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Shen, Kuan-Hsuan. "Modeling ion conduction through salt-doped polymers: Morphology, ion solvation, and ion correlations." The Ohio State University, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=osu1595422569403378.
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Kidd, Bryce Edwin. "Multiscale Transport and Dynamics in Ion-Dense Organic Electrolytes and Copolymer Micelles." Diss., Virginia Tech, 2016. http://hdl.handle.net/10919/82525.
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Understanding molecular and ion dynamics in soft materials used for fuel cell, battery, and drug delivery vehicle applications on multiple time and length scales provides critical information for the development of next generation materials. In this dissertation, new insights into transport and kinetic processes such as diffusion coefficients, translational activation energies (Ea), and rate constants for molecular exchange, as well as how these processes depend on material chemistry and morphology are shown. This dissertation also aims to serve as a guide for material scientists wanting to expand their research capabilities via nuclear magnetic resonance (NMR) techniques. By employing variable temperature pulsed-field-gradient (PFG) NMR diffusometry, which can probe molecular transport over nm – μm length scales, I first explore transport and morphology on a series of ion-conducting materials: an organic ionic plastic crystal, a proton-exchange membrane, and a polymer-gel electrolyte. These studies show the dependencies of small molecule and ion transport on modulations to material parameters, including thermal or magnetic treatment, water content, and/or crosslink density. I discuss the fundamental significance of the length scale over which translational Ea reports on these systems (~ 1 nm) and the resulting implications for using the Arrhenius equation parameters to understand and rationally design new ion-conductors. Next, I describe how NMR spectroscopy can be utilized to investigate the effect of loading a small molecule into the core of a spherical block copolymer micelle (to mimic, e.g., drug loading) on the hydrodynamic radius (rH) and polymer chain dynamics. In particular, I present spin-lattice relaxation (T1) results that directly measure single chain exchange rate kexch between micelles and diffusion results that inform on the unimer exchange mechanism. These convenient NMR methods thus offer an economical alternative (or complement) to time-resolved small angle neutron scattering (TR-SANS).Ph. D.
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Karo, Jaanus. "The Rôle of Side-Chains in Polymer Electrolytes for Batteries and Fuel Cells." Doctoral thesis, Uppsala universitet, Strukturkemi, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-100738.
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The subject of this thesis relates to the design of new polymer electrolytes for battery and fuel cell applications. Classical Molecular Dynamics (MD) modelling studies are reported of the nano-structure and the local structure and dynamics for two types of polymer electrolyte host: poly(ethylene oxide) (PEO) for lithium batteries and perfluorosulfonic acid (PFSA) for polymer-based fuel cells. Both polymers have been modified by side-chain substitution, and the effect of this on charge-carrier transport has been investigated. The PEO system contains a 89-343 EO-unit backbone with 3-15 EO-unit side-chains, separated by 5-50 EO backbone units, for LiPF6 salt concentrations corresponding to Li:EO ratios of 1:10 and 1:30; the PFSA systems correspond to commercial Nafion®, Hyflon® (Dow®) and Aciplex® fuel-cell membranes, where the major differences again lie in the side-chain lengths. The PEO mobility is clearly enhanced by the introduction of side-chains, but is decreased on insertion of Li salts; mobilities differ by a factor of 2-3. At the higher Li concentration, many short side-chains (3-5 EO-units) give the highest ion mobility, while the mobility was greatest for side-chain lengths of 7-9 EO units at the lower concentration. A picture emerges of optimal Li+-ion mobility correlating with an optimal number of Li+ ions in the vicinity of mobile polymer segments, yet not involved in significant cross-linkages within the polymer host. Mobility in the PFSA-systems is promoted by higher water content. The influence of different side-chain lengths on local structure was minor, with Hyflon® displaying a somewhat lower degree of phase separation than Nafion®. Furthermore, the velocities of the water molecules and hydronium ions increase steadily from the polymer backbone/water interface towards the centre of the proton-conducting water channels. Because of its shorter side-chain length, the number of hydronium ions in the water channels is ~50% higher in Hyflon® than in Nafion® beyond the sulphonate end-groups; their hydronium-ion velocities are also ~10% higher. MD simulation has thus been shown to be a valuable tool to achieve better understanding of how to promote charge-carrier transport in polymer electrolyte hosts. Side-chains are shown to play a fundamental rôle in promoting local dynamics and influencing the nano-structure of these materials.
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Shi, Jie. "Ion transport in polymer electrolytes." Thesis, University of St Andrews, 1993. http://hdl.handle.net/10023/15522.
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The ion-polymer and ion-ion interactions in polymer electrolytes based on high molecular weight, amorphous methoxy-linked PEO (PMEO) and lithium salts have been investigated by conductivity measurement, magic-angle spinning NMR (mas NMR) and pulsed field gradient NMR (pfgNMR) techniques. In the very dilute salt concentration region, ion pairing effects are dominant in these polymer electrolytes. Ion association is found to increase with temperature and salt concentration. Ion transport for these electrolytes is controlled both by segmental motion of the polymer and activation process, in which the former is important for the dilute concentration samples while the latter is important for the concentrated samples. The mass transport process in polymer electrolytes based on a zinc salt has been investigated by steady state dc polarisation and Hittorf techniques. Zinc ion constituents in these electrolytes are mobile with a limiting current fraction of about 0.2 at 80°C, and the transference number measured by the Hittorf method is less than 0.1. The main species in these electrolytes are proposed to be neutral mobile triples. The electrode-electrolyte interfaces in polymer electrolytes based on calcium and magnesium salts have been studied. Dc polarisation experiments for these polymer electrolytes were carried out using two electrode cells with the metal anode and mercury film amalgam cathode. The results of dc polarisation experiments suggest that calcium species are mobile in high molecular weight electrolytes, while magnesium species are immobile. The influence of the molecular weight of the polymer on the dynamics of cation constituents has been studied based on the experimental results of dc polarisation and pfg NMR, and on the theoretical analyses of the reptation theory and the Rouse model. It is found that the transport of the gravity centre of the polymer will influence the ion transport in polymer electrolytes based on PEO in a manner described by the Rouse model when the molecular weight of PEO is less than 3200.
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Sorrie, Graham A. "Liquid polymer electrolytes." Thesis, University of Aberdeen, 1987. http://digitool.abdn.ac.uk/R?func=search-advanced-go&find_code1=WSN&request1=AAIU499826.
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This thesis is concerned with ion-ion and ion-polymer interactions over a wide concentration range in polymer electrolytes with a view to shedding new light on the mechanism of ion migration. Additionally, the electrochemical stability window of these electrolytes on platinum and vitreous carbon electrodes has been thoroughly investigated. The final part of this thesis is concerned with determining the feasibility of polymer electrolytes as electrolytes in a new type of energy storage device, a double layer capacitor which incorporates activated carbon cloth electrodes. Conductivities and viscosities of solutions of Li, Na and K thiocyanates in low-molecular-weight, non-crystallizable liquid copolymers of ethylene oxide (EO) and propylene oxide (PO) have been measured. The curves of molar conductance versus sqrt c show well-defined maxima and minima. The conductivity is independent of copolymer molecular-weight but is enhanced by raising the EO content of the copolymer. The results are interpreted in terms of a model for ion migration in which ion association and redissociation effects play an important role. It is proposed that the characteristic properties of liquid polymer electrolytes can only be satisfactorily explained if the current is largely anionic. The electrochemical stability window of these electrolytes on platinum is dominated by the presence of a water reduction peak starting at approximately -1.0V which limits the overall stability to approximately 2V. The onset of water reduction is displaced to more negative potentials (-3.0V), thus increasing the stability window, on vitreous carbon electrodes. The value of the double layer capacitance on vitreous carbon electrodes (15-30muF cm-2) agrees well with published data. The double layer capacitance of activated carbon cloth electrodes is lower than anticipated. The importance of faradaic charging and discharging currents to the successful operation of double layer capacitors is indicated but no problems relating to the specific use of polymer electrolytes in such devices were found.
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McHattie, Gillian S. "Ion transport in liquid crystalline polymer electrolytes." Thesis, University of Aberdeen, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324432.
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A systematic study of structure-property relations has been carried out on a range of polymers, both with and without mesogenic moieties. These materials have been characterised using various thermal techniques, including DSC and DMTA. These polymers have been complexed with LiClO4 and the effects of the salt on thermal characteristics have been investigated. In addition, AC impedance spectroscopy has been employed to determine the temperature dependence of the conductivity of these complexes. Results suggest that polymers with mesogenic side groups have the potential to exhibit a conduction mechanism which is independent of both the glass transition temperature of the complex as determined by DSC and the corresponding structural relaxation detected using DMTA. It is found that the glass transition temperature of these materials is determined primarily by the side groups, and not by the polymer backbone. A model is thereby proposed in which ionic motion is decoupled from Tg, but still dependent on the local viscosity of the ionic environment. Appreciable conductivity is therefore observed below the glass transition temperature of the complex, thus resulting in dimensionally stable polymeric complexes with possible applications as solid state electrolytes in batteries.
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Lacey, Matthew James. "Electrodeposited polymer electrolytes for 3D Li-ion microbatteries." Thesis, University of Southampton, 2012. https://eprints.soton.ac.uk/348605/.
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The electropolymerisation of vinyl monomers has been investigated as a route to the conformal deposition of thin polymer electrolyte films on porous electrode surfaces, for application in 3D Li-ion microbatteries. The deposition of poly(acrylonitrile) and poly(poly(ethylene glycol) diacrylate) has been monitored using cyclic voltammetry and an electrochemical quartz crystal microbalance (EQCM). It was determined that the polymerisation reaction may be initiated either by direct reduction of the monomer or via a separate reactive intermediate such as the superoxide anion. Furthermore, it was established that film thickness was easily controlled under cyclic voltammetry conditions, for example by varying the number of cycles. However, the choice of solvent and electrode surface was found to be of critical importance. This electropolymerisation technique was adapted to achieve the single step electrodeposition of a gel polymer electrolyte based on poly(ethylene glycol) diacrylate (PEGDA). Modification of the polymer to improve the mechanical properties and ionic conductivity was achieved by the incorporation of silica nanoparticles and plasticising monoacrylates into the polymer matrix. Through these modification procedures a PEGDA-based electrolyte was prepared with an ionic conductivity of the order of 10−4 S cm−1 and demonstrated, for the first time, sufficient mechanical strength to be used as the separator in spring-pressured planar half- and full cell configurations. The conformal nature of the deposit was assessed by scanning electron microscopy (SEM) and it was found that a uniform film of thickness as low as 2 μm was easily achievable. An initial attempt at a full 3D Li-ion microbattery cell based on a carbon foam substrate using composite electrode materials was made. The electrodeposited polymer electrolyte showed good electronic isolation and the cell showed limited cycling ability. The internal structure of the 3D cell was investigated by SEM and x-ray computed tomography.
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Chen, Songela Wenqian. "Modeling ion mobility in solid-state polymer electrolytes." Thesis, Massachusetts Institute of Technology, 2019. https://hdl.handle.net/1721.1/122534.
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Thesis: S.B., Massachusetts Institute of Technology, Department of Chemistry, 2019Cataloged from PDF version of thesis.
Includes bibliographical references (pages 31-32).
We introduce a course-grained model of ion diffusion in a solid-state polymer electrolyte. Among many tunable parameters, we investigate the effect of ion concentration, ion-polymer attraction, and polymer disorder on cation diffusion. For the conditions tested, we find that ion concentration has little effect on diffusion. Polymer disorder creates local variation in behavior, which we call "trapping" (low diffusion) and "free diffusing" (high diffusion) regions. Changing ion-polymer attraction modulates the relative importance of trapping and free diffusing behavior. Using this model, we can continue to investigate how a number of factors affect cation diffusion both mechanistically and numerically, with the end goal of enabling rapid computational material design.
by Songela Wenqian Chen.
S.B.
S.B. Massachusetts Institute of Technology, Department of Chemistry
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Maranski, Krzysztof Jerzy. "Polymer electrolytes : synthesis and characterisation." Thesis, University of St Andrews, 2013. http://hdl.handle.net/10023/3411.
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Crystalline polymer/salt complexes can conduct, in contrast to the view held for 30 years. The alpha-phase of the crystalline poly(ethylene oxide)₆:LiPF₆ is composed of tunnels formed from pairs of (CH₂-CH₂-O)ₓ chains, within which the Li⁺ ions reside and along which the latter migrate.¹ When a polydispersed polymer is used, the tunnels are composed of 2 strands, each built from a string of PEO chains of varying length. It has been suggested that the number and the arrangement of the chain ends within the tunnels affects the ionic conductivity.² Using polymers with uniform chain length is important if we are to understand the conduction mechanism since monodispersity results in the chain ends occurring at regular distances along the tunnels and imposes a coincidence of the chain ends between the two strands.² Since each Li⁺ is coordinated by 6 ether oxygens (3 oxygens from each of the two polymeric strands forming a tunnel), monodispersed PEOs with the number of ether oxygen being a multiple of 3 (NO = 3n) can form either “all-ideal” or “all-broken” coordination environments at the end of each tunnel, while for both NO = 3n-1 and NO = 3n+1 complexes, both “ideal” and “broken” coordinations must occur throughout the structure. A synthetic procedure has been developed and a series of 6 consecutive (increment of EO unit) monodispersed molecular weight PEOs have been synthesised. The synthesis involves one end protection of a high purity glycol, functionalisation of the other end, ether coupling reaction (Williamson's type ether synthesis³), deprotection and reiteration of ether coupling. The parameters of the process and purification methods have been strictly controlled to ensure unprecedented level of monodispersity for all synthesised samples. Thus obtained high purity polymers have been used to study the influence of the individual chain length on the structure and conductivity of the crystalline complexes with LiPF₆. The results support the previously suggested model of the chain-ends arrangement in the crystalline complexes prepared with monodispersed PEO² over a range of consecutive chain lengths. The synthesised complexes constitute a series of test samples for establishing detailed mechanism of ionic conductivity. Such series of monodispersed crystalline complexes have been studied and characterised here (PXRD, DSC, AC impedance) for the first time. References: 1. G. S. MacGlashan, Y. G. Andreev, P. G. Bruce, Structure of the polymer electrolyte poly(ethylene oxide)₆:LiAsF₆. Nature, 1999, 398(6730): p. 792-794. 2. E. Staunton, Y. G. Andreev, P. G. Bruce, Factors influencing the conductivity of crystalline polymer electrolytes. Faraday Discussions, 2007, 134: p. 143-156. 3. A. Williamson, Theory of Aetherification. Philosophical Magazine, 1850, 37: p. 350-356.
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Hekselman, Aleksandra K. "Crystalline polymer and 3D ceramic-polymer electrolytes for Li-ion batteries." Thesis, University of St Andrews, 2014. http://hdl.handle.net/10023/11950.
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The research work presented in this thesis comprises a detailed investigation of conductivity mechanism in crystalline polymer electrolytes and development of a new class of ceramic-polymer composite electrolytes for Li-ion batteries. Firstly, a robust methodology for the synthesis of monodispersed poly(ethylene oxides) has been established and a series of dimethyl-protected homologues with 13, 15, 17, 28, 29, 30 ethylene oxide repeat units was prepared. The approach is based on reiterative cycles of chain extension and deprotection, followed by end-capping of the oligomeric chain ends with methyl groups. The poly(ethylene oxide) homologues show a superior level of monodispersity to previous work and were subsequently used to prepare crystalline PEO6:LiPF6 polymer electrolytes. A correlation between the number of ether oxygens in the polymer chain and the ionic conductivity of crystalline polymer electrolytes has been established. The structure and dynamics of the monodispersed complexes were studied using solid-state NMR spectroscopy for the first time. The results are in agreement with the proposed mechanism of ionic conductivity in crystalline polymer electrolytes. A new class of composite solid electrolytes for all-solid-state batteries with a lithium metal anode is reported. The composite material consists of a 3D interpenetrating network of a ceramic electrolyte, Li₁.₄Al₀.₄Ge₁.₆(PO₄)₃, and an inert polymer (polypropylene), providing continuous pathways for the ionic transport and excellent mechanical properties. 3D connectivity of this novel composite was confirmed using X-ray microtomography and AC impedance spectroscopy.
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Willgert, Markus. "Solid Polymer Lithium-Ion Conducting Electrolytes for Structural Batteries." Doctoral thesis, KTH, Ytbehandlingsteknik, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-144169.
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This work comprises the manufacture and characterization of solid polymer lithium ion conducting electrolytes for structural batteries. In the study, polymer films are produced in situ via a rapid versatile UV irradiation polymerization route, in which ethylene oxide methacrylates are polymerized into thermoset networks. In the first part of the study, the simplicity and efficiency of this manufacturing route is emphasized. Polymer electrolytes are pro-duced with an ionic conductivity ranging from 5.8×10-10 S cm-1 up to 1.5×10-6 S cm-1, and a storage modulus of up to 2 GPa at 20°C. In the sec-ond part, the effect of the lithium salt content is studied, both for tightly crosslinked systems with a glass transition temperature (Tg) above room temperature but also for sparsely crosslinked system with a Tg below. It is shown that for these systems, there is a threshold amount of 4% lithium salt by weight, above which the ion conducting ability is not affected to a larger extent when the salt content is increased further. It is also shown that the influence of the salt content on the ionic conductivity is similar within both systems. However, the Tg is more affected by the addition of lithium salt for the loosely crosslinked system, and since the Tg is the main affecting parame-ter of the conductivity, the salt content plays a larger role here. In the third part of the study, a thiol functional compound is added via thiol-ene chemistry to create thio-ether segments in the polymer network. This is done in order to expand the toolbox of possible building blocks usable in the design of structural electrolytes. It is shown that solid polymer electrolytes of more homogeneous networks with a narrower glass transition region can be produced this way, and that they have the ability to function as an electrolyte. Finally, the abilities of reinforcing the electrolytes by nano fibrilar cellulose are investigated, by means to improve the mechanical properties without decreasing the ionic conductivity at any larger extent. These composites show conductivity values close to 10-4 S cm-1 and a storage modulus around 400 MPa at 25 °C.QC 20140410
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Willgert, Markus. "Solid Polymer Lithium-ion Conducting Electrolytes for Structural Batteries." Licentiate thesis, KTH, Ytbehandlingsteknik, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-107182.
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Ainsworth, David A. "Crystalline polymer and small molecule electrolytes." Thesis, University of St Andrews, 2010. http://hdl.handle.net/10023/2156.
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The research presented in this thesis includes a detailed investigation into factors influencing ionic conductivity in the crystalline polymer electrolyte PEO₆:LiPF₆. It has previously been shown that preparing PEO₆:LiPF₆ with PEO modified with larger –OC₂H₅ end groups increases ionic conductivity by one order of magnitude [¹],primarily due to disruption of the crystal structure caused by the inclusion of the larger end groups. In this study it is shown that by reducing PEO molecular weight in crystalline PEO₆:LiPF₆ ionic conductivity is also increased. This was attributed to an increasing concentration of polymer chain end regions upon lowering molecular weight resulting in the creation of more defects, as well as possible increases in crystallite size resulting in longer continuous pathways for ion transport. Similar results were observed using both polydispersed and monodispersed PEO to prepare complexes. In addition, it is demonstrated here that ionic conductivity in crystalline polymerelectrolytes is not confined to PEO₆:LiXF₆ (X=P, As, Sb)[²][³] type materials. The structures and ionic conductivity data are reported for a series of new crystalline polymer complexes: the alkali metal electrolytes. They are composed of low molecular weight PEO and different alkali metal hexafluoro salts (Na⁺, K⁺ and Rb⁺), and include the best conductor poly(ethylene oxide)₈:NaAsF₆ discovered to date [⁴], with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)₆:LiAsF₆. A new class of solid ion conductor is reported: the crystalline small-molecule electrolytes. Such materials consist of lithium salts dissolved in low molecular weight glyme molecules [CH₃O(CH₂CH₂O)[subscript(n)]CH₃, n=1-12], forming crystalline complexes [⁵][⁶]. These materials are soft solids unlike ceramic electrolytes and unlike polymer electrolytes they are highly crystalline, are of low molecular weight and have no polydispersity. By varying the number of repeat units in the glyme molecule, many complexes may be prepared with a wide variety of structures. Here, ionic conductivity and cation transference number (t₊) data for several such complexes is presented [⁷][⁸][⁹].These complexes have appreciable ionic conductivities for crystalline complexes and their t₊ values vary markedly depending on the glyme molecule utilized. The differences in t₊ values can be directly attributed to differences in their crystal structures. [¹] Staunton, E., Andreev, Y.G. & Bruce, P.G. Factors influencing the conductivity of crystalline polymer electrolytes. Faraday Discussions 134, 143-156 (2007). [²] Gadjourova, Z., Andreev, Y.G., Tunstall, D.P. & Bruce, P.G. Ionic conductivity in crystalline polymer electrolytes. Nature 412, 6846 (2001). [³] Stoeva, Z., Martin-Litas, I., Staunton, I., Andreev, Y.G. & Bruce, B.G. Ionic Conductivity in the Crystalline Polymer Electrolytes PEO₆:LiXF₆, X = P, As, Sb. J. Am. Chem. Soc. 125, 4619-4626(2003). [⁴] Zhang, C., Gamble, S., Ainsworth, D., Slawin, A.M.Z., Andreev, Y.G. & Bruce, P.G. Alkali metal crystalline polymer electrolytes. Nature Materials 8, 580-584 (2009). [⁵] Henderson, W.A., Brooks, N.R., Brennessel, W.W. & Young Jr, V.G. Triglyme-Li⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (I). Chem. Mater. 15, 4679-4684 (2003). [⁶] Henderson, W.A., Brooks, N.R. & Young Jr, V.G. Tetraglyme-Li⁺ Cation Solvate Structures: Models for Amorphous Concentrated Liquid and Polymer Electrolytes (II). Chem. Mater. 15, 4685-4690 (2003). [⁷] Zhang, C., Andreev, Y.G. & Bruce, P.G. Crystalline small-molecule electrolytes. Angewandte Chemie, International Edition 46, 2848-2850 (2007). [⁸] Zhang, C., Ainsworth, D., Andreev, Y.G. & Bruce, P.G. Ionic Conductivity in the Solid Glyme Complexes [CH₃O(CH₂CH₂O)[subscript(n)]CH₃]:LiAsF₆ (n = 3,4). J. Am. Chem. Soc. 129, 8700- 8701 (2007). [⁹] Zhang, C., Lilley, S.J., Ainsworth, D., Staunton, E., Andreev, Y.G., Slawin, A.M.Z. & Bruce, P.G. Structure and Conductivity of Small-Molecule Electrolytes [CH₃O(CH₂CH₂O)[subscript(n)]CH₃]:LiAsF₆ (n = 8-12). Chem. Mater. 20, 4039-4044 (2008).
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Bayrak, Pehlivan İlknur. "Functionalization of polymer electrolytes for electrochromic windows." Doctoral thesis, Uppsala universitet, Fasta tillståndets fysik, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-204437.
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Saving energy in buildings is of great importance because about 30 to 40 % of the energy in the world is used in buildings. An electrochromic window (ECW), which makes it possible to regulate the inflow of visible light and solar energy into buildings, is a promising technology providing a reduction in energy consumption in buildings along with indoor comfort. A polymer electrolyte is positioned at the center of multi-layer structure of an ECW and plays a significant role in the working of the ECW. In this study, polyethyleneimine: lithium (bis(trifluoromethane)sulfonimide (PEI:LiTFSI)-based polymer electrolytes were characterized by using dielectric/impedance spectroscopy, differential scanning calorimetry, viscosity recording, optical spectroscopy, and electrochromic measurements. In the first part of the study, PEI:LiTFSI electrolytes were characterized at various salt concentrations and temperatures. Temperature dependence of viscosity and ionic conductivity of the electrolytes followed Arrhenius behavior. The viscosity was modeled by the Bingham plastic equation. Molar conductivity, glass transition temperature, viscosity, Walden product, and iso-viscosity conductivity analysis showed effects of segmental flexibility, ion pairs, and mobility on the conductivity. A connection between ionic conductivity and ion-pair relaxation was seen by means of (i) the Barton-Nakajima-Namikawa relation, (ii) activation energies of the bulk relaxation, and ionic conduction and (iii) comparing two equivalent circuit models, containing different types of Havriliak-Negami elements, for the bulk response. In the second part, nanocomposite PEI:LiTFSI electrolytes with SiO2, In2O3, and In2O3:Sn (ITO) were examined. Adding SiO2 to the PEI:LiTFSI enhanced the ionic conductivity by an order of magnitude without any degradation of the optical properties. The effect of segmental flexibility and free ion concentration on the conduction in the presence of SiO2 is discussed. The PEI:LiTFSI:ITO electrolytes had high haze-free luminous transmittance and strong near-infrared absorption without diminished ionic conductivity. Ionic conductivity and optical clarity did not deteriorate for the PEI:LiTFSI:In2O3 and the PEI:LiTFSI:SiO2:ITO electrolytes. Finally, propylene carbonate (PC) and ethylene carbonate (EC) were added to PEI:LiTFSI in order to perform electrochromic measurements. ITO and SiO2 were added to the PEI:LiTFSI:PC:EC and to a proprietary electrolyte. The nanocomposite electrolytes were tested for ECWs with the configuration of the ECWs being plastic/ITO/WO3/polymer electrolyte/NiO (or IrO2)/ITO/plastic. It was seen that adding nanoparticles to polymer electrolytes can improve the coloring/bleaching dynamics of the ECWs. From this study, we show that nanocomposite polymer electrolytes can add new functionalities as well as enhancement in ECW applications.
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Chintapalli, Mahati. "Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries." Thesis, University of California, Berkeley, 2017. http://pqdtopen.proquest.com/#viewpdf?dispub=10250632.
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When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes.
In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS- b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale ~1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions preferentially into the endgroup-rich regions. On the other hand, the SEO/LiTFSI electrolytes are fully microphase-separated, solid, lamellar materials in which the PS block provides mechanical rigidity and the PEO block solvates the ions. In these electrolytes longer length scale structure (∼10 nm – 1 μm) influences ion transport. We study the relationships between the lamellar grain size, salt concentration, and ionic conductivity using ac impedance spectroscopy, small angle X-ray scattering, electron microscopy, and finite element simulations. In experiments, decreasing grain size is found to correlate with increasing salt concentration and increasing ionic conductivity. Studies on both of these polymer electrolytes illustrate that structure and ion transport are closely linked.
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Spence, Graham Harvey. "New polymer and gel electrolytes for potential application in smart windows." Thesis, Heriot-Watt University, 1998. http://hdl.handle.net/10399/614.
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Yu, Zhou. "Molecular Structure and Dynamics of Novel Polymer Electrolytes Featuring Coulombic Liquids." Diss., Virginia Tech, 2019. http://hdl.handle.net/10919/87049.
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Polymer electrolytes are indispensable in numerous electrochemical systems. Existing polymer electrolytes rarely meet all technical demands by their applications (e.g., high ionic conductivity and good mechanical strength), and new types of polymer electrolytes continue to be developed. In this dissertation, the molecular structure and dynamics of three emerging types of polymer electrolytes featuring Coulombic liquids, i.e., polymerized ionic liquids (polyILs), nanoscale ionic materials (NIMs), and polymeric ion gels, were investigated using molecular dynamics (MD) simulations to help guide their rational design.
First, the molecular structure and dynamics of a prototypical polyILs, i.e., poly(1-butyl-3-vinylimidazolium hexafluorophosphate), supported on neutral and charged quartz substrates were investigated. It was found that the structure of the interfacial polyILs is affected by the surface charge on the substrate and deviates greatly from that in bulk. The mobile anions at the polyIL-substrate interfaces diffuse mainly by intra-chain hopping, similar to that in bulk polyILs. However, the diffusion rate of the interfacial mobile anions is much slower than that in bulk due to the slower decay of their association with neighboring polymerized cations.
Second, the structure and dynamics of polymeric canopies in the modeling NIMs where the canopy thickness is much smaller than their host nanoparticle were studied. Without added electrolyte ions, the polymeric canopies are strongly adsorbed on the solid substrate but maintain modest in-plane mobility. When electrolyte ion pairs are added, the added counter-ions exchange with the polymeric canopies adsorbed on the charged substrate. However, the number of the adsorbed electrolyte counter-ions exceeds the number of desorbed polymeric canopies, which leads to an overscreening of the substrate's charge. The desorbed polymers can rapidly exchange with the polymers grafted electrostatically on the substrate.
Finally, the molecular structure and dynamics of an ion gel consisting of PBDT polyanions and room-temperature ionic liquids (RTIL) were studied. First, a semi-coarse-grained model was developed to investigate the packing and dynamics of the ions in this ion gel. Ions in the interstitial space between polyanions exhibit distinct ordering, which suggests the formation of a long-range electrostatic network in the ion gel. The dynamics of ions slow down compared to that in bulk due to the association of the counter-ions with the polyanions' sulfonate groups. Next, the RTIL-mediated interactions between charged nanorods were studied. It was discovered that effective rod-rod interaction energy oscillates with rod-rod spacing due to the interference between the space charge near each rod as the two rods approach each other. To separate two rods initially positioned at the principal free energy minimum, a significant energy barrier (~several kBT per nanometer of the nanorod) must be overcome, which helps explain the large mechanical modulus of the PBDT ion gel reported experimentally.Ph. D.
Polymer electrolytes are an indispensable component in numerous electrochemical devices. However, despite decades of research and development, few existing polymer electrolytes can offer the electrochemical, transport, mechanical, and thermal properties demanded by practical devices and new polymer electrolytes are continuously being developed to address this issue. In this dissertation, the molecular structure and dynamics of three emerging novel polymer electrolytes, i.e., polymerized ionic liquids (polyILs), nanoscale ionic materials (NIMs), and polymeric ion gels, are investigated to understand how their transport and mechanical properties are affected by their molecular design. The study of polyILs focused on the interfacial behavior of a prototypical polyILs supported on neutral and charged quartz substrates. It was shown that the structure and diffusion mechanism of the interfacial polyILs are sensitive to the surface charges of the substrate and can deviate strongly from that in bulk polyILs. The study of NIMs focused on how the transport properties of the dynamically grafted polymers are affected by electrolyte ion pairs. It was discovered that the contaminated ions can affect the conformation the polymeric canopies and the exchange between the “free” and “grafted” polymers. The study of polymeric ion gels focused on the molecular and mesoscopic structure of the ionic liquids in the gel and the mechanisms of ion transport in these gels. It was discovered that the ions exhibit distinct structure at the intermolecular and the interrod scales, suggesting the formation of extensive electrostatic networks in the gel. The dynamics of ions captured in simulations is qualitatively consistent with experimental observations.
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Brandell, Daniel. "Understanding Ionic Conductivity in Crystalline Polymer Electrolytes." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis : Univ.-bibl. [distributör], 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-5734.
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Liivat, Anti. "Ordering in Crystalline Short-Chain Polymer Electrolytes." Doctoral thesis, Uppsala : Acta Universitatis Upsaliensis, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-7853.
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Törmä, Erik. "Synthesis and characterisation of solid low-Tg polymer electrolytes for lithium-ion batteries." Thesis, Uppsala universitet, Institutionen för kemi - Ångström, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-226754.
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Electrolytes of poly(trimethylene carbonate-co-ε-caprolactone), poly(TMC-co-CL), and LiTFSI have been prepared and characterised. The copolymers were analysed with GPC and NMR, which showed that random high molecular weight copolymers of desired compositions had been obtained. The electrolytes with varied salt concentration were examined with TGA, DSC, FTIR and impedance spectroscopy. The highest ionic conductivities were measured for the copolymer of 60:40 ratio of TMC:CL and for the homopolymer poly(ε-caprolactone), PCL, both electrolytes with 28 wt% LiTFSI. The ionic conductivity was measured to of the order of 10−3 S cm−1 for the PCL electrolyte and 10−4 S cm−1 for the 60:40 copolymer at 50 °C.
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Guo, Jiao. "Development of Ion Conductive Polymer Gel Electrolytes and Their Electrochemical and Electromechanical Behavior Studies." University of Akron / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=akron1279140041.
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Otaduy, Maria Concepcion Garcia. "A nuclear magnetic resonance study of ionic dynamics in solid polymer electrolytes." Thesis, University of Kent, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263697.
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LINGUA, GABRIELE. "Newly designed single-ion conducting polymer electrolytes enabling advanced Li-metal solid-state batteries." Doctoral thesis, Politecnico di Torino, 2022. http://hdl.handle.net/11583/2969103.
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Plylahan, Nareerat. "Electrodeposition of Polymer Electrolytes into Titania Nanotubes as Negative Electrode for 3D Li-ion Microbatteries." Thesis, Aix-Marseille, 2014. http://www.theses.fr/2014AIXM4049.
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Des nanotubes de dioxyde de titane (TiO2nts) sont étudiés comme électrodes négatives potentielles pour des microbatteries Li-ion 3D. Ces TiO2nts lisses et hautement auto-organisés sont élaborés par anodisation du Ti dans des électrolytes organiques à base de glycérol ou d'éthylène glycol contenant des ions fluor et de l'eau en faible quantité. Les structures présentant un diamètre de 100 nm et une longueur variant de 1,5 à 14 µm sont particulièrement appropriés pour l'application visée. Les TiO2nts ont été tapissés de manière conforme par un électrolyte polymère (PMA-PEG) comportant un sel de lithium (LiTFSI) grâce à la technique d'électropolymérisation. Les études morphologiques menées par SEM et TEM ont montré que les nanotubes sont entièrement recouverts d'un film mince polymère de 10 nm d'épaisseur, ce qui permet de préserver la structure 3D de l'électrode. Les tests électrochimiques portant sur les nanotubes seuls ainsi que sur les TiO2nts tapissés d'électrolyte polymère ont été effectués en demi-cellule et en cellule complète en utilisant un électrolyte polymère à base de MA-PEG contenant du LiTFSI. En demi-cellule, les TiO2nts de 1,5 µm de long delivrent une capacité surfacique de 22 µAh cm-2 relativement stable sur 100 cycles. La performance de la demi-cellule est améliorée de 45% à une cinétique de 1C lorsque les TiO2nts sont tapissés de manière conforme par un electrolyte polymère (PMA-PEG). Cet effet résulte d'un meilleur transport de charges lié à l'augmentation de la surface de contact entre l'électrode et l'électrolyteTitania nanotubes (TiO2nts) as potential negative electrode for 3D lithium-ion microbatteries have been reported. Smooth and highly-organized TiO2nts are fabricated by electrochemical anodization of Ti foil in glycerol or ethylene glycol electrolyte containing fluoride ions and small amount of water. As-formed TiO2nts shows the open tube diameter of 100 nm and the length from 1.5 to 14 µm which are suitable for the fabrication of the 3D microcbatteries. The deposition of PMA-PEG polymer electrolyte carrying LiTFSI salt into TiO2nts has been achieved by the electropolymerization reaction. The morphology studies by SEM and TEM reveal that the nanotubes are conformally coated with 10 nm of the polymer layer at the inner and outer walls from the bottom to the top without closing the tube opening. 1H NMR and SEC show that the electropolymerization leads to PMA-PEG that mainly consists of trimers. XPS confirms the presence of LiTFSI salt in the oligomers.The electrochemical studies of the as-formed TiO2nts and polymer-coated TiO2nts have been performed in the half-cells and full cells using MA-PEG gel electrolyte containing LiTFSI in Whatman paper as separator. The half-cell of TiO2nts (1.5 µm long) delivers a stable capacity of 22 µAh cm-2 over 100 cycles. The performance of the half-cell is improved by 45% at 1C when TiO2nts are conformally coated with the polymer electrolyte. The better performance results from the increased contact area between electrode and electrolyte, thereby improving the charge transport
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Fujimura, Koji. "Theoretical Studies of Lithium-Ion Diffusion in LISICON-Type Solid Electrolytes." Master's thesis, 京都大学 (Kyoto University), 2013. http://hdl.handle.net/2433/180501.
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Agapov, Alexander. "Decoupling Phenomena in Dynamics of Soft Matter." University of Akron / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=akron1321922264.
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Andersson, Jonas. "Synthesis of polycarbonate polymer electrolytes for lithium ion batteries and study of additives to raise the ionic conductivity." Thesis, Uppsala universitet, Strukturkemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-259513.
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Polymer electrolyte films based on poly(trimethylene carbonate) (PTMC) mixed with LiTFSI salt in different compositions were synthesized and investigated as electrolytes for lithium ion batteries, where the ionic conductivity is the most interesting material property. Electrochemical impedance spectroscopy (EIS) and DSC were used to measure the ionic conductivity and thermal properties, respectively. Additionally, FTIR and Raman spectroscopy were used to examine ion coordination in the material. Additives of nanosized TiO2 and powders of superionically conducting Li1.3Al0.3Ti1.7(PO4)3 were investigated as enhancers of ionic conductivity, but no positive effect could be shown. The most conductive composition was found at a [Li+]:[carbonate] ratio of 1, corresponding to a salt concentration of 74 percent by weight, which showed an ionic conductivity of 2.0 × 10–6 S cm–1 at 25 °C and 2.2 × 10–5 S cm–1 at 60 °C, whereas for even larger salt concentrations, the mechanical durability of the polymeric material was dramatically reduced, preventing use as a solid electrolyte material. Macroscopic salt crystallization was also observed for these concentrations. Ion coordination to carbonyls on the polymer chain was examined for high salt content compositions with FTIR spectroscopy, where it was found to be relatively similar between the samples, possibly indicating saturation. Moveover, with FTIR, the ion-pairing was found to increase with salt concentration. The ionic conductivity was found to be markedly lower after 7 weeks of aging of the materials with highest salt concentrations.
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Guha, Thakurta Soma. "Anhydrous State Proton and Lithium Ion Conducting Solid Polymer Electrolytes Based on Sulfonated Bisphenol-A-Poly(Arylene Ethers)." University of Akron / OhioLINK, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=akron1239911460.
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Vijayakumar, V. "Preparation, characterization and application of proton, lithium and zinc-ion conducting polymer electrolytes for supercapacitors, lithium- and zinc-metal batteries." Thesis(Ph.D.), CSIR-National Chemical Laboratory, 2021. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/5972.
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The use of liquid electrolytes in energy storage devices are associated with several constraints pertaining to safety. Polymer electrolytes are suitable candidates to overcome several problems associated with free-flowing liquid electrolytes. The current thesis deals with the development of proton, lithium, and zinc conducting gel polymer electrolytes for electrochemical energy storage devices such as supercapacitors, lithium-metal batteries, and zinc-metal batteries. Special emphasis is given to the improvement of electrode|electrolyte interface in polymer electrolyte-based energy storage devices by the ultraviolet-light-induced in situ processing strategy. Ultimately, the prospects of employing polymer electrolytes as an alternative to liquid electrolytes in energy storage devices is revisited in this dissertation through four dedicated working chapters.University Grants Commissions (UGC), India CSIR, India
AcSIR
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Kyeremateng, Nana Amponsah. "Advanced materials based on titania nanotubes for the fabrication of high performance 3D li-ion microbatteries." Thesis, Aix-Marseille, 2012. http://www.theses.fr/2012AIXM4772/document.
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Le développement des dispositifs microélectroniques a dopé la recherche dans le domaine des microbatteries tout solide rechargeables. Mais actuellement, les performances de ces microbatteries élaborées par des technologies couche mince (2D) sont limitées et le passage à une géométrie 3D adoptant le concept “Li-ion” ou“rocking chair” est incontournable. Cette dernière condition implique de combiner des matériaux de cathode comme LiCoO2, LiMn2O4 or LiFePO4 avec des anodes pouvant réagir de manière réversible avec les ions lithium. Parmi tous les matériaux pouvant servir potentiellement d'anode, les nanotubes de TiO2 révèlent des propriétés intéressantes pour concevoir des microbatteries Li-ion 3D. Facilement réalisable, la nano-architecture auto-organisée a montré des résultats très prometteurs en termes de capacités à des cinétiques relativement modérées. L'utilisation des nanotubes de TiO2 en tant qu'anode conduit à des cellules présentant de faible autodéchargeet élimine le risque de surcharge grâce au haut potentiel de fonctionnement (1.72 V vs. Li+/Li). Dans ce travail de thèse, nous avons étudié la substitution des ions Ti4+ par Sn4+ et Fe2+ dans les nanotubes de TiO2. Bien que la présence d'ions Fe2+ n'ait pas amélioré les performances électrochimiques des nanotubes, nous avons pu mettre en évidence l'effet bénéfique des ions Sn4+. Nous avons aussi pu montré que la fabrication de matériaux composites à base de nanotubes de TiO2 et d'oxyde de métaux de transition électrodéposés se présentant sous forme de particules (NiO et Co3O4 ) augmentait les capacités d'un facteur 4The advent of modern microelectronic devices has necessitated the search for high-performance all-solid-state (rechargeable) microbatteries. So far, only lithium-based systems fulfill the voltage and energy density requirements of microbatteries. Presently, there is a need to move from 2D to 3D configurations, and also a necessity to adopt the “Li-ion” or the “rocking-chair” concept in designing these lithium-based (thin-film) microbatteries. This implies the combination of cathode materials such as LiCoO2, LiMn2O4 or LiFePO4 with the wide range of possible anode materials that can react reversibly with lithium. Among all the potential anode materials, TiO2 nanotubes possess a spectacular characteristic for designing 3D Li-ion microbatteries. Besides the self-organized nano-architecture, TiO2 is non-toxic and inexpensive, and the nanotubes have been demonstrated to exhibit very good capacity retention particularly at moderate kinetic rates. The use of TiO2 as anode provides cells with low self-discharge and eliminates the risk of overcharging due to its higher operating voltage (ca. 1.72 V vs. Li+/Li). Moreover, their overall performance can be improved. Hence, TiO2 nanotubes and their derivatives were synthesized and characterized, and their electrochemical behaviour versus lithium was evaluated in lithium test cells. As a first step towards the fabrication of a 3D microbattery based on TiO2 nanotubes, electrodeposition of polymer electrolytes into the synthesized TiO2 nanotubes was also studied; the inter-phase morphology and the electrochemical behaviour of the resulting material were studied
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Wang, Ying. "Development and Characterization of Advanced Polymer Electrolyte for Energy Storage and Conversion Devices." Diss., Virginia Tech, 2017. http://hdl.handle.net/10919/83859.
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Among the myraid energy storage technologies, polymer electrolytes have been widely employed in diverse applications such as fuel cell membranes, battery separators, mechanical actuators, reverse-osmosis membranes and solar cells. The polymer electrolytes used for these applications usually require a combination of properties, including anisotropic orientation, tunable modulus, high ionic conductivity, light weight, high thermal stability and low cost. These critical properties have motivated researchers to find next-generation polymer electrolytes, for example ion gels.
This dissertation aims to develop and characterize a new class of ion gel electrolytes based on ionic liquids and a rigid-rod polyelectrolyte. The rigid-rod polyelectrolyte poly (2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT) is a water-miscible system and forms a liquid crystal phase above a critical concentration. The diverse properties and broad applications of this rigid-rod polyelectrolyte may originate from the double helical conformation of PBDT molecular chains.
We primarily develop an ionic liquid-based polymer gel electrolyte that possesses the following exceptional combination of properties: transport anisotropy up to 3.5×, high ionic conductivity (up to 8 mS cm⁻¹), widely tunable modulus (0.03 – 3 GPa) and high thermal stability (up to 300°C). This unique platform that combines ionic liquid and polyelectrolyte is essential to develop more advanced materials for broader applications.
After we obtain the ion gels, we then mainly focus on modifying and then applying them in Li-metal batteries. As a next generation of Li batteries, the Li-metal battery offers higher energy capacity compared to the current Li-ion battery, thus satisfying our requirements in developing longer-lasting batteries for portable devices and even electric vehicles. However, Li dendrite growth on the Li metal anode has limited the pratical application of Li-metal batteries. This unexpected Li dendrite growth can be suppressed by developing polymer separators with high modulus (~ Gpa), while maintaining enough ionic conductivity (~ 1 mS/cm). Here, we describe an advanced solid-state electrolyte based on a sulfonated aramid rigid-rod polymer, an ionic liquid (IL), and a lithium salt, showing promise to make a breakthrough. This unique fabrication platform can be a milestone in discovering next-generation electrolyte materials.Ph. D.
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Álvarez, Daniel Jardón. "Study of advanced ion conducting polymers by relaxation, diffusion and spectroscopy NMR methods." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/18/18158/tde-19102016-114611/.
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Advances on secondary lithium ion batteries imply the use of solid polymer electrolytes, which represent a promising solution to improve safety issues in high energy density batteries. Through dissolution of lithium salts into a polymeric host, such as poly(ethylene oxide) (PEO), ion conducting polymers are obtained. The Li+ ions will be localized in the proximity of the oxygen atoms in the PEO chains and thus, their motion strongly correlated with the segmental reorientation of the polymer. Nuclear magnetic resonance (NMR) spectroscopy, translational diffusion coefficients and transverse relaxation times (T2) contribute to the understanding of the involved structures and the ongoing dynamical processes in ionic conductivity. Nuclei with different motional freedom can present different T2 times. T2xT2 exchange experiments enable studying exchange processes between nuclei from different motional regimes. In this work, three different ion conducting polymers were studied. First, PEG was doped with different amounts of LiClO4. 7Li NMR relaxometry measurements were done to study dynamical behavior of the lithium ions in the amorphous phase. All samples presented two lithium types with clearly differentiated T2 times, indicating the presence of two regions with different dynamics. The mobility and consequently the T2 times, increases with temperature. It was observed, that the doping ratio strongly influences the dynamics of the lithium ions, as the amount of crystalline PEG is reduced while increasing the polarity of the sample. A local maximum of the mobility was observed for y = 8. With the T2xT2 exchange experiments exchange rates between both lithium sites were quantified. Second, the triblock copolymer PS-PEO-PS doped with LiTFSI was studied with high resolution solid state NMR techniques as well as with 7Li relaxometry measurements. T1ρ and spin diffusion measurements gave insight on the influence of the doping and the PS/PEO ratio on the mobility of the different segments and on interdomain distances of the lamellar phases. Third, multiple quantum diffusion measurements were applied on poly(ethylene glycol) distearate (PEGD) doped with LiClO4. Therefore, triple quantum states of the 3/2 nucleus 7Li were excited. After optimizing the experimental procedure, it was possible to obtain reliable diffusion coefficients using triple quantum states.O avanço da tecnologia em baterias secundárias de íons lítio envolve o uso de polímeros condutores iônicos como eletrólitos, os quais representam uma solução promissora para obter baterias de maior densidade de energia e segurança. Polímeros condutores são formados através da dissolução de sais de lítio em uma matriz polimérica, como o poli(óxido de etileno) (PEO). Os íons de lítio estão localizados próximos aos oxigênios do PEO, de tal forma que seu movimento está correlacionado com a reorientação das cadeias poliméricas. Espectroscopia por Ressonância magnética nuclear (RMN), junto com medidas de difusão translacional e tempos de relaxação transversal (T2) contribuem para elucidar as estruturas e os processos dinâmicos envolvidos na condutividade iônica. Núcleos com diferente liberdade de movimentação podem ter tempos de T2 diferentes. Experimentos de T2xT2 permitem correlacionar sítios de diferentes propriedades dinâmicas. Neste trabalho, três diferentes polímeros condutores iônicos foram estudados. Primeiro, PEG foi dopado com LiClO4. As propriedades dinâmicas dos íons lítio na fase amorfa foram estudadas com medidas de relaxometria por RMN do núcleo 7Li. Todas as razões de dopagem apresentaram dois T2 diferentes, indicando dos tipos de lítio com dinâmica diferente. A mobilidade, e consequentemente os tempos T2 aumentam com aumento da temperatura. Foi identificado que a dopagem fortemente influencia a dinâmica dos íons lítio, devido à redução da fase cristalina PEG e o aumento da polaridade na amostra. Um máximo local da mobilidade foi observado para y = 8. Com o experimento T2xT2 foram quantificadas as rações de troca entre os dois tipos de lítio. Segundo, o copolímero tribloco PS-PEO-PS dopado com LiTFSI foi analisado através de técnicas de RMN de estado sólido de alta resolução assim como através de medidas de relaxação de 7Li. Medidas de T1ρ e difusão de spin mostraram a influência da dopagem e da razão PS/PEO na mobilidade dos diferentes segmentos e nas distâncias interdomínio das fases lamelares. Terceiro, medidas de difusão através de estados de múltiplos quanta foram feitas em diesterato de polietileno glicol (PEGD) dopado com LiClO4. Estados de triplo quantum foram criados no núcleo 7Li, spin 3/2. Após garantir a eficiência das ferramentas desenvolvidas, foi possível obter coeficientes de difusão confiáveis.
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Park, Chanbum. "Structure, dynamics and phase behavior of concentrated electrolytes for applications in energy storage devices." Doctoral thesis, Humboldt-Universität zu Berlin, 2021. http://dx.doi.org/10.18452/22389.
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Diese Arbeit widmet sich der Untersuchung der dynamischen und strukturellen Eigenschaften sowie des Phasenverhaltens konzentrierter flüssiger Elektrolyte und ihrer Anwendung in Energiespeichern mittels Methoden der statistischen Mechanik und mithilfe atomistischer Molekulardynamik (MD) Simulationen.
Zuerst untersuchen wir die Struktur-Eigenschafts-Beziehungen in konzentrierten Elektrolytlösungen wie sie in Lithium-Schwefel (Li/S), durch wir ein MD Simulationsmodell repräsentativer state-of-the-art Elektrolyt-Systeme für Li/S-Batterien bestehend aus Polysulfiden, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) und LiNO 3 Elektrolyten mit jeweils unterschiedlichen Kettenlängen gemischt in organischen Lösungsmitteln aus 1,2-dimethoxyethane and 1,3-dioxolane erstellen.
Als Zweites befassen wir uns mit der Phasenseparation, die auftritt, wenn sich die physikalisch-chemischen Eigenschaften flüssiger Gemische voneinander unterscheiden. Diese Systeme bestehen üblicherweise aus einem konzentrierten anorganischen Salz und einer ionischen Flüssigkeit. In dieser Arbeit untersuchen wir eine Vielfalt von hochkonzentrierten wässrigen Elektrolytlösungen, die aus unterschiedlichen Zusammensetzungen von LiCl und LiTFSI bestehen. Daraufhin beantworten wir die Frage, wie unterschiedlich die Komponenten in der wässrigen Lösung gemischt sein sollten, damit eine solche flüssig-flüssig-Phasentrennung stattfinden kann.
Als letztes untersuchen wir die Ladungsabschirmung, die ein grundlegendes Phänomen ist, das die Struktur von Elektrolyten im Bulk und an Grenzflächen bestimmt. Wir haben in dieser Arbeit die Abschirmlängen für verschiedene Elektrolyte von niedrigen bis zu hohen Konzentrationen untersucht.Electrolytes can be found in numerous applications in daily life as well as in scientific research. The increases in demand for energy-storage systems, such as fuel cells, supercapacitors and batteries in which liquid electrolyte properties are critical for optimal function, draw critical attention to the physical and chemical properties of electrolytes. Those energy-storage devices contain intermediate or highly concentrated electrolytes where established theories, like the Debye-Hückel (DH) theory, are not applicable. Despite the efforts to describe the physical properties of intermediate or highly concentrated electrolytes, theoretical atomistic-level studies are still lacking. This thesis is devoted to critically investigate the transport/structural properties and a phase behavior of concentrated liquid electrolytes and their application in energy-storage devices, using statistical mechanics and atomistic molecular dynamics (MD) simulations. Firstly, we investigate the structure-property relationship in concentrated electrolyte solutions in next-generation lithium-sulfur (Li/S) batteries. Secondly, phase separation may exist if the physio-chemical properties of liquid mixtures are very different. Recently, the coexistence phase of two aqueous solutions of different salts at high concentrations was found, called aqueous biphasic systems. We explore a wide range of compositions at room temperature for highly concentrated aqueous electrolytes solutions that consist of LiCl and LiTFSI. Lastly, charge screening is a fundamental phenomenon that governs the structure of liquid electrolytes in the bulk and at interfaces. From the DH theory, the screening length is expected to be extremely small in highly concentrated electrolytes. Yet, recent experiments show unexpectedly high screening lengths in those. This intriguing phenomenon has prompted a new set of theoretical works. We investigate the screening lengths for various electrolytes from low to high concentrations.
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Crisanti, Samuel Nathan Crisanti. "Effect of Alumina and LAGP Fillers on the Ionic Conductivity of Printed Composite Poly(Ethylene Oxide) Electrolytes for Lithium-Ion Batteries." Case Western Reserve University School of Graduate Studies / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=case1522756200308156.
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Chen, Chao-Hsu. "Atomistic Computer Simulations of Diffusion Mechanisms in Lithium Lanthanum Titanate Solid State Electrolytes for Lithium Ion Batteries." Thesis, University of North Texas, 2014. https://digital.library.unt.edu/ark:/67531/metadc700110/.
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Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Perovskite-structured LLT is a promising solid electrolyte with high lithium ion conductivity. LLT also serves as a good model system to understand lithium ion diffusion behaviors in solids. In this thesis, molecular dynamics and related atomistic computer simulations were used to study the diffusion behavior and diffusion mechanism in bulk crystal and grain boundary in lithium lanthanum titanate (LLT) solid state electrolytes. The effects of defect concentration on the structure and lithium ion diffusion behaviors in LLT were systematically studied and the lithium ion self-diffusion and diffusion energy barrier were investigated by both dynamic simulations and static calculations using the nudged elastic band (NEB) method. The simulation results show that there exist an optimal vacancy concentration at around x=0.067 at which lithium ions have the highest diffusion coefficient and the lowest diffusion energy barrier. The lowest energy barrier from dynamics simulations was found to be around 0.22 eV, which compared favorably with 0.19 eV from static NEB calculations. It was also found that lithium ions diffuse through bottleneck structures made of oxygen ions, which expand in dimension by 8-10% when lithium ions pass through. By designing perovskite structures with large bottleneck sizes can lead to materials with higher lithium ion conductivities. The structure and diffusion behavior of lithium silicate glasses and their interfaces, due to their importance as a grain boundary phase, with LLT crystals were also investigated by using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces were investigated. It was found that there existed a minor segregation of lithium ions at the glass/crystal interface. Lithium ion diffusion energy barrier at the interface was found to be dominated by the glass phase.
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Costa, Luciano Tavares da. "Simulação computacional de eletrólitos poliméricos baseados em poli (oxietileno) e líquidos iônicos." Universidade de São Paulo, 2007. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-19102007-074147/.
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Simulações por Dinâmica Molecular (MD) de eletrólitos poliméricos baseados em poli (oxietileno), POE, e líquidos iônicos derivados do cátion 1-alquil-3-metilimidazólio e ânion hexafluorfosfato foram realizadas. Os parâmetros do potencial intermolecular e intramolecular foram obtidos de simulações MD prévias, a partir de um modelo de átomos unidos para POE e cátions imidazólio, ou seja, átomos de hidrogênio não são considerados explicitamente. Investigação sistemática da concentração de líquido iônico (LI), temperatura, e comprimento da cadeia 1-alquil, [1,3-dimetilimidazólio]PF6 e [1-butil-3-metilimidazólio]PF6, bem como seus efeitos sobre a estrutura de equilíbrio foram realizadas, constatando completa dispersão dos líquidos iônicos na matriz polimérica. Foram observadas mudanças conformacionais na cadeia de POE, devido à interação POE-LI. Além disso, os sistemas apresentaram ordem em escala intermediária (IRO) similar aos eletrólitos poliméricos de sais inorgânicos simples. Estes resultados foram motivadores para realização de ensaios experimentais com de poli (etileno glicol) dimetil éter, PEGdME, e hexafluorfosfato de 1-butil-3-metilimidazólio, caracterizado por análises térmicas TG e DSC, difração de raio-X e espectroscopia por impedância eletroquímica. Correlações com a previsão teórica foram reveladas, em especial quanto à coordenação POE-LI, que ocorre principalmente na fase amorfa. Condutividades da ordem de 10-3 S.cm-1 a altas temperaturas foram observadas. O estudo computacional sobre a dinâmica dos sistemas revelou mobilidade iônica em POE/[bmim]PF6 maior que em POE/[dmim]PF6, além de mostrar que a adição de líquido iônico ao polímero causa diminuição na dinâmica das cadeias de POE. Condutividades calculadas para POE/[bmim]PF6 estão em concordância qualitativa com as obtidas para o sistema PEGdME-[bmim]PF6. A redução dos pares iônicos frente aos eletrólitos poliméricos de sais inorgânicos é a distinta evolução no tempo da função de van Hove para ânions e cátions, bem como a razão κ/κNE maior, por exemplo, em comparação ao sistema POE- LiClO4.Molecular dynamics simulations of polymer electrolytes based on poly (oxyethylene), POE, and ionic liquids derived from 1-alkyl-3-methylimidazolium hexafluorophosphate were performed. We used united atom models, i.e. hydrogen atoms of the PEO chain and 1,3-dialkylimidazolium cations are not explicitly considered. All of the potential parameters for intramolecular terms can be found in previous MD simulations of POE-LiCLO4 and ionic liquids systems. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl-chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix and conformational changes on PEO chains upon addition of the ionic liquid are identified. Long-range correlations are assigned to non-uniform distribution of ionic species within the simulation box. Experimental data were obtained from thermal analysis, x-ray diffraction and electrochemical impedance spectroscopy from poly (ethylene glycol) dimethyl ether, PEGdME, and 1-butyl-3-methylimidazolium hexafluorophosphate. Correlations with previous theoretical results were revealed and coordination of the IL by the polymer occurs mainly in the amorphous phase. It has been obtained ionic conductivity κ ~ 10-3 S.cm-1 for polymer electrolytes at high temperatures. Ionic mobility in PEO/[bmim]PF6 is higher than in PEO/[dmim]PF6 and the structural relaxation in PEO/[dmim]PF6 and PEO/[bmim]PF6 also indicated that the material containing the smaller cation [dmim]+ exhibits more significant slowing down on the dynamics of PEO chains. Clear indications of reduced strength in ion correlations are the distinct time evolution of van Hove correlation functions for anions and cations, and the higher κ/κNE ratio in comparison with, for instance, the PEO/LiClO4.
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Frenck, Louise. "Study of a buffer layer based on block copolymer electrolytes, between the lithium metal and a ceramic electrolyte for aqueous Lithium-air battery." Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAI041/document.
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La technologie Lithium-air développée par EDF utilise une électrode à air qui fonctionne avec un électrolyte aqueux ce qui empêche l’utilisation de lithium métal non protégé comme électrode négative. Une membrane céramique (LATP:Li1+xAlxTi2-x(PO4)3) conductrice d’ion Li+ est utilisée pour séparer le milieu aqueux de l’électrode négative. Cependant, cette céramique n'est pas stable au contact du lithium, il est donc nécessaire d'intercaler entre le lithium et la céramique un matériau conducteur des ions Li+. Celui-ci devant être stable au contact du lithium et empêcher ou fortement limiter la croissance dendritique. Ainsi, ce projet s'est intéressé à l'étude d'électrolytes copolymères à blocs (BCE).Tout d'abord, l'étude des propriétés physico-chimiques spécifiques de ces BCEs en cellule lithium-lithium symétrique a été réalisée notamment les propriétés de transport (conductivités, nombre de transport), et la résistance à la croissance dendritique du lithium. Puis dans un second temps, l'étude des composites BCE-céramique a été mise en place. Nous nous sommes en particulier focalisés sur l'analyse du transfert ionique polymère-céramique.Plusieurs techniques de caractérisation ont été utilisées telles que la spectroscopie d'impédance électrochimique (transport et interface), le SAXS (morphologies des BCEs), la micro-tomographie par rayons X (morphologies des interfaces et des dendrites).Pour des électrolytes possédant un nombre de transport unitaire (single-ion), nous avons obtenus des résultats remarquables concernant la limitation à la croissance dendritique. La micro-tomographie des rayons X a permis de montrer que le mécanisme de croissance hétérogène dans le cas des single-ion est très différent de celui des BCEs neutres (t+ < 0.2)The lithium-air (Li-air) technology developed by EDF uses an air electrode which works with an aqueous electrolyte, which prevents the use of unprotected lithium metal electrode as a negative electrode. A Li+ ionic conductor glass ceramic (LATP:Li1+xAlxTi2-x(PO4)3) has been used to separate the aqueous electrolyte compartment from the negative electrode. However, this glass-ceramic is not stable in contact with lithium, it is thus necessary to add between the lithium and the ceramic a buffer layer. In another hand, this protection should ideally resist to lithium dendritic growth. Thus, this project has been focused on the study of block copolymer electrolytes (BCE).In a first part, the study of the physical and chemical properties of these BCEs in lithium symmetric cells has been realized especially transport properties (ionic conductivities, transference number), and resistance to dendritic growth. Then, in a second part, the composites BCE-ceramic have been studied.Several characterization techniques have been employed and especially the electrochemical impedance spectroscopy (for the transport and the interface properties), the small angle X-ray scattering (for the BCE morphologies) and the hard X-ray micro-tomography (for the interfaces and the dendrites morphologies). For single-ion BCE, we have obtained interesting results concerning the mitigation of the dendritic growth. The hard X-ray micro-tomography has permitted to show that the mechanism involved in the heterogeneous lithium growth in the case of the single-ion is very different from the one involved for the neutral BCEs (t+ < 0.2)
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Hanot, Samuel. "L'eau confinée dans des matériaux nanostructurés." Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAY058/document.
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L'eau est partout et joue un rôle déterminant dans une multitude deprocessus. Cependant, on la trouve souvent au sein de minusculescellules, pores, ou canaux. En de tels cas, les proprietés“macroscopiques” de l'eau sont modifiées par les restrictions spatialeset les interactions entre les molécules d'eau et le matériau confinant.Elucider les propriétés de l'eau en confinement est crucial, et unecompréhension générale peut seulement être obtenue à traversl'utilisation de modèles. Alors que l'eau confinée dans des matériauxdurs tels que les nanotubes de carbone est bien documentée, nous n'avonspas trouvé de modèle général pour l'étude de l'eau confinée a desmatériaux mous, et ce en dépit de décénies de recherches sur de nombreuxmodèles spécifiques à une biomolécule ou un polymère en particulier.Dans cette thèse, nous présentons un modèle numérique d'eau confinéedans des géométries molles, générées par auto-assemblage. Nouscomprenons la manière dont les interactions réciproques entre l'eau etla matrice confinante déterminent la structure des assemblages et lespropriétés de transport de l'eau. Nous avons choisi un modèle desurfactant ioniques, matériaux très versatiles qui sont capables des'auto-assembler en diverses géométries confinantes.Nous nous concentrons sur l'effet des interfaces sur la formation de lananostructure et sur les propriétés de transport à l'échelle de lananoseconde. Nous nous distancons de l'approche traditionnelle auproblème du transport de l'eau dans des nanomatériaux. Nous montrons quel'hypothèse habituelle du transport diffusif est invalide car la matriceconfinante piège les molécules d'eau à l'interface. Nous proposons deremplacer cette hypothèse par celle du transport sous-diffusif, et nousmettons en évidence le rôle de l'échelle de taille et des propriétéstopologiques du confinement. Nous montrons que cette approche expliquedes résultats expérimentaux pour léau confinée dans des matériaux desynthèse, et qu'elle est compatible avec les développements récents liésà l'eau biologiqueWater is omnipresent and plays a decisive role in a myriad of processes.However, it is often found hidden in tiny cells, pores, or channels. Insuch cases, the usual “bulk” features of water are modified by thelimited available space and the interactions of individual moleculeswith the confining material. Elucidating the properties of water in suchconfined states is critical and general understanding can only beachieved through models. While water confined in model hard materialssuch as carbon nanotubes is well documented, we found that there existno general model to study water confined in soft materials, althoughthis has been an active research topic for decades and despite thenumerous models specific to one biomolecule or polymer that have beendeveloped. In this thesis, we present a numerical model of waterconfined in soft self-assembled environments, and we provide anunderstanding of how the interplay between water and the confiningmatrix affects the structure of the assemblies and transport propertiesof water. Our model confining matrix is composed of ionic surfactants.This versatile model is able to self-assemble to a wide variety ofconfining geometries.We focus on the role of interfaces in shaping the nanometer scalestructure, and nanosecond scale transport properties. This work is adeparture from the traditional approach to the problem of transport ofwater confined in soft nanomaterials. We show that the usual hypothesisof diffusive water transport does not hold due to trapping of moleculesat the interface with the confining matrix. Instead, we support apicture where transport is sub-diffusive, and we highlight the role ofthe length-scale of the confinement and of its topological features. Wefind that this rationale explains experimental results for waterconfined in synthetic materials, and that it is compatible with recentadvances in the understanding of biological water
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Szotkowski, Radek. "Gelové polymerní elektrolyty s nanočásticemi." Master's thesis, Vysoké učení technické v Brně. Fakulta elektrotechniky a komunikačních technologií, 2017. http://www.nusl.cz/ntk/nusl-319296.
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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.
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Dam, Tapabrata. "Study of Relaxation Dynamics and Ion Conduction Mechanism of Composite Polymer Electrolyte and Gel Polymer Electrolyte." Thesis, 2017. http://ethesis.nitrkl.ac.in/8736/1/2017_PhD_511PH103_TDam.pdf.
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The increasing demand for miniaturized portable electrical energy sources has led towards intensive research on developing efficient electrochemical energy storage/conversion devices. Based on the capability of delivering continuous energy for a longer period of time or quick charge-discharge capabilities, these devices can be divided into energy and current sourcing devices. Among these devices, batteries show intermediate power density along with energy density. At present in most of the commercially available devices, liquid organic carbonate electrolytes having conductivity values close to 103 Scm1 are being used. Although liquid electrolyte shows a high conductivity value, they possess a serious safety concern. Therefore, prior importance is given to developing a polymer electrolyte with comparable ionic conductivity at ambient temperature. Polymer electrolyte has the prospect to improve various key properties of lithium based batteries when used as the electrolyte. These properties include design flexibility, safety, cyclability, energy and power density etc. However, polymer electrolytes are having a serious drawback of low ionic conductivity limiting its potential application. Therefore primary interest is given in the preparation of polymer electrolytes with high ionic conductivity at room temperature. Achievement of the desired level of ambient temperature ionic conductivity (_ 103 Scm1) is still an open problem. Literature suggests that to improve the ionic conductivity of polymer electrolytes several strategies such as plasticization, copolymerization, fabrication of composite/nano-composite etc. have been studied extensively. These techniques mainly concentrate on increasing the amorphous content of polymer electrolytes in order to favour ion mobility to increase the ionic conductivity. In this regard, optimization of ionic conductivity of polymer electrolytes is carried out in the present investigation for composite polymer electrolytes and gel polymer electrolytes. In addition to the process of optimization, prior importance is also given on the understanding the ion conduction mechanism in these two class of polymer electrolytes.
In this study three different series of polymer composite electrolytes are prepared using polyethylene oxide as the host polymer, lithium triflate as salt and nanocrystalline zirconia, titania and organo-modified hydrophobic montmorillonite clay as fillers. In addition to this a series of gel polymer electrolyte is also prepared by blending polymer host and 1 molar lithium triflate electrolyte solution consisting of a mixture of ethylene carbonate and diethyl carbonate as solvent. Phase formation of the filler materials, composite nature of polymer composite electrolytes and blended polymer host matrix prepared for gel polymer electrolytes are studied using X-ray diffraction technique. Surface morphology of all these materials is studied using FE-SEM. Polymer salt interactions are investigated using FTIR. Ionic conductivity is measured over a wide range of temperature for getting proper idea about its temperature dependent behaviour. In all these electrolytes, we have achieved room temperature ionic conductivity up to the order of 105 S cm1. This is nearly two order higher in magnitude than conventional polymer-salt complexes at room temperature. Though we are successful in increasing the ionic conductivity by almost two orders in magnitude at room temperature, there exist a huge scope for further improvement in terms of the magnitude of the ionic conductivity. For this reason, a proper understanding of ion conduction mechanism is necessary. Ionic transport mechanism is probed using broadband dielectric spectroscopy over a wide range of frequency and temperature. Relaxation dynamics at different length and time scale is analyzed using broadband dielectric spectroscopy in order to get a proper idea about the ion conduction processes taking place at the microscopic level. The physical parameters that aids in increasing the ionic conductivity of these materials are also studied with observations made from broadband dielectric spectroscopy.
An in-depth step by step analysis of the data obtained from electrical characterizations are carried out. The temperature-dependent ionic conductivity for polymer composite electrolytes are found to follow VTF behaviour, indicating there exist coupling between ionic conductivity and polymer segmental motion. Segmental relaxation time also follow similar behaviour. To explain and investigate the coupled nature of ion conduction mechanism, ion diffusivity analysis is carried out by employing Trukhan model. The outcome of these analysis also supports the coupled nature of ion conduction process. Empirical laws like Jonscher power law, double power law and different models like RFEBM, Ngai coupling model, MIGRATION model are used to describe the frequency and temperature dependent ionic conductivity of polymer electrolytes. Havriliak -Negami expression is used to analyze the relaxation phenomenon present in polymer electrolytes. Study of ion conduction mechanism in polymer nanocomposite electrolyte suggest ionic conduction and segmental relaxation are coupled physical process. In the case of polymer gel electrolytes, polymer host does not play any significant role in ionic conduction but only provide the mechanical stability to the absorbed liquid electrolytes.
Proper understanding of ion conduction mechanism will help us for preparing good quality polymer electrolytes with high room temperature ionic conductivity, excellent mechanical, thermal and electrochemical stability. By achieving the aforementioned desired properties, the solid polymer electrolytes can replace the organic carbonate liquid based electrolytes commonly used in most of the portable energy storage/conversion devices.
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Kubisiak, Piotr. "Teoretyczne badanie oddziaływań jon-polimer w stałych elektrolitach polimerowych." Praca doktorska, 2011. http://ruj.uj.edu.pl/xmlui/handle/item/42165.
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Lee, Lien-Feng, and 李連峰. "Molecular Dynamics Simulation of Solid Polymer Electrolytes." Thesis, 2001. http://ndltd.ncl.edu.tw/handle/42885031995616046984.
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碩士淡江大學
化學學系
89
Molecular dynamics simulation is used to study the interaction between the ions (e.g. Na+、I-、Li+、CF3SO3- ) and PEO chain in polymer electrolytes in order to understand the behavior of ionic transport .We first calculated the ionic diffusion coefficient based on the data collected from the simulation , and observed :1)Increasing temperature will enhance the ionic conductivities;2) Decreasing concentration also will enhance the ionic conductivities .These two qualitative results are in good agreement with the experiment data. We then established the relationship between the coordinating environment of ions and its conductivities using radial distribution function analysis. Indeed, molecular dynamics simulation technique is a complement tool for studying the mechanism of conductivity in polymer electrolytes.
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Indris, Sylvio. "Ion Dynamics in Solid Electrolytes: Li+, Na+, O2−, H+." 2017. https://ul.qucosa.de/id/qucosa%3A31578.
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Chelmecki, Marcin [Verfasser]. "Cellulose based lithium ion polymer electrolytes for lithium batteries / Marcin Chelmecki." 2005. http://d-nb.info/975876422/34.
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Brooks, Daniel James. "Computational Investigation of Ionic Diffusion in Polymer Electrolytes for Lithium-Ion Batteries." Thesis, 2018. https://thesis.library.caltech.edu/10995/5/brooks_thesis_6_1_18.pdf.
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Energy storage is a critical problem in the 21st century and improvements in battery technology are required for the next generation of electric cars and electronic devices. Solid polymer electrolytes show promise as a material for use in long-lifetime, high energy density lithium-ion batteries. Improvements in ionic conductivity, however, for the development of commercially viable materials, and, to this end, a series of computational studies of ionic diffusion were performed. First, pulsed charging is examined as a technique for inhibiting the growth of potentially dangerous lithium dendrites. The effective timescale for pulse lengths is determined as a function of cell geometry. Next, the atomistic diffusion mechanism in the leading polymer electrolyte, PEO-LiTFSI, is characterized as a function of temperature, molecular weight, and ionic concentration using molecular dynamics simulations. A novel model for describing coordination of lithium to the polymer structure is developed which describes two types of interchain motion "hops" and "shifts," the former of which is shown to contribute significantly to ionic diffusion. The methodology developed in this study is then applied to a new problem – the adsorption of CO2 at the surface of semi-permeable polymer membranes. Finally, a new method, PQEq, is developed, which provides an improved description of electrostatic interactions with the inclusion of explicit polarization, Gaussian shielding, and charge equilibration. The dipole interaction energies obtained from PQEq are shown to be in excellent agreement with QM and a preliminary application of PQEq to a polymer electrolyte suggest that it can provide an improved description of ionic diffusion. Taken as a whole, these techniques show promise as tools to explore and characterize novel materials for lithium-ion batteries.
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Hsin-WeiFeng and 馮信為. "Maleic Anhydride Modified Atactic Polypropylene for Gel Polymer Electrolytes of Lithium Ion Batteries." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/51200375897911701126.
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碩士國立成功大學
化學工程學系
103
In this study, atactic-polypropylene grafted maleic anhydride (aPP-g-MA), which was reacted with special poly(ethylene oxide) (PEO), JEFFAMINE® ED-2003 Polyetheramine (XTJ-502), to make polymer thin films, was synthesized. Lithium ion batteries with gel polymer electrolytes are made from our polymer thin films soaked in liquid electrolyte, which consists of 1 M lithium hexafluorophosphate (LiPF6) with EC/DMC/DEC in 1:1:1 wt%. FTIR and TGA were used for characterizing aPP-g-MA. The result of TGA reveals that there is a clear increase in temperature of 5 wt% degradation. The electrochemical windows of our systems for lithium ion batteries reach 4.5 V, and they successfully absorb liquid electrolyte. The relationship between temperature and ionic conductivity obeys Vogel-Tammann-Fulcher (VTF) behavior, and as increasing amount of XTJ-502 in films, the activation energy of ionic conductivity also increases, which is contributed to confinement effect. All of lithium ion transport numbers are smaller than 0.1, because of existence of associated lithium salts and high mobility of negative ions, which are made lithium ion transport numbers relatively small. Finally, the capacities of discharge curves of lithium iron phosphate (LiFePO4) half cell reach 140 mAh/g, but it cannot bear many times of charge and discharge.
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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.
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博士國立成功大學
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.
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洪哲倫. "Study on properties of nano-composites solid polymer electrolytes for rechargeable lithium ion batteries." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/81400207126876239529.
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碩士國立臺灣科技大學
化學工程系
91
The main objective of the present investigation is to develop high ionic conducting and mechanically stable nano-composite solid polymer electrolyte and understanding the mechanism of the lithium ion transport in the composite solid polymer electrolyte. The addition of nano-sized inorganic fillers to the solid polymer electrolyte will improve the ionic conductivity of the polymer electrolyte. The conductivity of the solid polymer electrolyte was depends upon the particle size of the TiO2 nano-particles. The grain growth of TiO2 particles was calcinated at higher temperature could be inhibited successfully by surface modification with HMDS. The TiO2 powder sintered at 500 0C resulted the grain size of the order of less than 5 nm. In the conductivity measurement, the resistance of solid state electrolyte is dependent with the content and particle size of nano-sized TiO2 powder. Especially, PEO—10%LiClO4—5%TiO2 has a highest conductivity of 1.40×10-4S/cm at 30oC. At the same preparation condition, the conductivity of solid state electrolyte with TiO2 additives is ten times higher than that without TiO2 additives. The conductivity increases slightly with the decrease of the particle size of TiO2. In addition, the additives of TiO2 is not only improving the mechanical property of the electrolyte, but also increasing the transfer number of Li+ from 0.25 to 0.5. Furthermore, the electrolysis potential is 5.4 V in solid state electrolyte higher than 4.9 V in liquid electrolyte. In the present investigation, the lithium ion mechanisms, the higher ionic conductivity of PEO-based nano-composite solid polymer electrolyte was due to the addition of TiO2 nano-particles. The addition of nano-particle would be suppressing the crystallinity, which blocks the li ion and improving the amorphous region of the polymer film was observed from DSC results. The Li ion environment in the polymer electrolyte was analyzed by using solid state NMR. We observed that three kinds of possible environment for Li ion exhibits in the composite solid polymer electrolyte, the first, second and third Li ions are, respectively, coordinated with ClO4- anion, oxygen-PEO chain and TiO2 nanoparticles. The C-H stretching energy and dipole moment of the PEO based polymer electrolyte with addition of TiO2 nano-particles was observed from IR spectroscopy. The mobility of the nano-composite solid polymer electrolytes is higher than conventional solid polymer electrolytes which results higher ionic conductivity and lithium ion transference number.
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Ward, Ian M., J. J. Kaschmitter, Glen P. Thompson, Simon C. Wellings, H. V. St A. Hubbard, and H. P. Wang. "Separator-free rechargeable lithium ion cells produced by the extrusion lamination of polymer gel electrolytes." 2006. http://hdl.handle.net/10454/3332.
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NoPolymer gel electrolytes (PGE) based on polyvinylidene fluoride (PVDF), lithium salts and appropriate solvent systems, developed at Leeds University, have been shown to form tough rigid films with conductivities approaching 10¿2 S cm¿1. A continuous process has now been developed for the construction of rechargeable lithium cells by extruding the PGE as a melt and directly laminating between the anode and cathode electrodes. On cooling, the solid PGE acts as electrolyte and separator and binds the cell laminate together from within requiring no external case. This process has been successfully applied for the fabrication of cells with electrodes developed by SpectraPower Inc. in a commercial process enabling cell laminates with PGE thickness less than 0.1 mm and with energy densities approaching 170 Wh kg¿1. A prototype manufacturing facility has been set up to produce rechargeable cells of high specific capacity and high energy density. Future developments will enable rechargeable lithium ion cells to be produced on a continuous process as flat sheets opening the way for novel battery geometries.
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Hou-MingSu and 蘇侯名. "Syntheses of Ionized Gel Polymer Electrolytes based on Crosslinked Polyether-Siloxane Hybrids for Lithium-Ion Battery Applications." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/5uzkja.
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碩士國立成功大學
化學工程學系
103
Synthesis of quaternary ammonium salt has been accomplished and characterized with 1H-NMR and FTIR. And this quaternary ammonium salt is added to polyether/siloxane networks via sol-gel approach to form Ionized Gel Polymer Electrolytes based on Crosslinked polyether-Siloxane Hybrids. From SEM analysis and TGA test, we find out microphase separation in polymer system when the proportion of quaternary ammonium salt increases to three quarters. The ionic polymer electrolytes has great electrochemical window and thermal stability up to 4.5 V (vs. Li/Li+) and 400℃. The DSC results indicate that the glass transition temperature of ionic gel polymer electrolyte decreases with the addition of quaternary ammonium.Then the ionic conductivity of ionic polymer electrolyte is enhanced to 5.93*10-3 S cm-1 at 30℃, compared to that of the original polyether/siloxane hybrid(2.18*10-4 S cm-1). Furthermore, the lithium-ion transference number of ionic gel polymer electrolyte is up to 0.568. For battery application, the half-cell specific discharge capacity of gel polymer electrolyte increase from 35mAh/g to 90mAh/g at 5C with the addition of quaternary ammonium salt. Moreover, the full-cell performance of gel polymer electrolyte is as good as commercial separator (100mAh/g at 1C). The above advantages of the ionized gel polymer electrolytes allow it to act as a separator in lithium-ion battery.