Ion Transport And Structure In Polymer Electrolytes With Applications In Lithium Batteries
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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.
The Impact Of Polymer Electrolyte Properties On Lithium Ion Batteries
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Author : Nacer Badi
language : en
Publisher: Eliva Press
Release Date : 2022-08-23
The Impact Of Polymer Electrolyte Properties On Lithium Ion Batteries written by Nacer Badi and has been published by Eliva Press this book supported file pdf, txt, epub, kindle and other format this book has been release on 2022-08-23 with categories.
In this review, different types of electrolytes and their electrical and mechanical properties have been reported and studied to evaluate their effect on LIB performance. It was noticed that the electrolyte component and solvent in polymer electrolytes have a great influence on the ionic conductivity, Li+ migration, interfacial contact between electrolyte and electrode, mechanical properties, and the performance of the entire battery. The morphology of incorporated additive materials (nanoparticles, nanowires, nanofillers, salt, etc.) may well contribute to the amelioration of the ion transport pathway, which raises the lithium-ion conductivity. A basic understanding of the chemical reaction routes and the electrolyte structure would facilitate innovation in the battery. The structural, electrochemical, and mechanical properties of new promising materials should be investigated in advance for application in advanced lithium-ion batteries. The electrochemical behavior is inextricably related to the structure. IL-based solid polymer electrolytes appear as a promising material for long-term lithium-ion batteries despite showing low ionic conductivity but exhibiting more advantages than conventional carbonate electrolytes such as good safety, stability, good electrochemical performance, good mechanical stability, and enhanced energy density. Since solid electrolytes exhibit low ionic conductivity, ILs used in SPEs increased their conductivity. In a battery, porous materials appear to offer good properties in terms of lithium ionic conductivity, with no leakage and low interface resistance, and gel-based LIBs demonstrate a good working performance, long cycling life, and high energy density. Good polymer electrolytes need to be highly conductive, safe, highly mechanically and thermally stable, and easy for film formation.
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 ...
Polymer Based Solid State Batteries
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Author : Daniel Brandell
language : en
Publisher: Walter de Gruyter GmbH & Co KG
Release Date : 2021-07-19
Polymer Based Solid State Batteries written by Daniel Brandell and has been published by Walter de Gruyter GmbH & Co KG this book supported file pdf, txt, epub, kindle and other format this book has been release on 2021-07-19 with Technology & Engineering categories.
Recent years has seen a tremendous growth in interest for solid state batteries based on polymer electrolytes, with advantages of higher safety, energy density, and ease of processing. The book explains which polymer properties guide the performance of the solid-state device, and how these properties are best determined. It is an excellent guide for students, newcomers and experts in the area of solid polymer electrolytes.
Polymer Electrolytes And Their Composites For Energy Storage Conversion Devices
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Author : Achchhe Lal Sharma
language : en
Publisher: CRC Press
Release Date : 2022-11-28
Polymer Electrolytes And Their Composites For Energy Storage Conversion Devices written by Achchhe Lal Sharma and has been published by CRC Press this book supported file pdf, txt, epub, kindle and other format this book has been release on 2022-11-28 with Science categories.
Polymer Electrolytes and their Composites for Energy Storage/Conversion Devices presents a state-of-the-art overview of the research and development in the use of polymers as electrolyte materials for various applications. It covers types of polymer electrolytes, ion dynamics, and the role of dielectric parameters and a review of applications. Divided into two parts, the first part of the book focuses on the types of polymer electrolytes, ion dynamics, and the role of dielectric parameters, while the second part provides a critical review of applications based on polymer electrolytes and their composites. This book: Presents the fundamentals of polymer composites for energy storage/conversion devices Explores the ion dynamics and dielectric properties role in polymer electrolytes Provides detailed preparation methods and important characterization techniques to evaluate the electrolyte potential Reviews analysis of current updates in polymer electrolytes Includes various applications in supercapacitor, battery, fuel cell, and electrochromic windows The book is aimed at researchers and graduate students in physics, materials science, chemistry, materials engineering, energy storage, engineering physics, and industry.
Ion Transport In Polymer Electrolytes
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Author : Fei Fan
language : en
Publisher:
Release Date : 2015
Ion Transport In Polymer Electrolytes written by Fei Fan and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2015 with Lithium ion batteries categories.
Batteries with superior performance will advance many technologies, such as the field of energy storage and electrochemical devices. Traditional lithium ion batteries based on liquid electrolytes have intrinsic problems such as leaking, dendrite growth, and those problems are associated with fire or even explosion hazard. Extensive efforts have been devoted into the development of solid polymer electrolytes (SPEs), which would not only reduce the size and weight of the batteries, but also solve safety related issues. However, none of current dry SPEs have reached the desired conductivity of 10-3 [0.001] S/cm at ambient temperature. The ion conductivity is controlled by two parameters, the free ion concentration and ion diffusivity. Despite the generally accepted theory that ion diffusion is facilitated by the segmental relaxation of the polymer, the mechanism of ion transport in SPEs is not completely understood. In this dissertation, the ion transport in different SPEs systems were studied with a combination of experimental techniques: dielectric spectroscopy, differential scanning calorimetry and rheology. The ion transport mechanism was investigated in poly(propylene glycol) (PPG) doped with LiClO4 [lithium perchlorate]. A comprehensive analysis was performed by systematically varying the temperature, pressure, polymer molecular weight and salt concentration. It was found that the ion transport was controlled by the segmental relaxation of the "ion-rich" phase in the system, which obeyed the traditional theory. On the contrary, decoupling was observed in several carbonate and styrene based polymer electrolytes. Analysis indicated that the decoupling feature might be related to the packing frustration in those systems. Polymerized ionic liquids (PolyILs) offer an opportunity of combining the high conductivity of ionic liquids and the superior mechanical strength of polymer. Unlike their small molecule analogue-aprotic ionic liquids, decoupling feature was observed in studied PolyILs. The variation of the pendant group structures altered the fragility index of the samples and thus the degree of decoupling. Unraveling the mechanisms of the ion transport and structure-property relationship in SPEs is of obvious fundamental and industrial importance. Findings in this work suggested new routes for future polymer electrolytes design of desired properties.
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.
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.
Structure And Dynamics Of Soft Materials For Flexible Electronics And Lithium Ion Battery
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Author : Pengfei Zhan
language : en
Publisher:
Release Date : 2017
Structure And Dynamics Of Soft Materials For Flexible Electronics And Lithium Ion Battery written by Pengfei Zhan and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2017 with categories.
Organic semiconductors and solid polymer electrolytes are promising soft materials for the realization of future electronics and better batteries. Both series of materials demonstrate considerable advantages over the current materials used in application. For example, organic semiconductors such as poly(3-alkylthiophene)s (P3ATs) and 2,7-dioctyl-benzothenobenzothiophene (dC8-BTBT) demonstrate significantly higher mechanical flexibility over inorganic semiconducting materials. These organic materials dissolve in various organic solvents and can be printed on plastic substrates, thus decreasing the processing cost. Replacing silicon with organic semiconductors not only increases the flexibility and lowers the cost, but also makes the device smaller and lighter. In Lithium ion battery, polyethylene oxide (PEO) based solid polymer electrolytes are an attractive alternative to the flammable and toxic liquid/gel electrolytes currently used in rechargable lithium ion batteries. The higher mechanical modulus of solid PEO can slow the growth of dendrites (Li metal that grows through the electrolyte and causes battery failure) and prolong battery life. Because the membrane is mechanically stable, a hard casing is not required and thus the battery is lighter and flexible.In polymer semiconductors, side-chains are added to increase the solubility of the conjugated polymer in common solvents. However, our study of amorphous materials suggested adding side-chains can harm the charge transport. It is well established that structure is a critical factor for charge transport. In amorphous materials, side-chains length has minimal effect on structure. We suspect the polymer dynamic is influenced by side-chain length. Although the role of molecular motion on charge mobilities is still not well understood. We experimentally measured the dynamic in amorphous conjugated polymers poly(3-alkylthiophene)s (P3ATs) with quasi-elastic neutron scattering (QENS). The analysis of the QENS data shows that longer side-chains relax faster compared with shorter side-chains and our further analysis of the elastic incoherent structure factor (EISF) suggests that the amplitude of proton motion on the thiophene rings increases by a factor of 3 as the side-chain length increases from 6 to 12, demonstrating that longer side chains lead to enhanced motion of conjugated rings.To fully understand the effect of side-chain on dynamic of charge transport unit, we expand our investigation to highly ordered crystalline material. The lattice vibration of benzothinobenzothiophene (BTBT), 2-octyl-benzothionbenzothiophene (mC8-BTBT), and 2,7-dioctyl-benzothionbenzothiophene (dC8-BTBT) is measured with inelastic neutron scattering (INS). The charge mobility of BTBT and its alkylated derivatives has shown an increase upon the addition of alkyl side-chains and INS experiment shows a suppressed vibration in the sample with two alkyl side chains. We hypothesize the lattice vibration can influence the charge transport via electron-phonon interaction and lattice dynamics should be another factor to be taken into consideration in future material design.In solid polymer electrolyte, crystalline PEO6LiX complex has shown to be more conductive than amorphous counterparts. Since its discovery in 1999, it has attracted tremendous amount of attention in the field of solid polymer electrolyte. However, as of now, none of commercialized electrolyte is based on this complex structure. This is because the original study used low molecular weight PEO that is liquid at room temperature. Increasing the molecular weight of PEO introduces higher degree of disorder to the complex which sacrifices the PEO6LiX crystallinity and decreases the conductivity. In this study, the PEO molecular weight we use is 600K Da. We use acidic cellulose nanowhisker to assist the nucleation of PEO6LiX crystalline complex at room temperature. These polymer-cellulose composite electrolytes have demonstrated room temperature conductivity higher than 10-5 S/cm and low Li+ transport activation energy. X-ray diffraction (XRD) shows high cellulose surface acidity increases the PEO6LiX crystallinity and promotes the conduction around the room temperature. The energy barrier for Li+ hopping through PEO6 channel decreases significantly as the cellulose nanowhisker surface acidity increases. With quasi-elastic neutron scattering (QENS) we demonstrate ion transport is decoupled with polymer relaxation time, suggesting PEO6 is likely the conduction media. To fully take advantage of the conduction mechanism of PEO6, the channel should be aligned. In this work, we investigate different options for alignment and proposed a device design for this purpose.Another important salt concentration in PEO-salt mixture is the eutectic concentration. From many polymer electrolyte studies, the conductivity maximized at eutectic concentration. To understand the influence of eutectic concentration on conduction, we select a series of PEOxLiX electrolytes with eutectic concentrations (ester oxygen to Li+ ratio) that vary from 7 to 100. We demonstrate that conductivity directly correlates to the distance from the eutectic concentration. We demonstrate the maximum gain when these electrolytes are filled with -Al2O3 nanoparticles is at the eutectic concentration. Both findings are important for effective design of polymer electrolytes for Li ion batteries.
Functional Design Of Advanced Polymer Architectures For Improved Lithium Ion Batteries
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Author : David G Mackanic
language : en
Publisher:
Release Date : 2020
Functional Design Of Advanced Polymer Architectures For Improved Lithium Ion Batteries written by David G Mackanic and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2020 with categories.
Lithium ion batteries (LIBs) are ubiquitous for applications in consumer electronics, electric vehicles, and grid-scale energy storage. Despite rapidly increasing demand, modern LIBs face significant challenges with regards to their safety and energy density. Additionally, the rigid nature of existing LIBs precludes their use in emerging applications in flexible/wearable electronics. Polymeric materials promise to address many of the issues facing LIBs, yet the existing polymers used commercially fall short of this goal. In this work, we design functional polymer materials to address three major challenges for next-generation LIBs. We explore the structure-property relationships of these polymer architectures in the context of ion transport, mechanical properties, and electrochemical performance. In the first project, a new polymer electrolyte is designed to replace the flammable liquid electrolyte in conventional LIBs. We study the effect of lithium ion coordination in polymer electrolytes and discover a modified polymeric backbone that loosely coordinates to lithium ions. The loose coordination of this new polymer electrolyte enables an improved lithium transference number of 0.54, compared to 0.2 achieved in conventional polymer electrolytes. This polymer electrolyte is demonstrated to operate effectively in a battery with a lithium-metal anode. In the second project, the learnings of the lithium coordination environment from the first project are used to design a multifunctional polymer coating to stabilize high energy density lithium metal anodes. We combined loosely-coordinating fluorinated ligands dynamically bonded with single-ion-conductive metal centers. The resulting supramolecular polymer network functions as an excellent lithium metal coating, allowing for achievement of one of the highest-reported coulombic efficiencies and cycle lives of a lithium metal anode. A systematic investigation of the chemical structure of the coating reveals that the properties of dynamic flowability, single-ion transport, and electrolyte blocking are synergistic in improving Li-metal coating performance. This coating is applied in a commercially relevant lithium metal full-cell and increases the cycle life over two-fold compared to an uncoated anode. The final project uses supramolecular polymer design to create ultra-robust ion transport materials. We show that when soft ion conducting segments are combined with strong dynamically bonded moieties in the polymer backbone, the ion transport properties can be decoupled from the mechanical properties. This decoupling enables for the creation of polymer electrolytes with extremely high toughness and high ionic conductivity. These supramolecular materials enable the fabrication of stretchable and deformable batteries that demonstrate respectable energy density even when stretched to 70% of their original length. Overall, the work demonstrated in this thesis provides a robust understanding towards designing polymer networks with tunable ion transport and mechanical properties. Additionally, the polymer materials demonstrated here provide promising avenues toward improving the safety, energy density, and flexibility of LIBs.