Large specific gravimetric/volumetric energy density, environmental benignity and safe low working voltage. All of these points have been used to describe the lithium sulfur (Li-S) battery in the past, but often times it is short cycle life and poor capacity retention that is associated with the Li-S battery. In order to realize the full potential of the Li-S battery in society today, many obstacles must be overcome. In a typical Li-S cell with an organic liquid electrolyte sulfur is reduced by lithium during discharge and subsequent lithium polysulfide species (Li2Sx where x, 2 < x < 8) are formed. These species are readily soluble in typical organic electrolytes and can lead to low Coulombic efficiency and most challenging: active mass loss. Through the loss of active mass, rapid capacity fading occurs over long-term cell cycling. Overcoming the loss of active mass and stabilizing cell capacity at high rates is pivotal to the realization of practical Li-S cells. In this thesis, four separate concepts and materials were studied and prepared with the aim to improve the Li-S batteries capacity, cycle life and capacity retention.

Large specific gravimetric/volumetric energy density, environmental benignity and safe low working voltage. All of these points have been used to describe the lithium sulfur (Li-S) battery in the past, but often times it is short cycle life and poor capacity retention that is associated with the Li-S battery. In order to realize the full potential of the Li-S battery in society today, many obstacles must be overcome. In a typical Li-S cell with an organic liquid electrolyte sulfur is reduced by lithium during discharge and subsequent lithium polysulfide species (Li2Sx where x, 2 < x < 8) are formed. These species are readily soluble in typical organic electrolytes and can lead to low Coulombic efficiency and most challenging: active mass loss. Through the loss of active mass, rapid capacity fading occurs over long-term cell cycling. Overcoming the loss of active mass and stabilizing cell capacity at high rates is pivotal to the realization of practical Li-S cells. In this thesis, four separate concepts and materials were studied and prepared with the aim to improve the Li-S batteries capacity, cycle life and capacity retention.

With the rapid development of portable electronics, hybrid-electric and electric cars, there is great interest in utilization of sulfur as cathodes for rechargeable lithium batteries. Lithium/sulfur batteries implement inexpensive, the earth-abundant elements at the cathode while offering up to a five-fold increase in energy density compared with the present Li-ion batteries. However, electrically insulating character of sulfur and solubility of intermediate polysulfides in organic liquid electrolytes, which causes rapid capacity loss upon repeated cycling, restrict the practical application of Li/S batteries. In this thesis, the gel polymer and solid polymer electrolytes were synthesized and applied in Li/S batteries. A gel polymer electrolyte (GPE) was formed by trapping 1 M lithium bistrifluoromethane-sulfonamide (LiTFSI) in tetraethylene glycol dimethyl ether (TEGDME) electrolyte in a poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) /poly(methylmethacrylate) (PMMA) polymer matrix. The electrochemical properties of the resulting GPE were investigated in lithium/sulfur battery. The gel polymer battery exhibited a high specific capacity of 753.8 mAh gˉ¹ at the initial cycle, stable reversible cycling and a capacity retention about 80% over 40 cycles along with a high Coulombic efficiency. Comparative studies conducted with the 1 M LiTFSI liquid electrolyte cell demonstrated that a cell with liquid electrolyte has remarkably low capacity retention and Coulombic efficiency compared with the GPE cell. In the further studies, a solid polymer electrolyte (SPE) based on poly- (ethylene-oxide)/nanoclay composite was prepared and used to assemble an all-solid-state lithium/sulfur battery. The ionic conductivity of the optimized electrolyte has achieved about 3.22×10ˉ¹ mS cmˉ¹ at 60 °C. The Li/S cell with this SPE delivered an initial discharge capacity of 998 mAh gˉ¹ when operated at 60 °C, and retained a reversible capacity of 634 mAh gˉ¹ after 100 cycles. These studies has revealed that the electrochemical performance of lithium/sulfur cells, including charge-discharge cyclability and Coulombic efficiency, can be significantly improved by replacing liquid electrolytes with solid polymer and gel polymer electrolytes, which reduce the polysulfide shuttle effect and could protect the lithium anode from the deposition of the electrochemical reaction, leading to higher sulfur utilization in the cell.

With the rapid development of portable electronics, hybrid-electric and electric cars, there is great interest in utilization of sulfur as cathodes for rechargeable lithium batteries. Lithium/sulfur batteries implement inexpensive, the earth-abundant elements at the cathode while offering up to a five-fold increase in energy density compared with the present Li-ion batteries. However, electrically insulating character of sulfur and solubility of intermediate polysulfides in organic liquid electrolytes, which causes rapid capacity loss upon repeated cycling, restrict the practical application of Li/S batteries. In this thesis, the gel polymer and solid polymer electrolytes were synthesized and applied in Li/S batteries. A gel polymer electrolyte (GPE) was formed by trapping 1 M lithium bistrifluoromethane-sulfonamide (LiTFSI) in tetraethylene glycol dimethyl ether (TEGDME) electrolyte in a poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) /poly(methylmethacrylate) (PMMA) polymer matrix. The electrochemical properties of the resulting GPE were investigated in lithium/sulfur battery. The gel polymer battery exhibited a high specific capacity of 753.8 mAh gˉ¹ at the initial cycle, stable reversible cycling and a capacity retention about 80% over 40 cycles along with a high Coulombic efficiency. Comparative studies conducted with the 1 M LiTFSI liquid electrolyte cell demonstrated that a cell with liquid electrolyte has remarkably low capacity retention and Coulombic efficiency compared with the GPE cell. In the further studies, a solid polymer electrolyte (SPE) based on poly- (ethylene-oxide)/nanoclay composite was prepared and used to assemble an all-solid-state lithium/sulfur battery. The ionic conductivity of the optimized electrolyte has achieved about 3.22×10ˉ¹ mS cmˉ¹ at 60 °C. The Li/S cell with this SPE delivered an initial discharge capacity of 998 mAh gˉ¹ when operated at 60 °C, and retained a reversible capacity of 634 mAh gˉ¹ after 100 cycles. These studies has revealed that the electrochemical performance of lithium/sulfur cells, including charge-discharge cyclability and Coulombic efficiency, can be significantly improved by replacing liquid electrolytes with solid polymer and gel polymer electrolytes, which reduce the polysulfide shuttle effect and could protect the lithium anode from the deposition of the electrochemical reaction, leading to higher sulfur utilization in the cell.

This thesis was devised as a fundamental study of the Li-S system by the use of 7Li Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR), X-ray Absorption Near- Edge Structure (XANES), and Non-Resonant Inelastic X-ray Scattering (NRIXS). The first part of this thesis reports the first evidence of a stable solid-phase intermediate between elemental sulfur (α-S8) and Li2S, Li2S6, which can be used to understand deeper Li-S battery. The second part of this thesis is based on operando XANES measurements made in the Argonne Photon Source (APS).Linear combination fit (LCF) analyses are performed to interpret the data; and, noticeably, the distinction between short-chain and long-chain polysulfides can be made due to the use of proper reference materials. The results reveal the first detailed observation of typical sulfur redox chemistry upon cycling, showing how sulfur fraction (under-utilization) and sulfide precipitation impact capacity. It also gives new insights into the differences between the charge and discharge mechanisms, resulting in the hysteresis of the cycling profile. Operando XANEs were also performed on het-treated material, which exhibits a particular electrochemical signature, which has never explained. After a preliminary electrochemical study by potentiodynamic cycling with galvanostatic acceleration (PCGA), operando XANES measurements at the sulfur K-edge are performed on heat-treated PCNS. Noticeably, the difference in the XANES signatures of the pristine and the recharged state shows the irreversible process that occurs during the first discharges. At last, electrolytes are investigated by the compilation of quantitative physico-chemical parameters – viscosity, ionic conductivity, and solubility of Li2S and Li2S6 – on novel class of solvents that are glymes with non-polar groups and acetonitrile (ACN) complexed with LiTFSI. 1,1,2,2-Tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (HFE) is chosen to decrease their viscosities. (ACN)2:LiTFSI attracts particular attention because of the particularly low Li2Sn solubility and. Its good electrochemical performance when mixed with 50 vol% HFE. Operando XANES proves the formation of polysulfides in this electrolyte, although constrains imposed by this novel electrolyte to the XANES experiment complicate the data analysis. The low energy feature evolution shows a more progressive mechanism involved in this electrolyte, which could be linked to the particularly low Li2Sn solubility

Indiana University-Purdue University Indianapolis (IUPUI) / Recent innovations in portable electronics, electric vehicles and power generation by wind and solar have expanded the need for effcient battery storage. Lithium-ion batteries have been the frontline contender of battery storage yet are not able to match current demands. Alternatively, lithium-sulfur batteries are a promising technology to match the consumer demands. Elemental sulfur cathodes incur a variety of problems during cycling including the dissolution of intermediate lithium polysul- fides, an undesirable volume change (~ 80%) when completely reduced and a high dependence on liquid electrolyte, which quickly degrades the cell's available energy density. Due to these problems, the high theoretical capacity and energy density of lithium sulfur cells are unattainable. In this work, A new class of phenyl polysul- fides, C6H5SxC6H5(4 < x <6), are developed as liquid sulfur containing cathode materials. This technology was taken a step further to fulfill and emerging need for exible electronics in technology. Phenyl tetrasulfide (C6H5S4C6H5) was polymerized to form a high energy density battery with acute mobility. Lithium half-cell testing shows that phenyl hexasulfide (C6H5S6C6H5) can provide a specific capacity of 650mAh/g and capacity retention of 80% through 500 cycles at 1C rate along with superlative performance up to 10C. Furthermore, 1, 302W h/ kg and 1, 720W h/L are achievable at a low electrolyte/active material ratio. Electrochemical testing of polymer phenyl tetrasulfide reveals high specific capacities of 634mAh /g at 1C, while reaching 600mAh /g upon mechanical strain testing. This work introduces novel cathode materials for lithium-sulfur batteries and provides a new direction for the development of alternative high-capacity flexible cathode materials.

Lithium batteries have revolutionized emerging electronic applications and will play more important roles in the future. Unfortunately, the energy density of commercial lithium-ion batteries (100-265 Wh kg-1) cannot satisfy the fast-growing demand for energy storage technologies. Lithium-sulfur (Li-S) batteries stand out for high energy density (2567 Wh kg-1), low-cost, and environmentally benign attributes. However, the development of Li-S full-batteries is still hindered by the dissolution of polysulfides into the organic electrolytes and poor ions transfer at the interfaces of electrolytes and lithium-intercalated electrodes (e.g., lithiated graphite). Improving the electrolytes is a crucial aspect for the development of battery technologies, but the knowledge concerning the electrolyte microstructures remains elusive. This dissertation unravels the microstructures of organic electrolytes and paves the way to the development of Li-S batteries. Firstly, we demonstrate the key role of electrolyte chemistry in the battery performances by showing a synergetic effect of electrolytes coupled with designed sulfur cathodes. Secondly, we investigate the microstructure of electrolytes and discover previously unexplored solvent-solvent and solvent-anion interactions. We show that the interactions are useful to elucidate important battery operations, such as ions transfer at electrolyte-electrode interfaces, and reveal a potential probe for developing battery electrolytes. Thirdly, we optimize the electrolyte composition to obtain a highly reversible Li+ intercalation/deintercalation at the graphite anode, giving high performances of Li-S full-batteries in a dilute electrolyte concentration. Finally, we unravel the key role of additives in suppressing Li+ solvation in the electrolytes. Nitrate (NO3-) anions are observed to incorporate into the solvation shells, change the local environment of Li+ cations, and then lead to an effective Li+ desolvation followed by improved battery performances. Key significances of this dissertation are (i) observation of detailed electrolyte microstructures showing a potential probe for developing battery electrolytes; (ii) evidences of the electrolyte chemistry plays a predominant role in the electrolyte-electrode interfacial reactions, which prevails over the role of commonly believed solid electrolyte interphase (SEI); and (iii) new mechanistic insights into the key role of additives in the electrolyte microstructures. Furthermore, the presented methodology paves the way for developing electrolytes for broad electrochemical applications.

The main concerns of air travel are the operating costs of general aviation aircraft. Hybrid-electric system design provides a great opportunity for future aircraft models to be environmentally friendly. The Hybrid-electric power propulsion system experienced a growing interest driven by determined targets. Electric technologies have proven promising success to achieve a successful result in the near- and long-term. Combining fuel cells and batteries, this technology can enable a significant reduction in fuel consumption, noise, and emissions. Different types of fuel cells and batteries are proposed and discussed during this work. The Cessna C-172 is a candidate to test the combination of the most promising fuel cells and batteries for a hybridization or complete electrification strategy.

Lithium-ion batteries are leading the path for the power sources for various portable applications, such as laptops and cellular phones, which is due to their relatively high energy density, stable and long cycle life. However, the cost, safety and toxicity issues are restricting the wider application of early generations of lithium-ion batteries. Recently, cheaper and less toxic cathode materials, such as LiFePO₄ and a wide range of derivatives of LiMn₂O₄, have been successfully developed and commercialized. Furthermore, cathode material candidates, such as LiCoPO₄, which present a high redox potential at approximately 4.8 V versus Li⁺/Li, have received attention and are being investigated. However, the theoretical capacity of all of these materials is below 170 mAh g⁻¹, which cannot fully satisfy the requirements of large scale applications, such as hybrid electric vehicles and electric vehicles. Therefore, alternative high energy density and inexpensive cathode materials are needed to make lithium batteries more practical and economically feasible. Elemental sulfur has a theoretical specific capacity of 1672 mAh g⁻¹, which is higher than that of any other known cathode materials for lithium batteries. Sulfur is of abundance in nature (e.g., sulfur is produced as a by-product of oil extraction, and hundreds of millions of tons have been accumulated at the oil extraction sites) and low cost, and this makes it very promising for the next generation of cathode materials for rechargeable batteries. Despite the mentioned advantages, there are several challenges to make the sulfur cathode suitable for battery use, and the following are the main: (i) sulfur has low conductivity, which leads to low sulfur utilization and poor rate capability in the cathode; (ii) multistep electrochemical reduction processes generate various forms of soluble intermediate lithium polysulfides, which dissolve in the electrolyte, induce the so-called shuttle effect, and cause irreversible loss of sulfur active material over repeat cycles; (iii) volume change of sulfur upon cycling leads to its mechanical rupture and, consequently, rapid degradation of the electrochemical performance. A variety of strategies have been developed to improve the discharge capacity, cyclability, and Coulombic efficiency of the sulfur cathode in Li/S batteries. Among those techniques, preparation of sulfur/carbon and sulfur/conductive polymer composites has received considerable attention. Conductive carbon and polymer additives enhance the electrochemical connectivity between active material particles, thereby enhancing the utilization of sulfur and the reversibility of the system, i.e., improving the cell capacity and cyclability. Incorporation of conductive polymers into the sulfur composites provides a barrier to the diffusion of polysulfides, thus providing noticeable improvement in cyclability and hence electrochemical performance. Among the possible conductive polymers, polypyrrole (PPy) is one of the most promising candidates to prepare electrochemically active sulfur composites because PPy has a high electrical conductivity and a wide electrochemical stability window (0-5 V vs Li/Li⁺). In the first part of this thesis, the preparation of a novel nanostructured S/PPy based composites and investigation of their physical and electrochemical properties as a cathode for lithium secondary batteries are reported. An S/PPy composite with highly developed branched structure was obtained by a one-step ball-milling process without heat-treatment. The material exhibited a high initial discharge capacity of 1320 mAh g⁻¹ at a current density of 100 mA g⁻¹ (0.06 C) and retained about 500 mAh g⁻¹ after 40 cycles. Alternatively, in situ polymerization of the pyrrole monomer on the surface of nano-sulfur particles afforded a core-shell structure composite in which sulfur is a core and PPy is a shell. The composite showed an initial discharge capacity of 1199 mAh g⁻¹ at 0.2 C with capacity retention of 913 mAh g⁻¹ after 50 cycles, and of 437 mAh g⁻¹ at 2.5 C. Further improvement of the electrochemical performance was achieved by introducing multi-walled carbon nanotubes (MWNT), which provide a much more effective path for the electron transport, into the S/PPy composite. A novel S/PPy/MWNT ternary composite with a core-shell nano-tubular structure was developed using a two-step preparation method (in situ polymerization of pyrrole on the MWNT surface followed by mixing of the binary composite with nano-sulfur particles). This ternary composite cathode sustained 961 mAh g⁻¹ of reversible specific discharge capacity after 40 cycles at 0.1 C, and 523 mAh g⁻¹ after 40 cycles at 0.5 C. Yet another structure was prepared exploring the large surface area, superior electronic conductivity, and high mechanical flexibility graphene nanosheet (GNS). By taking advantage of both capillary force driven self-assembly of polypyrrole on graphene nanosheets and adhesion ability of polypyrrole to sulfur, an S/PPy/GNS composite with a dual-layered structure was developed. A very high initial discharge capacity of 1416 mAh g⁻¹ and retained a 642 mAh g⁻¹ reversible capacity after 40 cycles at 0.1 C rate. The electrochemical properties of the graphene loaded composite cathode represent a significant improvement in comparison to that exhibited by both the binary S/PPy and the MWCNT containing ternary composites. In the second part of this thesis, polyacrylonitrile (PAN) was investigated as a candidate to composite with sulfur to prepare high performance cathodes for Li/S battery. Unlike polypyrrole, which, in addition of being a conductive matrix, works as physical barrier for blocking polysulfides, PAN could react with sulfur to form inter- and/or intra-chain disulfide bonds, chemically confining sulfur and polysulfides. In the preliminary tests, PAN was ballmilled with an excess of elemental sulfur and the resulting mixture was heated at temperatures varying from 300°C to 350°C. During this step some H₂S gas was released as a result of the formation of rings with a conjugated π-system between sulfur and polymer backbone. These cyclic structures could ‘trap’ some of the soluble reaction products, improving the utilization of sulfur, as it was observed experimentally: the resulting S/PAN composite demonstrated a high sulfur utilization, large initial capacity, and high Coulombic efficiency. However, the poor electronic conductivity of the S/PAN binary composite compromises the rate capability and sulfur utilization at high C-rates. These issues were addressed by doping the composite with small amounts of components that positively affected the conductivity and reactivity of the cathode. Mg₀.₆Ni₀.₄O prepared by self-propagating high temperature synthesis was used as an additive in the S/PAN composite cathode and considerably improved its morphology stability, chemical uniformity, and electrochemical performance. The nanostructured composite containing Mg₀.₆Ni₀.₄O exhibited less sulfur agglomeration upon cycling, enhanced cathode utilization, improved rate capability, and superior reversibility, with a second cycle discharge capacity of over 1200 mAh g⁻¹, which was retained for over 100 cycles. Alternatively, graphene was used as conductive additive to form an S/PAN/Graphene composite with a well-connected conductive network structure. This ternary composite was prepared by ballmilling followed by low temperature heat treatment. The resulting material exhibited significantly improved rate capability and cycling performance delivering a discharge capacity of 1293 mAh g⁻¹ in the second cycle at 0.1 C. Even at up to 4 C, the cell still achieved a high discharge capacity of 762 mAh g⁻¹. Different approaches for the optimization of sulfur-based composite cathodes are described in this thesis. Experimental results indicate that the proposed methods constitute an important contribution in the development of the high capacity cathode for rechargeable Li/S battery technology. Furthermore, the innovative concept of sulfur/conductive polymer/conductive carbon ternary composites developed in this work could be used to prepare many other analogous composites, such as sulfur/polyaniline/carbon nanotube or sulfur/polythiophene/graphene, which could also lead to the development of new sulfur-based composites for high energy density applications. In particular, exploration of alternative polymeric matrices with high sulfur absorption ability is of importance for the attainment of composites that possess higher loading of sulfur, to increase the specific energy density of the cathode. Note that the material preparation techniques described here have the advantage of being reproducible, simple and inexpensive, compared with most procedures reported in the literature.

This thesis was devised as a fundamental study of the Li-S system by the use of 7Li Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR), X-ray Absorption Near-Edge Structure (XANES), and Non-Resonant Inelastic X-ray Scattering (NRIXS). The first part of this thesis is dedicated to the synthesis of solid state linear chain polysulfides in order to use them as reference compounds in the following experiments. 7Li NMR shows that Li2S and Li2S6 exhibit single but different Li environments, while the others stoichiometry targeted consist of a mixture of them. This is the first report of a stable solid-phase intermediate between elemental sulfur (α-S8) and Li2S. The second part of this thesis is based on operando XANES measurements made in the Argonne Photon Source (APS). Linear combination fit (LCF) analyses are performed to interpret the data; and, noticeably, the distinction between short-chain and long-chain polysulfides can be made due to the use of proper reference materials. The results reveal the first detailed observation of typical sulfur redox chemistry upon cycling, showing how sulfur fraction (under-utilization) and sulfide precipitation impact capacity. It also gives new insights into the differences between the charge and discharge mechanisms, resulting in the hysteresis of the cycling profile. Heat-treated PCNS/S exhibits a particular electrochemical signature, which has never explained. Operando XANES measurements at the sulfur K-edge are performed on heat-treated PCNS. Noticeably, the difference in the XANES signatures of the pristine and the recharged state shows the irreversible process that occurs during the first discharges. At last, electrolytes are investigated by the compilation of quantitative physico-chemical parameters on novel class of solvents that are glymes with non-polar groups and acetonitrile (ACN) complexed with LiTFSI. (ACN)2:LiTFSI attracts particular attention because of the particularly low Li2Sn solubility and. Its good electrochemical performance when mixed with 50 vol% HFE. Operando XANES proves the formation of polysulfides in this electrolyte, and the low energy feature evolution shows a more progressive mechanism involved in this electrolyte, which could be linked to the particularly low Li2Sn solubility.