Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Bibliography: leaves 254-255. / by Chau-Chyun Chen. / Sc.D.

Lithium-ion battery (LIB) is an indispensable energy storage device in portable electronics, and its applications in electric vehicles and grid-level energy storage are increasing dramatically in recent years due to high demands. To meet energy demands and address fire hazards, next generation batteries with better safety, higher energy density, and longer cycle life have been actively investigated. In this thesis, works on polymer and ceramic solid electrolytes to improve safety and energy density of rechargeable solid-state batteries are discussed. In the first section, a flexible composite solid electrolyte is presented. Since ceramic electrolytes have high conductivities but are fragile, and polymer electrolytes are easy to process but have low conductivities, we propose a composite structure that combines these advantages. A vertically aligned and connected ceramic electrolyte is realized through the ice-templating method to improve the ionic conduction. Then a polyether-based polymer electrolyte is added to make the composite electrolyte flexible. Specifically, vertically aligned and connected LATP and LAGP nanoparticles (NPs) in the polyethylene oxide (PEO) matrix are made. The conductivity reaches 0.52 × 10-4 S/cm for LATP/PEO, and 1.67 × 10-4 S/cm for aligned LAGP/PEO composite electrolytes, which are several times higher than that with randomly dispersed LATP/LAGP NPs in PEO. Compared to the pure PEO electrolyte, the mechanical and thermal stabilities of the composite solid electrolyte are higher. The LFP-LAGP/PEO-Li cell with 148.7 mAh/g during the first discharge at 0.3C has over 95% capacity retention after 200 cycles. This method opens a new approach to optimize ion conduction in composite solid electrolytes for solid-state batteries. In the next section, polyether-based polymer electrolytes such as PEO and PEG are studied. Polyether-based electrolytes are electrochemically unstable above 4 V, restricting their use with high voltage cathodes such as NMC for high energy density. A technique involving atomic layer deposition (ALD) of Al2O3 to stabilize the polyether-based electrolyte with 4 V class cathodes is described. With a 2 nm Al2O3 coating, the capacity retention stays at 84.7% after 80 cycles and 70.3% after 180 cycles for the polyether-based electrolyte. Without the coating, the capacity drops more than 50% after only 20 cycles. This study opens new opportunity to develop safe electrolytes for lithium batteries with high energy density. In the final section, we propose a new polymer electrolyte, a poly(vinylidene fluoride) (PVDF) polymer electrolyte with organic plasticizer dimethylformamide (DMF), which possesses compatibility with 4V cathode for high energy density and high ionic conductivity (1.2×10-4 S/cm) at room temperature. This polymer electrolyte can be used as a supplement for the polyether-based electrolytes we discussed in the first two sections. In this polymer electrolyte, palygorskite ((Mg,Al)2Si4O10(OH)) nanowires are introduced to form composite solid electrolytes (CPE) to enhance both stiffness and toughness of PVDF/DMF-based polymer electrolyte. With 5 wt % of palygorskite nanowires, the elastic modulus of the PVDF-DMF CPE increases from 9.0 MPa to 96 MPa, and its yield stress increases by 200%. We further demonstrate that full cells composed of Li(Ni1/3Mn1/3Co1/3)O2 (NMC 111) cathode, PVDF-DMF/palygorskite CPE, and lithium metal anode, can be cycled over 200 times at 0.3 C, with 97% capacity retention. Moreover, the PVDF-DMF electrolyte is nonflammable, making it a safer alternative to the conventional liquid electrolyte. Our work illustrates that the PVDF-DMF/palygorskite CPE is a promising electrolyte for solid state batteries with better safety and cycling performance. Collectively, we study the polyether-based polymer electrolyte and ceramic electrolyte to combine their advantages through the ice-templating method in a battery, use ALD technique to stabilize polyether-based electrolyte for high energy density, and propose an alternative PVDF/DMF-based polymer electrolyte with nanowire additives for high energy density and stable cycling, contributing to the rechargeable solid-state batteries, with better safety, higher energy density and better cycling stability.

Introdução: Apesar da falta de evidência cientifica, costuma-se pensar que crianças obesas apresentam desvantagens e são menos tolerantes ao se exercitarem no calor. Objetivo: Comparar a sudorese, balanço hidro-eletrolítico e a tolerância ao exercício no calor entre meninos pré-púberes obesos e eutróficos que pedalam no calor. Métodos: Trinta meninos pré-púberes foram alocados para o grupo de obesos (GO, n=15) e eutróficos (GE, n=15). Após uma sessão de avaliação, os meninos vieram ao laboratório para a sessão de exercício no calor (35C, 40-45%UR). Eles pedalavam por 30 minutos a 50-60% do seu VO2pico pré determinado. Para coletar o suor, adesivos foram fixados sobre 4 regiões da pele (costas, peito, antebraço e coxa) e as amostras foram analisadas para eletrólitos (AVL, 9180). Após o exercício, amostras de urina foram coletadas para análise de volume e eletrólitos para coleta regional de suor (AVL, 9180). Após a pedalada, os meninos descansaram por 10 min e pedalaram a 90% do VO2pico até a exaustão e o tempo de desempenho foi registrado. Durante a sessão, a ingestão “ad libitum” de uma bebida esportiva foi avaliada. Sensação subjetiva de calor foi avaliada durante toda a sessão. Resultados: A taxa de sudorese relativa a área de superfície corporal foi similar entre eutróficos e obesos (488  232 e 417  89.6 ml.m2.min-1, respectively; p=0,004) e as [Na+] e [Cl-] no suor foram maiores nos meninos obesos (p=0,005), enquanto a [K+] foi similar entre os grupos (p = 0,004). Ambos os grupos apresentaram um balanço hidroeletrolítico negativo, mas não existiu diferença entre os grupos. O tempo de desempenho foi maior no GE (89.6  64.1) que o GO (41.2  29.6 seg; p=0,005). A sensação subjetiva de calor foi maior no GO que no GE em todos os momentos (p = 0,005). Conclusão: Meninos pré-púberes obesos apresentaram uma similar taxa de sudorese relativa à área de superfície corporal, menor tolerância ao exercício no calor, e maior [Na+] e [Cl-] no suor comparado aos eutróficos. Crianças obesas não diferem das eutróficas em relação ao balanço hidroeletrolítico. / Introduction: Despite the lack of scientific evidence, it is generally thought that obese children have disadvantages and are less tolerant to exercise in the heat when compared to lean children. Purpose: To compare sweating, water and electrolyte balance, and exercise tolerance heat between obese and lean boys who cycled in the heat. Methods: Thirty prepubertal boys formed an obese (OG, n=15) and a lean (LG, n=15) group. After a screening session and evaluation of physical characteristics and VO2peak, the boys came to the laboratory for the exercise session in the heat (35C, 40-45%RU). They cycled for 30 minutes at 50-60% of their pre-determined VO2peak. To collect sweat, patches were attached on 4 regions of the skin (back, chest, forearm and thigh) and samples were analyzed for electrolytes (AVL 9180). After exercise, urine samples were collected for volume and electrolyte analyses (AVL 9180). After this cycling, the boys rested 10 min and cycled at 90% VO2peak until exhaustion and the performance time was registered. During the whole session, a sports drink was available to drink “ad libitum” and the intake was registered. Heat subject sensation (HSS) was evaluated during the whole session. Results: Sweat rate relative to body surface area was similar between lean and obesity boys (488  232 and 417  89.6 ml.m2.min-1, respectively; p=0.004) and sweat [Na+] and [Cl-] were higher in the obese boys (p=0.005), whereas [K+] was similar between groups (p = 0.004). Both groups showed a negative water and electrolyte balance, but there was no difference between groups. The performance time was longer in the LG (89.6  64.1) than OG (41.2  29.6 sec; p=0.005). The heat subjective sensation was higher in GO than in GE at all times (p = 0.005). Conclusion: Obese prepubescent boys showed similar sweat rate relative to body surface area, lower exercise heat tolerance, and increased [Na+] and [Cl-] sweat loss compared to lean children. Obese children did not differ from lean children related to water and electrolyte balance.

Polímeros naturais são muito interessantes para obtenção de eletrólitos sólidos (ESPs). A grande vantagem é devida as suas propriedades de biodegradação por causa de sua procedência como também baixo custo de obtenção e boas propriedades físico-químicas. Estes polímeros contem na suas estrutura heteroatomos e por esta razão podem complexar prótons ou íons de lítio levando a condução iônica. Dentre diversos polímeros naturais os ESPs a base de Quitosana mostram boas características opto-eletroquímicas e podem ser aplicados em dispositivos eletrocrômicos. Nesta dissertação estão apresentados os resultados de preparação e caracterização de novos eletrólitos sólidos poliméricos (ESPs) obtidos através da plastificação da Quitosana com Glicerol, Sorbitol e Etileno Glicol, onde o próprio solvente, Ácido Clorídrico (HCl), é o doador de prótons responsáveis pala condução iônica dos ESPs. Alem disso foram estudadas também as amostras contendo LiCF3SO3. A caracterização dos materiais na forma de filmes foi realizada utilizando-se as técnicas básicas de caracterização de materiais tais como: análises térmicas (DSC), análises estruturais (raios-X), medidas óticas (UV-Vis), visualização da superfície das amostras através de microscopia eletrônica de varredura (MEV), espectroscopia (FTIR), Titulação Potenciométrica e como a mais importante: medidas de condutividade iônica por espectroscopia de impedância complexa (EIE). Os filmes de ESPs contendo Glicerol apresentaram-se flexíveis, transparentes (acima de 80% de transmitância na região do visível de espectro eletromagnético )e visualmente com boa aderência ao vidro e ao aço inox. A plastificação com diferentes quantidades de Glicerol, mas mantendo a mesma concentração de HCl, revelou que a amostra contendo 59% de Glicerol apresentou os melhores valores de condutividade iônica. Para esta quantidade de plastificante foi feito o estudo da influência de concentração do Ácido Clorídrico (HCl) nos valores de condutividade iônica. Este ensaio demonstrou que a amostra com 0,048 mol.L-1 apresentou maior valor de condutividade, sendo 9,54.10-4Scm-1 a temperatura ambiente. Ainda com adição de 48% do Glicerol e a inserção de 13% em massa do LiCF3SO3 foi obtida a condutividade de 2,19x10-5Scm-1. Os filmes plastificados com Etileno Glicol apresentaram melhor valor de condutividade iônica de 2,4.10-4Scm-1 a temperatura ambiente, para amostra contendo 68% de plastificante e concentração de 0,048 molL-1 de HCl. Também são transparentes, flexíveis e aderentes. Os filmes de Quitosana plastificada com Sorbitol não apresentaram boas condutividades, i.e. de ordem de 10-6 Scm-1 a temperatura ambiente para amostra contendo 59% de Sorbitol e 0,048 mol.L-1, contudo são transparentes, mas não são aderentes ao vidro e ainda são quebradiços. Os resultados demonstraram que os novos ESPs obtidos a base de filmes de Quitosana plastificada com EG e Glicerol são ótimos candidatos a serem utilizados em dispositivos eletrocrômicos. / Natural polymers are very interesting matrix to obtain solid polymeric electrolytes (SPE). The principal advantage comes from its particularly interesting biodegradation properties due to the natural precedence and also very low cost and good physical and chemical properties. These polymers contain heteroatoms in its structure and for this reason can complex protons or lithium ions leading to the ionic conduction. Among different natural polymers, chitosan-based SPEs show good opto-electrochemical characteristics and can be applied in electrochemical devices. This work presents the results of chitosan-based electrolytes, which were characterized by impedance spectroscopy (EIE), thermal analysis (DSC) and scanning microscopy (SEM). The SPEs samples were obtained from chitosan plasticized with glycerol, ethylene glycol and sorbitol and containing HCl and lithium salt LiClO4. Different compositions of SPEs i.e. salt and plasticizer quantities were investigated, where it was observed that the ionic conductivity results obtained for these SPEs varied from 10-6 S/cm to 10-4 S/cm at room temperature depending on the sample and increased following Arrhenius ionic conductivity models. The best results of ionic conductivity values of 9,54.10-4Scm-1 were obtained for SPEs of chitosan plasticized with 48% of glycerol and containing 0,048 molL-1 of HCl. The samples containing 68% of ethylene glycol showed ionic conductivity of 2,4.10-4Scm-1 at room temperature and the samples with 59% of sorbitol showed the ionic conductivity values of 10-6 Scm-1. Thermal analysis using calorimetry (DSC) was performed in order to observe the change in glass transition temperature caused by the changes performed on the samples. Good conductivity results combined with transparency and good adhesion to the electrodes have shown that chitosan-based SPEs are very promising materials to be used as solid electrolytes in electrochromic devices.

No description available.

Abstract not available

Includes bibliographical references

[Truncated abstract] New, double-doped, Bi2O3-based materials in the Bi2O3 Ln2O3 PbO (Ln = La, Nd, Er and Yb) and Bi2O3 WO3 PbO systems were prepared using solid-state reactions. For the Bi2O3 Er2O3 PbO and Bi2O3 Yb2O3 PbO systems, the air-quenchable compositional domain of the fcc fluorite-type phase was partially established. Temperature dependent conductivity measurements were performed on these quenched-in fluorite-type materials using AC impedance spectroscopy. Conductivity at 750[degrees Celsius] generally increased with increasing Pb2+/Ln3+ and decreasing (Ln3++Pb2+)/Bi3+ ratios. The material (BiO1.5)0.70(ErO1.5)0.15(PbO)0.15 had a conductivity of 0.66 [plus-minus] 0.05 S cm-1 at 750[degrees Celsius], placing it among the most highly conductive Bi2O3-based materials, and was the best new fluorite-type material from a combined conductivity and structural stability viewpoint. Some of the new materials in the Bi2O3 La2O3 PbO and Bi2O3 Nd2O3 PbO systems appeared to have the quenched-in fluorite type structure based on powder X-ray diffraction data. These materials had very high conductivities at 750[degrees Celsius] of `~ 1 S cm-1, but underwent rapid symmetry lowering transformations during heating, thus making them unsuitable for use as solid electrolytes. The fluorite-type structure was not air-quenchable in the Bi2O3 WO3 PbO system, for the compositions synthesised. Room temperature neutron powder diffraction data were collected for quenched-in fluorite-type materials in the (BiO1.5)0.80(LnO1.5)0.20-x(PbO)x, Ln = Er and Yb, x = 0, 0.03, 0.06 and 0.09, and (BiO1.5)0.97-y(ErO1.5)y(PbO)0.03, y = 0.27, 0.17 and 0.12, series. ... This suggests that Pb2+ dopant cations occupy face-centre positions in the fcc unit cell, and the Pb2+ lone pair electrons are likely to be orientated towards an oxide ion vacancy in an adjacent tetrahedral site. Pb2+/oxide ion vacancy interactions affect the migration of oxide ions/oxide ion vacancies through the structure, and are responsible for the significantly larger activation energy for oxide ion migration in the Pb2+-doped materials relative to the Pb2+-free materials. For example, the activation energies of (BiO1.5)0.80(ErO1.5)0.20-x(PbO)x, x = 0.03 and 0.06, were 1.50 [plus-minus] 0.02 and 1.54 [plus-minus] 0.02 eV, respectively, while the activation energy for (BiO1.5)0.80(ErO1.5)0.20 was 1.25 [plus-minus] 0.04 eV. Long-term annealing of the quenched in fluorite-type materials in the Bi2O3 Er2O3 PbO and Bi2O3 Yb2O3 PbO systems at 500 and 600[degrees Celsius] resulted in conductivity lowering structural transformations, making these materials unsuitable for practical use as solid electrolytes at these temperatures. For example, the materials (BiO1.5)0.80(ErO1.5)0.20-x(PbO)x, x = 0.03, 0.06 and 0.09, underwent a fluorite-type to tetragonal transformation during annealing at 500[degrees Celsius] due to <100> oxide ion vacancy ordering, and the rate of conductivity decay at 500[degrees Celsius] increased with increasing Pb2+/Er3+ ratio. Long-term annealing experiments at 500[degrees Celsius] performed on air quenched (Bi2O3)0.705(Er2O3)0.245(WO3)0.050 showed that the disordered fluorite-type structure of this material was not fully stabilised, as evidenced by the presence of superlattice reflections in selected area electron diffraction patterns for the material annealed for 2000 hours, and a gradual conductivity decay after ~ 150 hours annealing.

Lowering the operating temperature of the high-temperature, solid oxide fuel cell (SOFC) improves both the thermodynamic efficiency and the lifetime of this energy efficient technology. Unfortunately the rate of oxygen-ion transport through the solid electrolyte is temperature dependent, and materials previously employed as electrolytes in the high-temperature SOFC perform poorly at intermediate temperatures. Therefore new oxygen-ion conductors with enhanced ionic conductivity at intermediate temperatures are required. The bulk of the existing literature on high-temperature SOFCs has focussed on zirconia-based binary systems as electrolytes, due to their high ionic conductivity and negligible electronic conductivity. Only select compositions within the zirconia-scandia system have demonstrated acceptable ionic conductivity levels at intermediate temperatures; however unstable phase assemblage and the high economic cost of scandia are clear disadvantages. Ceria-based binary systems have demonstrated improved oxygen-ion conductivity at intermediate temperature compared to many zirconia systems, however significant levels of n-type electronic conductivity are observed at low oxygen partial pressures. Consequently it was thought unlikely that significant increases in ionic conductivity would be found in existing zirconia- and ceria-based binary systems, therefore another approach was required in an attempt to improve the performance of these established fluorite systems. The fluorite systems Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc) were prepared and investigated as possible, intermediate-temperature SOFC electrolytes in an attempt to combine the higher conductivity found in the ceria systems with the low electronic conductivity observed in the zirconia systems. Also it was anticipated that systems containing dopants not previously observed to confer high ionic conductivity in either zirconia- and ceria-based binary systems, might exhibit enhanced ionic conductivity with expansion of the zirconia lattice resulting from the addition of ceria. All the as-fired Zr0.75Ce0.08M0.17O1.92 compositions possessed the face-centred cubic structure and lattice parameter measurements revealed the anticipated unit cell enlargement as the size of the dopant cation increased. No unusual microstructural parameters were identified that could be expected to interfere with the ionic transport properties in the as-fired compositions. The electrical conductivity was found to be influenced by the dopant-ion radius, the presence of ceria, low oxygen partial pressures and, in some compositions, the formation of poorly conducting, ordered-pyrochlore microdomains dispersed amongst the cubic defect-fluorite matrix. In a second approach to the formulation of new oxygen-ion conductors suitable for the intermediate-temperature SOFC, compounds possessing structures other than the fluorite structure were considered. An examination of the literature for oxides having the pyrochlore, scheelite and perovskite structures showed that the Sr+2- and Mg+2-doped LaGaO3 perovskites (LSGM) possessed ionic conductivity equal to the highest conducting, zirconia and ceria binary compounds. Therefore the perovskite systems La0.9Sr0.1Ga(0.8-x)InxMg0.2O2.85 (X = 0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8) (I-LSGM) were prepared and examined, the objective being to favourably influence structural parameters believed responsible for optimal ionic conductivity, namely the unit cell symmetry and volume. It was found that In+3 systematically substituted for Ga+3 on to the B-site of LSGM at least up to the X = 0.4 composition. While In+3 was found to replace the Ga+3 as expected, Mg+2, which occupies the same crystallographic site, was also replaced by In+3. Up to the X = 0.2 composition, at least two trace level secondary phases were observed to form along with the bulk I-LSGM phase. For I-LSGM compositions with X > 0.2, significantly larger concentrations of the secondary phases were identified. Evidence of a strontium-rich, high-temperature liquid phase was observed also near the grain boundaries on as-sintered and thermally etched surfaces in LSGM and I-LSGM compositions. It is believed that the observed, high sintered density in the complex, doped-LaGaO3 systems is due to the formation of this high-temperature liquid phase. Increasing levels of diffuse scatter and superstructure formation were observed in electron diffraction patterns in the I-LSGM bulk phase (up to X = 0.2), indicating a possible decrease in vacancy concentration and reduced, localised unit cell symmetry. The electrical conductivity in the I-LSGM compositions was believed to be influenced by the distortion of the oxygen-ion conduction path, a reduction in vacancy concentration, formation of stronger dopant-vacancy associates at low temperature and the presence of ordered structures. In addition, phase instability, in the form of subtle ordering in specific crystalline planes, was observed to influence the electrical conductivity as a function of time at intermediate temperatures.

<p>The discovery of semi-conducting and conducting organic materials has opened new possibilities for electronic devices and systems. Applications, previously unattainable for conventional electronics, have become possible thanks to the development of conjugated polymers. Conjugated polymers that are both ion- and electron conducting, allow for electrochemical doping and de-doping via reversible processes as long as both forms of conduction remain available. Doping causes rearrangement of the -system along the polymer backbone, and creates new states in the optical band gap, resulting in an increased electronic conductivity and also control of the color (electrochromism). Doping can also occur by charge injection at a metal – semiconducting polymer interface. Electrochemical electronic devices and solid state devices based on these two types of doping are now beginning to enter the market.</p><p>This thesis deals with organic based-devices whose working mechanism involves electrolytes. After describing the properties of conjugated polymers, fundamentals on electrolytes (ionic conductivity, types, electric double layer and the electric field distribution) are briefly presented. Thereafter, a short review of the field of organic field effect transistors as well as a description of transistors that are gated via an electrolyte will be reviewed.</p><p>Paper I present a novel technique to visualize the electric field within a two-dimensional electrolyte by applying the electrolyte over an array of electronically isolated islands of electrochromic polymer material on a plastic foil. By observing the color change within each polymer island the direction and the magnitude of the electric field can be measured. This technology has applications in electrolyte evaluation and is also applicable in bio-analytical measurements, including electrophoresis. The focus of paper II lies on gating an organic field effect transistor (OFET) by a polyanionic proton conductor. The large capacitance of the electric double layer (EDL) that is formed at organic semiconductor/polyelectrolyte upon applying a potential to the gate, results in low operation voltages and fast response. This type of transistor that is gated via electric double layer capacitor is called EDLC-OFET. Because an electrolyte is used as a gate insulator, the role of the ionic conductivity of the electrolyte is considered in paper III. The effect on the electronic performance of the transistor is studied as well by varying the humidity level.</p>