performance. The hybrid Li-ion battery with the electrolyte of 30 wt.% Li2SnOS-550/ PVDF-HFP had the electrical capacity of 134.6 mAh/g and an efficiency of 95% for 30 cycle runs.
Chen, Yu-hsiu, and 陳育修. "Structural characterization and dynamic properties of organic-inorganic hybrid electrolytes based on alkoxysilane modification." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/34601708235558264454.
國立中央大學
化學研究所
95
This research focus on the preparation and characterization of organic–inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (ED600、ED900、ED2000) complexed with LiClO4 via the co-condensation of tetraethoxysilane (TEOS) and 3-(triethoxysilyl)propyl isocyanate. The dry organic–inorganic hybrid electrolytes thus obtained were also plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by volume). The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 2.11×10-3 S/cm of the polymer molecule weight 2000 at 30℃. A variety of techniques such as DSC、TGA、FT-IR、SEM、XRD、AC Impedance and solid state NMR spectroscopy are performed to elucidate the realtionship between the structural and dynamic properties of the hybrid electrolyte and the ion mobility. According to DSC results, the glass transition temperature (Tg) raised with increasing the lithium salt content. By means of 2D 1H-13C WISE (WIdeline SEparation) NMR, the dynamic information within such a hybrid system can be qualitatively assessed by examining the proton line shapes in the F1 dimension that are directly related to structural elements resolved in the 13C CP/MAS NMR spectrum in the F2 dimension. Furthermore, the 7Li diffusion coefficients of the dry hybrid electrolytes were determined by pulsed gradient spin-echo (PGSE) experiment to correlate with the behavior of the ion conductivity.
Liang, Wuu-Jyh, and 梁武智. "Studies on Preparation and Characterization of Lithium-ion Polymer Electrolytes Based on Polysiloxane Hybrid." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/a6g24j.
國立成功大學
化學工程學系碩博士班
92
In this dissertation, two categories of novel materials for polymer electrolytes based on polysiloxane hybrid were prepared, and their microstructures associated with ion conduction behavior were investigated. This monograph is divided into four parts as follows: 1. A new hybrid polymer electrolyte system containing polysiloxane and polyether segments is designed and prepared via epoxide-crosslinking. The thermal behavior, structure, and ionic conductivity of the hybrid materials are investigated and characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), 13C solid-state NMR, and alternating current (AC) impedance measurements. Two glass transition temperatures have been observed, showing their dependence on the composition and LiClO4/PC content. The miscibility of the polymer components in the hybrid has been studied by examining the 1H spin-relaxation times in the laboratory frame (T1(H)) and in the rotating frame (T1r(H)) with various compositions. Multi-relaxation T1r(H) behavior has been observed, indicative of the presence of structural heterogeneity at the time scale of T1r(H). These results are correlated and used to interpret the phenomena of conductivity of lithium ion in the matrix of hybrid networks. 2. Solid polymer electrolytes based on epoxide-crosslinked polysiloxane/polyether hybrid (SE55) were characterized by DSC, impedance measurements and 7Li MAS NMR spectra. The DSC results indicate that initially a cation complexation dominated by the crosslink site of SE55 is present, and subsequently the formation of transient cross-links between Li+ ions and the ether oxygens of polyether segment results in an increase in Tg of the polyether segment (Tg1). However, the Tg1 remains almost invariant at the highest salt concentration of O/Li+ = 4. A VTF-like temperature dependence of ionic conductivity is observed, implying that the diffusion of charge carrier is coupled with the segmental motions of the polymer chains, and furthermore, a maximum conductivity value is observed at O/Li+ = 20 in the analyzed temperature range. Significantly, the 7Li MAS NMR spectra provide high spectral resolution to demonstrate the presence of at least two distinct Li+ local environments in SE55-based electrolytes. Detailed analyses of DSC and 7Li MAS NMR spectra results are achieved and discussed in terms of ion-polymer and ion-ion interactions, and further correlated with ion transport behavior. 3. Hybrid organic-inorganic materials derived from 3-glycidoxypropyltrimethoxyl- silane (GPTMS) were prepared via two different synthetic routes: (1) HCl-catalyzed sol-gel approach of silane followed by lithium perchlorate (LiClO4)/HCl catalyzed opening of epoxide; (2) simultaneous gelation of tin/LiClO4 catalyzed silane/epoxide groups. LiClO4 catalyzes the epoxide polymerization, and its effects on the structure of these hybrid materials were studied by solid-state 13C and 29Si CP/MAS NMR. The different synthetic routes have been found to significantly affect the polymerization behaviors of organic and inorganic sides in the presence of LiClO4. Larger amount of LiClO4 promotes the opening of epoxide and leads to the formation of longer PEO chains via HCl-catalyzed sol-gel approach, whereas in the case of tin-catalyzed, the faster polymerization of inorganic side hinders the growth of the organic network. The addition of LiClO4 was proved to be without crystalline salt present in the hybrid networks by wide-angle X-ray powder diffraction. 4. A new class of hybrid ionic conductors with covalent bonds between the organic poly(ethylene oxide) chains and the siloxane phase were prepared based on poly(ethylene glycol) diglycidyl ether (PEGDE) and 3-glycidoxypropyltrisilane (GPTMS) in the presence of lithium perchlorate (LiClO4) which acted as both ionic source and the epoxide ring-opening catalyst. The effect of salt-doped level on the microstructure and ionic conductivity of these composite electrolytes were investigated by means of Fourier transform infra-red (FT-IR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), a. c. impedance and multinuclear solid-state nuclear magnetic resonance (NMR) measurements. Specially, DSC results indicate the formation of transient cross-links between Li+ ions and the ether oxygens on complexation with LiClO4 results in an increase in polyether segment Tg. However, the polyether segment Tg decreases at the highest salt concentration (5.0 mmol LiClO4 /g PEGDE). This is ascribed to the plasticizing effect, and can be further confirmed by 13C, 1H and 7Li MAS NMR spectra. Moreover, the behavior of ion transport is coupled with the segmental motions of polymer chains and also correlated with the interactions between ions and polymer host.
-zu, Hung, and 洪子迪. "Organic-Inorganic Hybrid Electrolytes Based on PPG-PEG-PPG Diamine, Alkoxysilanes, and Lithium Perchlorate." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/85032712347648602515.
國立中央大學
化學研究所
95
A novel organic-inorganic hybrid electrolyte based on the formation of ureasils through the reaction in different ratios of poly (propylene glycol)-block-poly (ethylene glycol)-block-poly (propylene glycol) bis (2-aminopropyl ether) (ED2000) with 3-isocyanatopropyltriethoxysilane (ICPTES), followed by the via the co-condensation of 3-Glycidoxypropyl -trimethoxysilane (GLYMO) in the presence of LiClO4, has been prepared. The structure and functionality of the materials thus obtained were characterized a variety of techniques including alternating current impedance, FT-IR spectroscopy, differential scanning calorimetry, and multinuclear solid-state NMR spectroscopy. The results of DSC measurements indicate the formation of transient cross-links between Li+ ions and the ether oxygens on complexation with LiClO4, resulting in an increase in the soft segment Tg. Behavior of ionic conductivity is Vogel-Tammann-Fulcher (VTF)-type. Solid-state NMR was used to probe the structure and dynamics of organic and inorganic components in the hybrid electrolyte and 13C cross-polarization/magic angle spinning NMR results from variable contact time measurements indicated that a significant decrease in the mobility of the polymer chains as the salt content was increased. 7Li NMR characterization was performed to study ionic mobility by measuring spectral line widths, T1 relaxation times, and diffusion coefficients. The results of the lithium diffusion coefficient measurements indicated that the ionic conductivity in the present electrolytes was mainly dominated by the mobility of the lithium cations.
Wu, Chen Yang, and 吳震洋. "Study on Refillable Bi-electrolyte Fuel Cell and the Method of Range-extending Charging Hybrid Mechanism." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/xfhm2p.
國立臺北科技大學
機電科技研究所
104
Nowadays proton exchange membrane fuel cell has been prosperously developed all over the world. Nevertheless, there exist a lot of obstacles about how to store, transport and fill up with fuel cell, no matter in solid, liquid or gas state. For safety concern, electric car runs short-distance trips only, and such inconvenience makes it unable to be promoted successfully. Therefore, we design an innovatively structured fuel cell, which takes add-on solid/liquid two-state electrolyte fuel cell as auxiliary power, and uses a new mechanical range-extending charging and driving mechanism. The fuel cell makes use of a wheel motor attached with planetary gear assembly, making an electric car have its mileage, speed and torsion increased, and be charged when running. It is hoped that zinc air fuel cell can step out of the laboratory to facilitate practical use of electric cars. In the study we firstly use micro-spherical Zn grains to synthesize hollowed Zn microspheres. Then the microspheres are mixed with KOH electrolyte to formZn plaster, but resulting in aggregation and precipitation. Later on, we employ a stirring technique to make Zn grains become permanently suspended, thus solving the problems of aggregation and precipitation.We also use 65 wt. % KOHelectrolyte to fabricate 35 wt. % Zn colloids. We test the current density7.41 mA/cm2, specific energy by mass840.14 Wh/kg, and capacitance of cell3023 mAh. The Zn grains purchased for the study this time are mixed with KOH electrolyte to form Zn colloids. Using constant voltage method, and when open-circuit voltage being 1.4V, reaction area being 25cm2, relative humidity being 100% and temperature being 60oC, the constant voltage is 0.3V; its current density is 70 mA / cm2; and the power is 0.53W. Due to use of various additives, unexpected product must adhere to it, and full reaction complexity must be caused, so the effect is not as good as expected. And it cannot solve Zn grains’most headachy and toughest problems, i.e. aggregation and precipitation. But we solve the corrosion and inactivation problems of Zn grains by refillable bi-electrolyte fuel cell. Special designs like press grinding and anode flow channel can solve the commercial Zn powder’s aggregation and precipitation problems. New cathode flow channel, which avoids cathode from using large amount of PTFE in order to prevent outflow of electrolyte, is yet followed by the problem of insufficient air intake. The special design of cathode flow channel can solve the problem of small-amount leakage easily caused at the entrance of flow channel where cells are accumulated. The solid electrolyte of anion exchange membrane is taken as reaction membrane. We do not use the nonwoven-cloth-made separation membrane, which may cause anode penetration and result in an extremely great danger ofshort circuit of cell. Therefore, add-on feeding can solve the inconvenient conventional way, by which Zn plaster was manually applied all over the anode power collection grid, and allows fuel cell to step out of the laboratory. In the process of reaction, air bubbles and produced water are produced continuously, proving that the fuel cell designed by the study is successful.
Su, Jia-Hong, and 蘇佳鴻. "The Preparation of PPG/SiO2/IL/LiClO4 Hybrid Ionogel Electrolyte and Its Application on Lithium Battery." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/62462502915834739210.
中原大學
奈米科技碩士學位學程
100
Most of the traditional preparation of polymer electrolytes are complicated and use organic solvent to dissolve the Polymer during the process. Besides, the solvent removing process usually causes energy loss and pollution problems, making the application of solid polymer electrolytes difficult to be pratical. In this study, the polymer/ionogel nanocomposite electrolyte membranes were successfully prepared by the one pot synthesis via sol-gel process with tetraethylorthosilicate (TEOS) as the precursor, 1-butyl-4-methyl imidazolium perchlorate [BMIM-ClO4], an ionic liquid, as ionic conductor, poly(propylene glycol) as reinforcer, lithium perchlorate (LiClO4) as Li-ion source and formic acid as catalyst. The as-prepared membranes were free-standing, translucent, flexible, non-crystallinity, solid-like electrolytes. Their physical and chemical properties were investigated by FT-IR, TGA, DSC, X-ray and SEM measurements. In addition, the capability and electrochemical properties were measured by performing charge-discharge cycles at different charge rate and temperature. The results showed that the one pot sol-gel process is a easier and cost effective method to prepare the polymer/ionogel nanocomposites without using organic solvents, avoiding the solvent removing problem.The highest conductivity of the polymer/ionogel nanocomposite electrolytes at room temperature was 5.88x10-4 S/cm exhibited by P5SI6C05. There is no weight loss until 237℃ from TGA study of P5SI6C05. The cyclic voltammetry measurement also showed that addition of the polymer enhanced the stability of electrochemical and interfaces properties of the nanocomposite elecatrolytes. Compared to the Ionic liquid electrolyte and ionogel electrolyte, the polymer/ionogel nanocomposite electrolyte showed better electrochemical properties and interface in the symmetric Li/ P5SI6C05/Li cells . The investigation of the effect of interactions among SiO2, BMIM,ClO4 and LiClO4 in the polymer/ionogel nanocomposite electrolyte showed that the activation energy of ionic migration in the nanocomposite electrolyte is lower than that in the ionic liquid electrolyte, revealing that the ion transport ability in the polymer/ionogel nanocomposite electrolyte is slightly better than that in the ionic liquid electrolyte. The capability of Li/P5SI6C05/LiFePO4 cell measured was unsatisfactory and is ascribed to the poor interface betweem the electrolyte membrane and the LiFePO4 electrode was that affected intercalation/outcalation ability of the Li+ to the cathode. Evan so, a commercial solar cell-LED was successfully assembled with the Li/P5SI6C05/LiFePO4 cell, and used the sun light to charge and discharge the cell. It is found that the cell is still functionable for more than 2 months, revealing the possiblility of application on the pocket eletronic products. As far as I understand, this is the first report of the half cell assembled by polymer/ionogel nanocomposite electrolyte with it’s lithium properties and applied to a pocket electronic device. The improvement of interface between the polymer/ionogels nanocomposite electrolyte and the electrodes of lithium battery is suggested for the future study.