A Study Of The Relationship Between Lithium Ion Transport And Structure And Dynamic Behavior In Polyethylene Oxide Melt Liclo4 Battery Electrolytes
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A Study Of The Relationship Between Lithium Ion Transport And Structure And Dynamic Behavior In Polyethylene Oxide Melt Liclo4 Battery Electrolytes
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Author :
language : en
Publisher:
Release Date : 2009
A Study Of The Relationship Between Lithium Ion Transport And Structure And Dynamic Behavior In Polyethylene Oxide Melt Liclo4 Battery Electrolytes written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2009 with categories.
An experimental study of the canonical SPE ("solid" polymer electrolyte) for rechargeable "rocking chair" lithium/polymer batteries, viz. LiClO4 dissolved in molten poly(ethylene oxide) (PEO), was carried out under DOE grant FG02-04ER15573. In this study, an improved understanding was obtained of the relationship between lithium ion transport and polymer behavior in these SPEs. Among other applications, these sturdy temperature-tolerant and powerful light-weight batteries would be used in electric and electric-hybrid vehicles to reduce greenhouse gas emissions, to store unused electrical energy for peak demand loads and as compact, light-weight energy sources for aircraft and spacecraft. During the period of the grant, the American/Canadian partnership company "Avestor" fabricated and successfully demonstrated a telecommunications application of shoe-box sized batteries and representatives from Avestor visited our research lab at UNLV. They found our results interesting and relevant to their work and invited us to visit Avestor and present a talk about our efforts at UNLV. Unfortunately Avestor (who was scheduled to build a battery production facility in Apex, Nevada just North of Las Vegas) folded before the visit could be made. In the grant work, two well characterized PEO samples having molar masses distinctly below and distinctly above the melt entanglement molar mass were used and three laser light scattering techniques employed as the principal noninvasive methods of investigating liquid poly(ethylene oxide) (PEO)/LiClO4 SPEs. These investigations considered the effects of temperature, dissolved salt concentration and scattering wavevector on SPE behavior. Classical or "static" light scattering and the dynamic light scattering techniques of photon correlation spectroscopy (PCS) and Fabry-Perot interferometry (FPI) were used to study SPE static, low frequency and high frequency dynamic behaviors, respectively. Static measurements provided information about system structure while low frequency results provided information about slower (0.1-10s) more global behavior and high frequency results provided information about faster (~10-11s) more local behavior. In addition, viscometry, rheometry and thermal analysis provided vital complementary results. It was found that liquid PEO/lithium salt solutions for both PEO molar masses are random transient physical networks with measureable network and intra-network relaxation times using PCS and FPI. Thus novel and informative results addressing both large scale and small scale behavior were obtained. For example, the high sensitivity of liquid PEO electrolytes to the presence of presumably undesirable trace amounts of residual water and/or methanol was clearly evident in PCS measurements. In "unentangled" melts the activation energies for diffusive relaxation in liquid PEO/lithium salt electrolytes measured using PCS and the activation energies for viscous flow in these systems determined by viscometry were identical while thermal analyses detected no phase transitions for these systems. These results reinforced an earlier assumption that the liquid PEO/LiClO4 system is a liquid polymer "bimorph" (to our knowledge the first of its kind to be reported) with the network comprising one form of the polymer while the second form corresponds to that of a viscous damping liquid. At a given temperature, FPI characteristic relaxation times for local, between-chain motions were consistent with PCS results so that increases with increasing salt concentration were accompanied by increases in the elastic modulus and corresponding increases in system stiffness. Note that corresponding decreases in polymer segmental mobility are accompanied by reduced ion diffusivity. For entangled melts, PCS network relaxations were again observed and these systems were also considered to be bimorphs even though diffusion activation energies were distinctly larger than viscous flow activation energies - a diff ...
Ion Transport And Structure In Polymer Electrolytes With Applications In Lithium Batteries
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Author : Mahati Chintapalli
language : en
Publisher:
Release Date : 2016
Ion Transport And Structure In Polymer Electrolytes With Applications In Lithium Batteries written by Mahati Chintapalli and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2016 with categories.
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 [mu]m) 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.
Exploring The Relationship Between Polymer Topology And Ionic Conductivity
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Author : Nam Quang Hai Nguyen
language : en
Publisher:
Release Date : 2021
Exploring The Relationship Between Polymer Topology And Ionic Conductivity written by Nam Quang Hai Nguyen and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2021 with Chemistry categories.
This dissertation will be mainly exploring the relationship between polymer topology and ion transport properties of single-ion conductors (SICs) in lithium-ion battery application. Specifically, we strive to understand the impact of precise 5-carbon spacing on ion transports behavior of precision single-ion conductor. In chapter 2, the investigation was conducted on blending lithium sulfonate salt of precise 5-carbon spacing polymer electrolyte (p5PhS-Li) with poly(ethylene oxide) (PEO), a popular solvating polymer. The highest ionic conductivity of this type of SIC was achieved on the order of 10-7 S/cm at 90 °C. Results from differential scanning calorimetry (DSC) also indicated that polymer blends are at least partial miscible. The conclusion was made due to strong ionic interactions between sulfonate anions and lithium cations that lead to small magnitude of interaction parameter as well as melting point depression in PEO with complicating interpretation of transference number. We were strived to improve the ionic conductivity of single-ion conductors by altering the chemical structures of anions from sulfonate to trifluoromethylsulfonylimide salt (TFSI) that has been shown to increase electrochemical, thermal stabilities and ionic conductivity in chapter 3. Upon characterizing with 1H NMR, 19F NMR and 13C NMR, the efficiency of post polymerization reaction was obtained as high as 90 %. The conversion of sulfonated into TFSI-containing SIC (p5PhTFSI-Li) was shown to improve thermal stability as well as plasticize by an appearance of glass transition temperature (Tg) with higher TFSI content corresponds to lower (Tg). The ionic conductivity of true SIC p5PhTFSI-Li was lower than previously studied p5PhS-Li which contradicted to our hypothesis. The improvement in ionic conductivity was only observed when p5PhTFSI-Li was doped with PEO. Study by DSC also revealed that no crystallinity in PEO was detected, and these blends exhibited a single Tg which is attributed to the miscible behavior of the components. X-ray scattering also complemented with DSC study as ionic aggregates are diluted by the introduction of PEO. Realizing the immediate effect of PEO addition on the ionic conductivity of SICs, chapter 4 of the thesis further expands wider range of blend composition between PEO and p5PhTFSI-Li. Study by DSC reveals one single Tg for every blend composition which is consistent with results obtained from chapter 3. The addition of p5PhTFSI-Li retarded crystallization kinetics of PEO until it fully disrupted the crystalline phase of PEO, which proves that these two components provide greater compatibility than PEO/p5PhS-Li. Highest ionic conductivity of 6.37 x 10-4 S cm-1 was also obtained at 42 wt% of p5PhTFSI-Li, which is on par with that observed in literature TFSI-based SICs. Transference number was also observed to approach unity for experimented compositions. The future of p5PhTFSI-Li is wide open as the material will be investigated in block polymer as well as electrochemical stability. Last but not least, a side project was researched on catechol-containing precision polymer in underwater adhesion applications in chapter 5. Even though the research was not timely done, the synthesis of catechol-containing precision polymer was investigated on monomer synthesis, thermodynamics of polymerization, efficiency of polymerization and copolymerization with a similar comonomer structure. This project will leave opportunities for incoming graduate student to take over and analyze the adhesion performance the catechol-containing precision polymer.
Polymer Electrolytes
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Author : Tan Winie
language : en
Publisher: John Wiley & Sons
Release Date : 2020-02-18
Polymer Electrolytes written by Tan Winie and has been published by John Wiley & Sons this book supported file pdf, txt, epub, kindle and other format this book has been release on 2020-02-18 with Science categories.
A comprehensive overview of the main characterization techniques of polymer electrolytes and their applications in electrochemical devices Polymer Electrolytes is a comprehensive and up-to-date guide to the characterization and applications of polymer electrolytes. The authors ? noted experts on the topic ? discuss the various characterization methods, including impedance spectroscopy and thermal characterization. The authors also provide information on the myriad applications of polymer electrolytes in electrochemical devices, lithium ion batteries, supercapacitors, solar cells and electrochromic windows. Over the past three decades, researchers have been developing new polymer electrolytes and assessed their application potential in electrochemical and electrical power generation, storage, and conversion systems. As a result, many new polymer electrolytes have been found, characterized, and applied in electrochemical and electrical devices. This important book: -Reviews polymer electrolytes, a key component in electrochemical power sources, and thus benefits scientists in both academia and industry -Provides an interdisciplinary resource spanning electrochemistry, physical chemistry, and energy applications -Contains detailed and comprehensive information on characterization and applications of polymer electrolytes Written for materials scientists, physical chemists, solid state chemists, electrochemists, and chemists in industry professions, Polymer Electrolytes is an essential resource that explores the key characterization techniques of polymer electrolytes and reveals how they are applied in electrochemical devices.
Polymer Single Crystals
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Author : Phillip Herbert Geil
language : en
Publisher:
Release Date : 1963
Polymer Single Crystals written by Phillip Herbert Geil and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1963 with Crystalline polymers categories.
De Brettes Seigneurs Du Cros De Cieux De Masrocher Etc Marquis De Brettes Du Cros En Limosin
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language : en
Publisher:
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De Brettes Seigneurs Du Cros De Cieux De Masrocher Etc Marquis De Brettes Du Cros En Limosin written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on with categories.
Handbook Of Solid State Batteries And Capacitors
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Author : M Z A Munshi
language : en
Publisher: World Scientific
Release Date : 1995-05-11
Handbook Of Solid State Batteries And Capacitors written by M Z A Munshi and has been published by World Scientific this book supported file pdf, txt, epub, kindle and other format this book has been release on 1995-05-11 with Science categories.
Solid state power sources have developed remarkably in the last three decades owing to improvements in technology and a greater understanding of the underlying basic sciences. In particular, a greater impetus has recently been placed in developing and commercializing small, lightweight, and highly energetic solid state power sources driven by demands from portable consumer electronics, medical technology, sensors, and electric vehicles. This comprehensive handbook features contributions by forerunners in the field of solid state power source technology from universities, research organizations, and industry. It is directed at the physicist, chemist, materials scientist, electrochemist, electrical engineer, science students, battery and capacitor technologists, and evaluators of present and future generations of power sources, as a reference text providing state-of-the-art reviews on solid state battery and capacitor technologies, and also insights into likely future developments in the field. The volume covers a comprehensive series of articles that deal with the fundamental aspects and experimental aspects of solid state power sources, an in-depth discussion on the state of the various technologies, and applications of these technologies. A description of the recent developments on solid state capacitor technology, and a comprehensive list of references in each and every article will help the reader with an encyclopedia of hidden information. The organization of the material has been carefully divided into thirty-one chapters to ensure that the handbook is thoroughly comprehensive and authoritative on the subject for the reader.
Ion Conduction In Crystalline Polymer Electrolytes For Lithium Ion Batteries
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Author : Shankar Ram Chithur Viswanathan
language : en
Publisher:
Release Date : 2021
Ion Conduction In Crystalline Polymer Electrolytes For Lithium Ion Batteries written by Shankar Ram Chithur Viswanathan and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2021 with categories.
Polyethylene oxide (PEO) based Solid Polymer Electrolytes (SPEs) are safe and efficient alternatives to liquid/gel-based electrolytes. In addition to improving safety and design flexibility, SPEs could allow the use of lithium metal anode which can theoretically improve energy density 10-folds than commercially used lithium graphite anode. However, SPEs suffer from low Li+ ion conductivity. In most SPEs, the conductivity is linked to PEO segmental motion. Attempts to increase polymer dynamics reduce the mechanical strength of SPEs. Thus, it is necessary to decouple conductivity from the mechanical strength of the polymer. Conduction through the crystalline domain was never considered possible until the discovery of a PEO/salt co-crystal [PEO6], which was found to be more conductive than its amorphous counterpart. In PEO6 [the crystal structure co-crystallizes 6 PEO ether oxygens to one Li-anion pair], two PEO chains fold around Li+ in a non-helical fashion forming an approximate cylindrical "tunnel" with lithium atoms distributed along the cylinder central axis. Each lithium atom coordinates five ether oxygens; the anions are outside the tunnel and there is no direct bonding between the anions and the Li+. Due to its unique tunnel-like structure, PEO6 conducts Li+ based on a mechanism that decouples the conductivity and segmental motion of the polymer. However, these polymer electrolytes have not been used for battery applications because these studies used low molecular weight PEO (1000 g/mol) to achieve high crystallinity of the PEO6 phase. At this low molecular weight, the polymer does not confer the high modulus required. In SPEs with high molecular weight PEO, conduction through PEO6 is unfavorable as the tunnels fold to form lamellar structures and increase the conduction pathway. In this study, we explore conduction in high molecular weight [600000 g/mol] crystalline polymer electrolytes at EO: Li = 6:1. At this molecular weight, although four lithium salts [LiPF6, LiAsF6, LiSbF6, and LiClO4] can form PEO6, we focus our study on PEO6-LiClO4, which displays the highest conductivity than with other salt complexes. But this conductivity of PEO6LiClO4 drops by an order of magnitude after 2 months of thermal annealing. This is also accompanied by the changes in the XRD pattern which is uncharacteristic of any phases of PEO-LiClO4. Thus to explain this change, we explore the possibility of defects like vacancy, extra salt, and interstitial lithium in PEO6. In addition to being enthalpically stable, these defects also display the peculiar peaks of long-time annealed samples. While the change in the XRD pattern of a long-time annealed PEO6 can be explained by a combination of defects, based on their relative stability, it is more likely to be due to the "trapped" PEO6 structure. In this structure, in contrast to PEO6 where lithium atoms are at the center of the tunnel, one of the Li+ is "trapped" in the periphery of the tunnel coordinating with four ether oxygens and one anion, distorting the PEO6 tunnel. Because this crystal transformation is detrimental to conduction in PEO6, we use a percolated network of high aspect ratio fillers (cellulose nanowhiskers) to stabilize PEO6 tunnels over long distances. The patterned arrangement of the --OH surface group, which has a Lewis acidic character allows it to interact with either the anions or ether oxygen on the PEO chain. In addition, the distance between primary alcohol groups on the cellulose surface along the axial direction closely matches with the lattice parameter of PEO6 along the tunnel direction. This results in a low energy penalty [0.08 eV] for constraining PEO6 on the surface of the whisker, making it a suitable nucleation agent for PEO6LiClO4. Although these patterned cellulose nanowhiskers do stabilize PEO6 tunnels resulting in no change in XRD pattern even after a year of annealing, the room temperature conductivity (6 x10-6 S/cm) is still below the target value (10-3 S/cm). To improve the conductivity further, we draw inspiration from crystalline ceramic conductors, which have utilized doping [adding or substituting a small percentage of impurities to the host material] strategies to increase conductivity. By replacing 0.5-10% LiClO4 with NaClO4 in PEO6LiClO4, we demonstrate an order of magnitude increase in room temperature conductivity with the highest effect at 1% doping. This increase is not correlated with the glass transition temperature. Up to 1%, doping disrupts PEO6 crystallization. Above 1 %, diffraction peaks arise between 10-15o which cannot be due to PEO6 but resemble another polymer salt co-crystal, PEO3. A stable structure for PEO6 with NaClO4 is determined computationally, whereas only structures for PEO3 and PEO8 have been observed experimentally. Due to doping, larger sodium cations could either be accommodated into PEO6 or could end up not being part of the PEO6 lattice, resulting in a vacancy in PEO6. From DFT calculations, we determine that it is 0.92 eV more energetically favorable to swap sodium with lithium in PEO6 than to form PEO6 with vacancy. We conclude the increase in conductivity to be a consequence of weaker coordination of sodium to ether oxygen which increases the "bottleneck" size for conduction. In the sodium doping study, the presence of PEO3 peaks in XRD was correlated with increase an increase in conductivity. This is contrary to the popular belief that PEO3 is non-conductive. In contrast to PEO6, in PEO3, only one chain wraps around the Li+ in a helical fashion resulting in three-fold coordination of ether oxygen and two-fold coordination of anions. Due to tighter coordination of the lithium atoms with the neighboring anions, and lack of uncoordinated neighboring sites in PEO3, the activation energy for lithium hop as reported in PEO3LiCF3SO3 was found to be high [~1 eV]1-2, resulting in low ionic conductivity. If this gridlock is reduced by creating more vacancies, lithium atoms in PEO3 could become more mobile. To test this hypothesis, we create vacancies in PEO3 by reducing the concentration of LiClO4 from EO: Li = 3:1. We observe several orders of improvement in conductivity with a 20% reduction in salt concentration from EO: Li = 3:1, with no change in crystal structure or crystallinity up to 30% concentration deviation. Surprisingly, this change in conduction is accompanied by an increase in activation energy, indicating a change in the mechanism of conduction. To explain this change, we use DFT to find the activation energy for several conduction pathways in PEO3 including lithium diffusion: along the strand, across the strand, into a vacancy, and anion diffusion. In contrast to the previously held view that PEO3 has activation energy [~1eV], we conclude that the activation energy of PEO3LiClO4 can vary from 0.42- 1.3 eV depending on the conduction pathway. Thus, using both experiments and simulations we demonstrate the potential of crystalline polymer electrolytes and develop tools to understand the conduction mechanism in them. Although we did not reach the target conductivity, the findings from this work are important to design fast conduction solid polymer electrolytes.
Final Report For De Fg02 93er14376 Ionic Transport In Electrochemical Media
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Author :
language : en
Publisher:
Release Date : 2009
Final Report For De Fg02 93er14376 Ionic Transport In Electrochemical Media written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2009 with categories.
This project was a molecular dynamics study of the relevant issues associated with the structure and transport of lithium in polymer electrolytes such as polyethylene oxide(PEO). In close collaboration with quantum chemist Larry Curtiss and neutron scatterers David Lee Price and Marie-Louise Saboungi at Argonne, we used molecular dynamics to study the local structure and dynamics and ion transport in the polymer. The studies elucidated the mechanism of Li transport in PEO, revealing that the rate limiting step is extremely sensitive to the magnitude of the torsion forces in the backbone of the polymer. Because the torsion forces are difficult to manipulate chemically, this makes it easier to understand why improving the conductivity of PEO based electrolytes has proven to be very difficult. We studied the transport properties of cations in ionic liquids as possible additives to polymer membranes for batteries and fuel cells and found preliminary indications that the transport is enhanced near phase separation in acid-ionic liquid mixtures.
The Influence Of Charged Species On The Phase Behavior Self Assembly And Electrochemical Performance Of Block Copolymer Electrolytes
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Author : Jacob Lloyd Thelen
language : en
Publisher:
Release Date : 2016
The Influence Of Charged Species On The Phase Behavior Self Assembly And Electrochemical Performance Of Block Copolymer Electrolytes written by Jacob Lloyd Thelen and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2016 with categories.
One of the major barriers to expanding the capacity of large-scale electrochemical energy storage within batteries is the threat of a catastrophic failure. Catastrophic battery pack failure can be initiated by a defect within a single battery cell. If the failure of a defective battery cell is not contained, the damage can spread and subsequently compromise the integrity of the entire battery back, as well as the safety of those in its surroundings. Replacing the volatile, flammable liquid electrolyte components found in most current lithium ion batteries with a solid polymer electrolyte (SPE) would significantly improve the cell-level safety of batteries; however, poor ionic conductivity and restricted operating temperatures compared to liquid electrolytes have plagued the practical application of SPEs. Rather than competing with the performance of liquid electrolytes directly, our approach to developing SPEs relies on increasing electrolyte functionality through the use of block copolymer architectures. Block copolymers, wherein two or more chemically dissimilar polymer chains are covalently bound, have a propensity to microphase separate into nanoscale domains that have physical properties similar to those of each of the different polymer chains. For instance, the block copolymer, polystyrene-b-poly(ethylene oxide) (SEO), has often been employed as a solid polymer electrolyte because the nanoscale domains of polystyrene (PS) can provide mechanical reinforcement, while the poly(ethylene oxide) microphases can solvate and conduct lithium ions. Block copolymer electrolytes (BCEs) formed from SEO/salt mixtures result in a material with the bulk mechanical properties of a solid, but with the ion conducting properties of a viscoelastic fluid. The efficacy SEO-based BCEs has been demonstrated; the enhanced mechanical functionality provided by the PS domains resist the propagation of dendritic lithium structures during battery operation, thus enabling the use of a lithium metal anode. The increase in the specific energy of a battery upon replacing a graphite anode with lithium metal can offset the losses in performance due to the poor ion conduction of SPEs. However, BCEs that enable the use of a lithium anode and have improved performance would represent a major breakthrough for the development of high capacity batteries. The electrochemical performance of BCEs has a complex relationship with the nature of the microphase separated domains, which is not well-understood. The objective of this dissertation is to provide fundamental insight into the nature of microphase separation and self-assembly of block copolymer electrolytes. Specifically, I will focus on how the ion-polymer interactions within a diverse set of BCEs dictate nanostructure. Combining such insight with knowledge of how nanostructure influences ion motion will enable the rational design of new BCEs with enhanced performance and functionality. In order to facilitate the study of BCE nanostructure, synchrotron-based X-ray scattering techniques were used to study samples over a wide range of length-scales (i.e., from Angstroms to hundreds of nanometers) under conditions relevant to the battery environment. The development of the experimental aspects of the X-ray scattering techniques, as well as an improved treatment of scattering data, played a pivotal role in the success of this work. The dissemination of those developments will be the focus of the first section. The thermodynamic impact of adding salt to a neutral diblock copolymer was studied in a model BCE composed of a low molecular weight SEO diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), a common salt used in lithium batteries. In neutral block copolymers (BCPs), self-assembly is a thermodynamically driven process governed by a balance between unfavorable monomer contacts (i.e., the enthalpic contribution) and the entropy of mixing. When the enthalpic and entropic contributions to free energy are similar in magnitude, a block copolymer can undergo a thermally reversible phase transition from an ordered to a disordered nanostructure (i.e., the order-to-disorder transition (ODT). We used temperature-dependent small angle X-ray scattering (SAXS) to observe this transition in the model SEO/LiTFSI system. Unlike neutral BCPs, which to a first approximation are single component systems, the SEO/LiTFSI system demonstrated the thermodynamically stable coexistence phases of ordered lamellae and disordered polymer over a finite temperature window. Analysis of the lamellar domains revealed an increase in salt concentration during the ODT, indicating local salt partitioning due to the presence of nanostructure. While the Gibbs phase rule predicts this behavior, this was the first result demonstrating a direct connection between ion-polymer interactions and block copolymer nanostructure. We found evidence of salt redistribution in BCEs wherein self-assembly has been kinetically arrested. Through the structural analysis of BCEs formed from a high molecular weight SEO sample over a wide range of LiTFSI concentrations, it was revealed that in some cases, coexisting nanostructures were stable. While it is likely that the stability of these nanostructures was kinetic in nature, the relationship between nanostructure and salt partitioning revealed previously indicates that the salt could redistribute between the nanostructures to achieve the lowest energetic state. Unusual trends in the ionic conductivity with respect to salt concentration support this hypothesis. In some cases, high salt concentrations lead to significant improvements in ionic conductivity, representing a strong departure from the behavior of standard SPEs, and a possible route to improving the performance of BCEs. The performance of BCEs can also be improved by chemically functionalizing one of the polymer blocks by covalently attaching the salt anion. Since the cation is the only mobile species, these materials are coined single-ion conducting block copolymers. Single ion conduction can improve the efficiency of battery operation. In order for cation motion to occur in single-ion conducting block copolymers, it must dissociate from the backbone of the anion-containing polymer block. Through the structural and electrochemical characterization of poly(ethylene oxide)-b-poly[(styrene-4-sulfonyltrifluoromethylsulfonyl)imide] (PEO-P(STFSI))-based single-ion conductors, we found that ion dissociation significantly influences nanostructure: when a large amount of ions are dissociated, the polymer blocks tend to mix, thus precluding microphase separation and the formation of nanostructure. This direct coupling of ion dissociation (and hence conduction) and nanostructure has interesting implications for BCE performance. For instance, without discreet microphases, the single-ion conducting polymers cannot provide the enhanced mechanical properties like those obtained in SEO/LiTFSI electrolytes. Future development in single-ion conducting block copolymers should investigate polymer architectures where a third polymer block, such as PS, facilitates microphase separation and improved mechanical properties. Additional analysis of the single-ion conducting block copolymers revealed that ion dissociation from the charge-containing backbone (P(STFSI)) could also influence the crystallization of the neutral polymer block (PEO). Interestingly, ion dissociation did not disrupt PEO crystallization by directly interfering with the PEO chains, rather the homogeneity of the polymer melt prior to PEO crystallization led to differences in crystallization behavior. In the cases where ion dissociation lead to significant mixing of the polymer block, PEO crystallites grew unimpeded and formed well-ordered lamellar structures. When ion dissociation did not occur, fluctuations in concentration due to the demixing of PEO and P(STFSI) interrupted the growth of PEO crystallites, slowing the crystallization process and leading to less-ordered nanostructures. The final study in this work highlights the capability of utilizing in situ electrochemical characterization techniques while monitoring polymer microstructure using synchrotron X-ray scattering. We studied the electrochemical oxidation (doping) of poly(3-hexylthiophene) (P3HT) in a block copolymer of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) mixed with LiTFSI. During the doping process, we monitored the charge mobility electrochemically and the crystalline structure of P3HT using wide angle X-ray scattering (WAXS). Combining the structural analysis with the transport measurements in situ allowed the observation of a clear correlation between doping-induced changes in the P3HT crystal lattice and improvements in charge mobility. Since the doping-induced structural changes involve the intercalation of a salt anion into the P3HT crystal lattice, tuning the nature of the anion present during electrochemical oxidation might provide a new route to improving hole mobility in P3HT.