Matching Items (12)
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- All Subjects: electrochemistry
- Creators: Sieradzki, Karl
- Creators: Angell, Charles A
Description
This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
ContributorsAnsari, Younes (Author) / Angell, Charles A (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase.
ContributorsChen, Qing (Author) / Sieradzki, Karl (Thesis advisor) / Friesen, Cody (Committee member) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic liquids where it is found that surface adsorption of residual amine and chloride from the organic synthesis affect growth characteristics. The drivers of this work are to understand the processes occurring at the electrode-electrolyte interface and with that knowledge, engineer systems yielding optimal performance. With this in mind, the design of a bulk supercapacitor electrode architecture with excellent composite specific capacitances, as well as develop conditions producing ideal Zn deposition morphologies was completed.
ContributorsEngstrom, Erika (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
Description
This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two techniques, are similar during reduction, but differ during oxidation due to non-linear stress relaxation phenomena. This stress relaxation appears to be due to homogenization of Li within graphite particles rather than viscous flow of the binder. The first Li reduction wave occurs simultaneously with formation of a passivating layer known as the solid electrolyte interphase (SEI). Preliminary experiments have shown the stress of SEI formation to be tensile (~+1.5 MPa).
ContributorsMickelson, Lawrence (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Venables, John (Committee member) / Arizona State University (Publisher)
Created2011
Description
The electrochemical behavior of nanoscale solids has become an important topic to applications, such as catalysis, sensing, and nano–electronic devices. The electrochemical behavior of elemental metal and alloy particles was studied in this work both theoretically and experimentally. A systematic thermodynamic derivation for the size–dependent Pourbaix Diagram for elemental metal particles is presented. The stability of Pt particles was studied by in situ electrochemical scanning tunneling microscopy (ECSTM). It is shown that small Pt particles dissolve at a lower potential than the corresponding bulk material. For the alloy particles, two size ranges of AuAg particles, ∼4 nm and ∼45 nm in diameter, were synthesized by co–reduction of the salts of Au and Ag from an aqueous phase. The alloy particles were dealloyed at a series of potential by chronoamperometry in acid, and the resulting morphology and composition were characterized by electron microscopy, energy dispersive X–ray spectroscopy (EDX). In the case of the smaller particles, only surface dealloying occurred yielding a core–shell structure. A porous structure was observed for the larger particles when the potential was larger than a critical value that was within 50 mV of the thermodynamic prediction.
ContributorsLi, Xiaoqian (Author) / Sieradzki, Karl (Thesis advisor) / Crozier, Peter (Committee member) / Buttry, Daniel (Committee member) / Friesen, Cody (Committee member) / Arizona State University (Publisher)
Created2012
Description
Diabetes mellitus is a disease characterized by many chronic and acute conditions. With the prevalence and cost quickly increasing, we seek to improve on the current standard of care and create a rapid, label free sensor for glycated albumin (GA) index using electrochemical impedance spectroscopy (EIS). The antibody, anti-HA, was fixed to gold electrodes and a sine wave of sweeping frequencies was induced with a range of HA, GA, and GA with HA concentrations. Each frequency in the impedance sweep was analyzed for highest response and R-squared value. The frequency with both factors optimized is specific for both the antibody-antigen binding interactions with HA and GA and was determined to be 1476 Hz and 1.18 Hz respectively in purified solutions. The correlation slope between the impedance response and concentration for albumin (0 \u2014 5400 mg/dL of albumin) was determined to be 72.28 ohm/ln(mg/dL) with an R-square value of 0.89 with a 2.27 lower limit of detection. The correlation slope between the impedance response and concentration for glycated albumin (0 \u2014 108 mg/dL) was determined to be -876.96 ohm/ln(mg/dL) with an R-squared value of 0.70 with a 0.92 mg/dL lower limit of detection (LLD). The above data confirms that EIS offers a new method of GA detection by providing unique correlation with albumin as well as glycated albumin. The unique frequency response of GA and HA allows for modulation of alternating current signals so that several other markers important in the management of diabetes could be measured with a single sensor. Future work will be necessary to establish multimarker sensing on one electrode.
ContributorsEusebio, Francis Ang (Author) / LaBelle, Jeffrey (Thesis director) / Pizziconi, Vincent (Committee member) / Barrett, The Honors College (Contributor) / Harrington Bioengineering Program (Contributor)
Created2014-05
Description
Lithium-ion batteries are one of the most widely used energy storage solutions today. As renewable energy sources proliferate to meet growth in worldwide energy consumption, it is important that lithium-ion batteries be improved to help capture this energy for use when the demand arises. One way to boost the performance of lithium-ion batteries is to replace the electrode active materials with materials of higher specific capacity. Silicon is one material that has been widely touted as a potential replacement for the graphite used in commercial anodes with a theoretical capacity of 3500 mAh/g as opposed to graphite's 372 mAh/g. However, bulk silicon is known to pulverize after experiencing large strains during lithiation. Here, silicon clathrates are investigated as a potential structure for accommodation of these strains. Silicon clathrates consist of covalently bonded silicon host cages surrounding a guest alkali or alkaline earth metal ion. Previous work has looked at silicon clathrates for their superconducting and thermoelectric properties. In this study, electrochemical properties of type I and II silicon clathrates with sodium guest ions (NaxSi46 and NaxSi136) and type I silicon clathrates with copper framework substitution and barium guest ions (Ba8CuxSi46-x) are examined. Sodium clathrates showed very high capacities during initial lithiation (>2500 mAh/g), but rapidly lost capacity thereafter. X-ray diffraction after lithiation showed conversion of the clathrate phase to lithium silicide and then to amorphous silicon after delithiation, indicating destruction of the clathrate structure as a possible explanation for the rapid capacity fade. Ba8CuxSi46-x clathrates were found to have their structures completely intact after 50 cycles. However, they had very low reversible capacities (<100 mAh/g) and potentially might not be electrochemically active. Further work is needed to better understand exactly how lithium is inserted into clathrates and if copper impurities detected during wavelength-dispersive X-ray spectroscopy could be inhibiting lithium transport into the clathrates.
ContributorsWagner, Nicholas Adam (Author) / Chan, Candace (Thesis director) / Sieradzki, Karl (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2014-05
Description
Over the last decade copper electrodeposition has become the dominant process by which microelectronic interconnects are made. Replacing ultra-high vacuum evaporative film growth, the technology known as the Cu damascene process has been widely implemented in the microelectronics industry since the early 2000s. The transition from vacuum film growth to electrodeposition was enabled by solution chemistries that provide "bottom-up" or superfilling capability of vias and trenches. While the process has been and is used widely, the actual mechanisms responsible for superfilling remain relatively unknown. This dissertation presents and discusses the background and results of experimental investigations that have been done using in situ electrochemical surface stress monitoring techniques to study the evolution of stress on Cu{111} thin film electrodes. Because of its extreme sensitivity to the structure on both the electrode and solution sides of the interface, surface stress monitoring as analytical technique is well suited for the study of electrodeposition. These ultra-high resolution stress measurements reveal the dynamic response of copper electrodes to a number of electrochemical and chemical experimental variables. In the case of constant current pulsed deposition and stripping, the surface stress evolution depends not only on the magnitude of the current pulse, but also shows a marked response to plating bath composition. The plating bath chemistries used in this work include (1) additive free, (2) deposition suppressing solutions that include polyethylene glycol (PEG) and sodium chloride (NaCl) as well as (3) full additive solution combinations which contain PEG, NaCl, and a one of two deposition accelerating species (bis-(sodiumsulfopropyl)disulfide (SPS) or mercaptopropane sulfonic acid (MPS)). The development of thin film stress is further investigated through a series of solution exchange experiments that correlate the magnitude of electrode exchange current density and the stress state of the film. Remarkably, stress changes as large as ~8.5 N/m are observed during solution exchanges at the open circuit potential. Overall, this research demonstrates that solution chemistry can have a large impact on thin film stress evolution, even for very small deposition thicknesses (e.g. <10 ML) or in the absence of net addition or removal of material from the electrode.
ContributorsHeaton, Thomas Stanley (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
Description
This thesis develops molecular models for electron transport in molecular junctions and intra-molecular electron transfer. The goal is to identify molecular descriptors that afford a substantial simplification of these electronic processes.
First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon’s tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer.
Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed.
Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of several intermediates in the catalytic cycle of a model NiFe complex, a hypothetical reaction mechanism, which very well agrees with the observed experimental results, is proffered.
Future work related to this thesis may involve the systematic analysis of chemical reactivity in constrained geometries, a subject of importance if the context of enzymatic activity. Another, more intriguing direction is related to the fundamental issue of reformulating Marcus theory in terms of the molecular dielectric response function.
First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon’s tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer.
Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed.
Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of several intermediates in the catalytic cycle of a model NiFe complex, a hypothetical reaction mechanism, which very well agrees with the observed experimental results, is proffered.
Future work related to this thesis may involve the systematic analysis of chemical reactivity in constrained geometries, a subject of importance if the context of enzymatic activity. Another, more intriguing direction is related to the fundamental issue of reformulating Marcus theory in terms of the molecular dielectric response function.
ContributorsKhezr Seddigh Mazinani, Shobeir (Author) / Mujica, Vladimiro (Thesis advisor) / Pilarisetty, Tarakeshwar (Committee member) / Angell, Charles A (Committee member) / Jones, Anne K (Committee member) / Arizona State University (Publisher)
Created2015
Description
Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for
future energy storage devices. Electrode materials that alloy with Li, such as Si, are one
of the most promising alternatives for Li-ion battery anodes due to their high capacities.
Tetrel (Si, Ge, Sn) clathrates are a class of host-guest crystalline structures in which
Tetrel elements form a cage framework and encapsulate metal guest atoms. These
structures can form with defects such as framework/guest atom substitutions and
vacancies which result in a wide design space for tuning materials properties. The goal of
this work is to establish structure property relationships within the context of Li-ion
battery anode applications. The type I Ba 8 Al y Ge 46-y clathrates are investigated for their
electrochemical reactions with Li and show high capacities indicative of alloying
reactions. DFT calculations show that Li insertion into the framework vacancies is
favorable, but the migration barriers are too high for room temperature diffusion. Then,
guest free type I clathrates are investigated for their Li and Na migration barriers. The
results show that Li migration in the clathrate frameworks have low energy barriers (0.1-
0.4 eV) which suggest the possibility for room temperature diffusion. Then, the guest
free, type II Si clathrate (Na 1 Si 136 ) is synthesized and reversible Li insertion into the type
II Si clathrate structure is demonstrated. Based on the reasonable capacity (230 mAh/g),
low reaction voltage (0.30 V) and low volume expansion (0.21 %), the Si clathrate could
be a promising insertion anode for Li-ion batteries. Next, synchrotron X-ray
measurements and pair distribution function (PDF) analysis are used to investigate the
lithiation pathways of Ba 8 Ge 43 , Ba 8 Al 16 Ge 30 , Ba 8 Ga 15 Sn 31 and Na 0.3 Si 136 . The results
show that the Ba-clathrates undergo amorphous phase transformations which is distinct
from their elemental analogues (Ge, Sn) which feature crystalline lithiation pathways.
Based on the high capacities and solid-solution reaction mechanism, guest-filled
clathrates could be promising precursors to form alloying anodes with novel
electrochemical properties. Finally, several high temperature (300-550 °C)
electrochemical synthesis methods for Na-Si and Na-Ge clathrates are demonstrated in a
cell using a Na β’’-alumina solid electrolyte.
ContributorsDopilka, Andrew (Author) / Chan, Candace K (Thesis advisor) / Zhuang, Houlong (Committee member) / Peng, Xihong (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021