Physical Chemistry Commons^™

Development And Optimization Of Solid Polymer Electrolyte For Lithium Ion Batteries, Ladan Eskandarian

Electronic Thesis and Dissertation Repository

This thesis focuses on the development of new poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) in order to enhance their ionic conductivity at ambient temperature and fabricate the prototypes of novel Li ion batteries using these SPEs. Different types of SPEs have been developed: (i) blends of high molecular weight PEO and low molecular weight poly(vinyl acetate) (PVAc); (ii) composites of high molecular weight PEO and titanium dioxide (TiO₂)nanoparticles; and (iii) blend-based composite electrolytes consisting of PEO and PVAc with dispersed TiO₂. The SPEs were characterized by scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and …

Synthesis And Characterization Of Polymeric Anion Exchange Membranes, Wenxu Zhang

Doctoral Dissertations

As alkaline anion exchange membrane fuel cells (AAEMFC) are regarded as promising and important energy devices, the development of high performance anion exchange membranes are in urgent need, as well as fundamental investigation on the structure-property relationship, which are the motivation of this dissertation. Three different polymer systems are presented and focused on polymer synthesis, material morphology, and ion transport phenomena. Crosslinked membranes are promising as practical materials, however, the understanding and further improvement of its performance is hindered by the lack of an ordered morphology or well-defined chemical structure. In Chapter 2, a series of crosslinked membranes were design …

Nanomaterials At Liquid/Liquid Interfaces: Assembly And Rheology, Tao Feng

Doctoral Dissertations

This dissertation concentrated on the behavior of nanomaterials at liquid/liquid interfaces. A strategy of segregating acid-treated SWCNTs at oil/water interfaces was developed by adding amine-terminated polystyrene (PS-NH₂) in the oil phase. Electrostatic binding between carboxylic acid of SWCNTs and amine drives the assembly of SWCNTs, monitored by pendant drop tensiometry and confocal microscopy. A sharp transition of interfacial segregation against SWCNT solution pH was revealed, with the transition point at the pKa of carboxyl. The reduced SWCNT surface charge density at low pH was found to be beneficial for segregation due to the attenuated repulsions between adsorbed …

Resonance Raman Studies Of Oxygenated Forms Of Myoglobin And Cyp2b4 And Their Mutants, Ying Wang

Dissertations (1934 -)

Important oxidative heme enzymes use hydrogen peroxide or activate molecular oxygen to generate highly reactive peroxo-, hydroperoxo- and feryl intermediates resulting from heterolytic O-O bond cleavage. Members of the cytochrome P450 superfamily catalyze difficult chemical transformations, including hydroxylations and C-C bond cleavage reactions. In mammals, these enzymes function to reliably produce important steroids with the required high degree of structural precision. On the other hand, certain other mammalian P450s serve a different role, efficiently metabolizing xenobiotics, including pharmaceuticals and environmental pollutants. Though so important, the precise mechanisms involved in such transformations are incompletely understood, because of difficulties in structurally characterizing …

Synthesis And Applications Of Lanthanide Sulfides And Oxides, Christopher Marin

Department of Chemistry: Dissertations, Theses, and Student Research

This dissertation focuses on two of the key fields where lanthanides find ready application: as optically active materials with a focus on the lanthanide sulfides, and as catalytic materials with a focus on cerium oxide.

The lanthanide sulfides have attracted considerable interest for their potential as solar energy conversion materials, pigments, infrared window materials, and phosphor host media. However, applications of these materials remain limited due to their synthetic difficulty along with their not well understood properties compounded by both their difficulty in manufacturing as well as in simulating largely due to the need to take into account f-shell electrons. …

Electrochemical And In Situ X-Ray Absorption Fine Structure Study Of Li-Rich Cathode Materials, Meng-Yan Hou, Hong-Liang Bao, Ke Wang, Jian-Qiang Wang, Yong-Yao Xia

Journal of Electrochemistry

A series of the lithium-rich and manganese-based layered structure xLi₂MnO₃•(1-x)LiMn_1/3Ni_1/3Co_1/3O₂ (x = 0.3，0.5，0.7) materials were synthesized by a co-precipitation method, and followed by a solid-state reaction process. By comparing the first cycle efficiency, the reversible discharge capacity, the cycling stability and the voltage decay during the charge/discharge cycling process, the material with the composition of 0.5Li₂MnO₃•0.5LiMn_1/3Ni_1/3Co_1/3O₂was found to show the best electrochemical performance. The lithium storage mechanism and thermal stability of the de-lithiated compound were also investigated …

The Electrochemical Behavior Of Li+ In Lif-Baf2-Licl Molten Salt System, Shao-Hua Yang, Jun Wang, Xiao-Hui Lai, Hao-Ran Wang

Journal of Electrochemistry

The electrochemical reduction process and rate determining step of Li ion on a tungsten electrode at 1203 K in a LiF-BaF₂-LiCl molten system were studied by cyclic voltammetry, chronoamperometry and chronopotentiometry methods using a three-electrode system and electrochemical workstation AUTOLAB. The results showed that the reduction potential of Li ion was at around -1.0 V on a tungsten electrode as compared with a platinum electrode. The reduction process of Li ion on a tungsten electrode occurred in a single step with the exchange of one electron. Chronoamperograms indicated that the cathode process was controlled by the diffusion step …

Electrochemiluminescence Immunosensor Based On Platinum Nanoparticles For The Determination Of Apolipoprotein A1, Liao Ni, Zhuo Ying, Yuan Ruo

Journal of Electrochemistry

In this paper, a novel electrochemiluminescence (ECL) immunosensor for the detection of apolipoprotein A1 was constructed based on flower-like platinum nanoparticles (PtNFs) via a one-pot chemical synthesis method. The PtNFs was used to immobilize the secondary antibody and enzyme (GOD). Then the prepared bioconjugates were introduced onto the electrode via sandwich immunoreactions. Accordingly, the ECL luminophore peroxydisulfate (S₂O₈^2- ) was presented in the working buffer solution containing an appropriate amount of glucose. Through the ECL responses of S₂O₈^2- and O₂, a dramatically amplified ECL signal was obtained for the reason …

The Progress Of Order-Structured Membrane Electrode Assembly, Shang-Feng Jiang, Bao-Lian Yi

Journal of Electrochemistry

Performances of proton exchange membrane fuel cells (PEMFCs) have been recently improved. However, the cost and Pt loading must be further reduced for the commercialization of PEMFCs. Previous researches have proved that the order-structured electrode is beneficial to the effective utilization of Pt-based catalysts, decreasing the Pt loading and increasing the three-phase boundary for reaction. Especially, the nanostructure thin films (NSTFs) electrode, an ultra-thin catalytic layer developed by 3M Company, demonstrates high performance and durability. Besides, some other researchers have employed the high conductive carbon nanotube arrays or high stable metal oxide arrays as the order-structured catalyst supports for fundamental …

Recent Progress In Solid-State Nmr Study Of Electrode/Electrolyte Materials For Lithium/Sodium Ion Batteries, Gui-Ming Zhong, Zi-Geng Liu, Da-Wei Wang, Qi Li, Ri-Qiang Fu, Yong Yang

Journal of Electrochemistry

Solid state NMR technique is a powerful tool for characterizing the local structure and compositions of solid materials quantitatively. A comprehensive understanding of the structure evolution during the electrochemical reactions of the materials for lithium/sodium ion batteries will be obtained with the combination of solid state NMR, XRD, and XAS methods. Through analyzing solid state NMR spectra, we can obtain the compositions, local structures and ion diffusion dynamics of electrodes, electrolytes and surface layers for lithium/sodium ion batteries, providing an important theoretical support for the design and development of high-performance materials for batteries. In this paper, we review the recent …

Developments Of Photo-Assisted Fuel Cells, Ling-Ling Zhang, Shao-Jun Dong

Journal of Electrochemistry

The exploitation and utilization of fossil fuels have led to serious energy crisis and environmental pollution. In this case, the development of renewable energy is an alternative to traditional energy consumption. Fuel cells (FCs) can convert chemical energy into electricity via the electrochemical reaction, which is green and environment-friendly. Photo-assisted FCs integrate photo-responsive components into FCs, leading to the dual routes of energy conversion including light energy to electricity and chemical energy to electricity, and thus, improving the energy utilization efficiency. The development of photo-assisted FCs is significant for practical application and promising to solve the coming energy crisis. In …

Reduced Graphene Oxide (Rgo) Hollow Network Cages For High-Performance Electrochemical Energy Storage, Chi Zhang, Xu-Jun He, Gao-Ren Li

Journal of Electrochemistry

The reduced graphese oxide (RGO) hollow network cages were synthesized via zinc oxide (ZnO) template-assisted electrodeposition. The as-prepared RGO hollow network cages exhibited the multi-level architectures, from nano sheets, porous structures, networks, to 3D microscaled hollow cages, which can simultaneously optimize transport of electroactive species, utilization rate of electrode material, and super capacitive performance. Electrochemical measurements confirmed the superior performance of RGO hollow network cages for supercapacitors (SCs), such as high Csp (393 F•g^-1 at 1.0 A•g^-11), excellent rate capability (21.2% Csp loss from 1.0 to 20 A•g^-1), and superior cycling stability (< 1% Csp loss after 10000 cycles).

3, 4-Ethylenedioxythiophene Monomer As Safety-Enhancing Additive For Lithium Ion Batteries, Wei-Xiao Ji, Feng Wang, Jiang-Feng Qian, Yu-Liang Cao, Xin-Ping Ai, Han-Xi Yang

Journal of Electrochemistry

Safety concern is a major obstacle hindering the wide applications of large-capacity lithium ion batteries (LIBs) in electric vehicles. In this paper, a polymerizable monomer of 3, 4-ethylenedioxythiophene (EDOT) was proposed and tested as an electrolyte additive for enhancing the safety of LIBs. The electro-oxidative polymerization behaviors and influence of PEDOT additive on the thermal behavior of LiCoO₂ cathode, as well as the safety performance and electrochemical properties of LiCoO₂-based LIBs were investigated. The results from cyclic voltammetry (CV) and transmission electron microscope (TEM) characterizations indicated that the monomer additive can be electro-oxidatively polymerized to form a …

Uniform Nanoshells For Functional Materials：Constructions And Applications, Shu-Yi Duan, Wei Zhang, Jun-Yu Piao, An-Min Cao, Li-Jun Wan

Journal of Electrochemistry

As a significant protocol for materials treatment, surface modification has found broad applications in different fields including catalyst, photochemistry, and electrochemistry. Herein, we introduced the representative synthetic methodologies for the constructions of different functional materials with a focus on their core-shell structures. By taking the electrode materials in lithium ion batteries as an example, we demonstrated the importance of surface modification on the electrode materials. Different coating materials ranging from metal oxides, metal phosphates to carbon have been discussed. We also showed that an accurate control on the surface layer can be crucial for optimizing the electrochemical performances of the …

Synthesis, Structural Diversity, And Redox Control Of Cyclometalated Monoruthenium Complexes, Zhong-Liang Gong, Jiang-Yang Shao, Zhong Yu-Wu

Journal of Electrochemistry

Cyclometalated ruthenium complexes have received increasing attractions recently due to their excellent redox and photophysical properties. One structural feature of these complexes is that there is a ruthenium-carbon (Ru-C) σ bond presented in the molecule. Three common methods, namely, the “late metalation”, “early metalation”, and “transmetalation” methods, for the synthesis of cyclometalated ruthenium complexes are discussed and summarized. General strategies for the design of cyclometalating ligand and cyclometalated ruthenium complexes are introduced. By using different ancillary ligands, such as pyridine, imidazole, triazole, and pyrimidine, a great number of ruthenium complexes can be prepared. The presence of the Ru-C bond significantly …

Conformational Dynamics And Stability Associated With Magnesium Or Calcium Binding To Dream In The Regulation Of Interactions Between Dream And Dna Or Presenilins, Khoa Ngoc Pham

FIU Electronic Theses and Dissertations

Downstream regulatory element antagonist modulator (DREAM) is involved in various interactions with targets both inside and outside of the nucleus. In the cytoplasm, DREAM interacts with the C-terminal fragments of presenilins to facilitate the production of β-amyloid plaques in Alzheimer’s disease. In the nucleus, Ca²⁺ free DREAM directly binds to specific downstream regulatory elements of prodynorphin/c-fos gene to repress the gene transcription in pain modulation. These interactions are regulated by Ca²⁺ and/or Mg²⁺ association at the EF-hands in DREAM. Therefore, understanding the conformational dynamics and stability associated with Ca²⁺ and/or Mg²⁺ binding to DREAM …

The Corrosion Of Carbon Steel Under Deep Geologic Nuclear Waste Disposal Conditions, Shannon L.W. Hill

Electronic Thesis and Dissertation Repository

The proposed disposal scenario for high-level nuclear waste (spent fuel) in Canada is emplacement within a sealed, deep geological repository (DGR) located in either granitic rock or sedimentary clay. Disposal is based on a multi-barrier approach, with the primary barrier being a sealed container which could be either dual-walled with a copper shell over an inner carbon steel vessel for granitic rock or a single thick-walled steel container for sedimentary clay. This study focuses on the corrosion behaviour of A516 Gr70 carbon steel as well as the corrosion products formed in a variety of groundwater compositions and concentrations expected within …

Friedrich Wöhler, John Alfred Heitmann

John A. Heitmann

Friedrich Wöhler synthesized urea in 1828 and thus first demonstrated that organic materials, heretofore believed to possess a vital force, need not be made exclusively within living organisms. He also isolated aluminum metal in 1827 and discovered the elements beryllium and yttrium.

The Treatment Of Exchange In Path Integral Simulations Via An Approximate Pseudopotential, Randall W. Hall

Randall W. Hall

An approximate form that includes the effects of exchange is suggested for the short time propagator used in path integral simulations. The form is inspired physically by the approximation made in Hartree–Fock treatments of atoms and molecules. The approximate propagator is used with q u a n t i t a t i v e accuracy in two systems: an ideal gas of fermions localized in a three‐dimensional harmonic well and the triplet state of the sodium dimer.

Path Integral Study Of The Correlated Electronic States Of Na4–Na6, Randall W. Hall

Randall W. Hall

Feynman’s path integral formulation of quantum mechanics is used to study the correlated electronic states of Na4–Na6. Two types of simulations are performed: in the first, the nuclei are allowed to move at finite temperature in order to find the most stable geometries. In agreement with previous calculations, we find that planar structures are the most stable and that there is significant vibrational amplitude at finite temperatures, indicating that the Born–Oppenheimer surface is relatively flat. In the second type of simulation, the nuclei are held fixed at symmetric and asymmetric geometries and the correlated electron density is found. Our results …