Sodium-ion batteries (SIBs) are rechargeable batteries analogous to lithium-ion batteries but use sodium ions (Na+) as the charge carriers. They are considered a promising alternative for lithium-ion batteries (LIBs) in renewable large-scale energy storage applications due to their similar electrochemical mechanisms and abundant sodium resources. Two-dimensional (2D) materials, with atomic or molecular thickness and large lateral lengths, have emerged as important functional materials due to their unique structures and excellent properties. These 2D nanosheets have been highly studied as sodium-ion battery anodes. They have large interlayer spacing, which can effectively buffer the big volume expansion and prevent electrode collapse during the charge-discharge process. Different strategies such as preparing composites, heterostructures, expanded structures, and chemical functionalization can greatly improve cycling stability and lead to high reversible capacity. In this dissertation, state-of-the-art SIB based on 2D material electrodes will be presented. In particular, Tin-based 2D materials and laser-scribed graphene anodes are discussed. Different strategies involving engineering both synthesis methods, intrinsic properties of materials, and device architecture are used to optimize the battery performance.

Philosophiae Doctor - PhD / With the rapid rise in energy demand and ever-escalating environmental hazards, the need for transition from fossil fuel to renewable energy sources is of paramount importance, requiring better and efficient energy storage devices such as supercapacitors. Supercapacitors are energy storage devices with high power density and long cycle life, but relatively low energy density when compared to batteries. New and advanced electrode materials are required to improve the energy density requirements of next-generation supercapacitors. However, the search for new types of active materials to be used as supercapacitors' electrodes continues to be a tough challenge. Herein, ruthenium antimony oxide (RuSbO) and ruthenium antimony oxide graphene (RuSbO-G) were synthesized via the microwave-assisted method for the first time and tested as a possible electrode material for an asymmetric supercapacitor. Graphene oxide prepared by modified Hummer’s method was exfoliated at low temperature and used for the synthesis of RuSbO-G. / 2025

With the growing global population comes the ever-increasing consumption of energy in powering cities, electric vehicles, and portable devices such as cell-phones. While the power grid is used to distribute energy to consumers, the energy sources needed to power the grid itself are unsustainable and inefficient. The primary energy sources powering the grid, being fossil fuels, natural gas, and nuclear, are unsustainable as the economically-accessible reserves are continually depleted in exchange for detrimental emissions and air-pollutants. Cleaner, renewable sources, such as solar, wind, and hydroelectric, are intermittent and unreliable during the peak hours of energy usage, that is dawn and dusk. However, during waking hours and nighttime sleeping hours, energy consumption plummets resulting in substantial losses of potential energy as these intermittent energy providers do not have the infrastructure to store unused energy. Therefore, the research and development of efficient energy storage materials and renewable energy sources is critical to meet the needs of society in their fundamental operation while reducing harmful emissions. The research presented in this thesis focuses on selected energy storage materials and electrocatalysts as attractive technology for sustainable and benign renewable energy chemistry. Specifically, (1) theoretical studies on magnesium chloride / aluminum chloride electrolytes provide insight for further development of Mg batteries; (2) theoretical and experimental studies on viologen derivatives for organic redox flow batteries advance the development of these two-electron storage systems; and (3) a new iron(II) polypyridine catalyst that was found to electrochemically reduce CO2 to produce renewable fuels such as carbon monoxide (CO), hydrogen (H2), and methane (CH4), as well as promote the photochemical CO2-to-methane conversion with visible light.

Rechargeable lithium ion batteries (LIBs) have long been used to power not only portable devices, e.g., mobile phones and laptops, but also large scale systems, e.g., electrical grid and electric vehicles. To meet the ever increasing demand for renewable energy storage, tremendous efforts have been devoted to improving the energy/power density of LIBs. Known for its high theoretical capacity (4200 mAh/g), silicon has been considered as one of the most promising negative electrode materials for high-energy-density LIBs. However, diffusion-induced stresses can cause fracture and, consequently, rapid degradation in the electrochemical performance of Si-based negative electrodes. To mitigate the detrimental effects of the large volume change, several strategies have been proposed. This dissertation focuses on two promising approaches to make high performance and durable Si electrodes for high capacity LIBs. First, the effect of polymeric binders on the performance of Si-based electrodes is investigated. By studying two types of polymeric binders, polyvinylidene fluoride (PVDF) and sodium alginate (SA) using peel tests, SEM, XPS, and FTIR, I show that the high cohesive strength at the binder-silicon interface is responsible for the superior cell performance of the Si electrodes with SA as a binder. Hydrogen bonds formed between SA and Si is the main reason for the high cohesive strength since neither PVDF nor SA bonds covalently with Si. Second, the fabrication of high performance Si/polyacrylonitrile (PAN) composite electrode via oxidative pyrolysis is investigated. We show that high performance Si/polyacrylonitrile (PAN) composite negative electrodes can be fabricated by a robust heat treatment in air at a temperature between 250 and 400oC. Using Raman, SEM, XPS, TEM, TGA, and nanoindention, we established that oxidation, dehydration, aromatization, and intermolecular crosslinking take place in PAN during the heat treatment, resulting in a stable cyclized structure which functions as both a binder and a conductive agent in the Si/PAN composite electrodes. With a Si mass loading of 1 mg/cm2, a discharge capacity of ~1600 mAh/g at the 100th cycle is observed in the 400oC treated Si/PAN composite electrode when cycled at a rate of C/3. These studies on the structure-property-performance relations of Si based negative electrode may benefit the LIB community by providing (1) a guide for the design and optimization of binder materials for Si electrodes and (2) a facile method of synthesizing Si-based composite negative electrodes that can potentially be applied to other Si/polymer systems for further increasing the power/energy density and lower the cost of LIBs for electric vehicle applications and beyond.

Indiana University-Purdue University Indianapolis (IUPUI) / Rechargeable lithium ion batteries are widely used in portable consumer electronics such as cellphones, laptops, etc. These batteries are capable to provide high energy density with no memory effect and they have small self-discharge when they are not in use, which increases their potential for future electric vehicles. Investigators are attempting to improve the performance of these cells by focusing on the energy density, cost, safety, and durability. The energy density improves with high operation voltage and high capacity. Before any further development of high voltage materials, safe electrolytes with high ionic conductivity, wide electrochemical window, and high stability with both electrodes need to be developed. In this thesis a new strategy was investigated to develop electrolytes that can contribute to the further development of battery technology. The first study is focused on preparing a hybrid electrolyte, the combination of inorganic solid and organic liquid, for lithium based rechargeable batteries to illustrate the effect of electrode/electrolyte interfacing on electrochemical performance. This system behaves as a self-safety device at higher temperatures and provides better performance in comparison with the solid electrolyte cell, and it is also competitive with the pure liquid electrolyte cell. Then a multilayer electrolyte cell (MEC) was designed and developed as a new tool for investigating electrode/electrolyte interfacial reactions in a battery system. The MEC consists of two liquid electrolytes (L.E.) separated by a solid electrolyte (S.E.) which prevents electrolyte crossover while selectively transporting Li+ ions. The MEC successfully reproduced the performance of LiFePO4 comparable with that obtained from coin cells. In addition, the origin of capacity fading in LiNi0.5Mn1.5O4full-cell (with graphite negative electrode) was studied using the MEC. The performance of LiNi0.5Mn1.5O4 MEC full-cell was superior to that of coin full-cell by eliminating the Mn dissolution problem on graphite negative electrode as evidenced by transmission electron microscopy (TEM) analysis. The MEC can be a strong tool for identifying the electrochemical performances of future high voltage positive electrode materials and their electrode/electrolyte interfacial reactions. Finally, by employing the multilayer electrolyte concept, a new application will be introduced to recycle the lithium. This study demonstrates the feasibility of using water and the contents of waste Li-ion batteries for the electrodes in a Li-liquid battery system. Li metal was collected electrochemically from a waste Li-ion battery containing Li-ion source materials from the battery’s anode, cathode, and electrolyte, thereby recycling the Li contained in the waste battery at the room temperature.

Indiana University-Purdue University Indianapolis (IUPUI) / Due to the drastic increase in the cost of fossil fuels and other environmental issues, the demand for energy and its storage has risen globally. Rather than being dependent on intermittent energy sources like wind and solar energy, focus has been on alternative energy sources. To eliminate the need for fossil fuels, advances are being made to provide energy for hybrid electric vehicles (HEV), plug-in hybrid vehicles (PHEV) and pure electric vehicles (EV) thus providing scope for much greener environment. Hence, focus has been on development in lithium ion batteries to provide with materials that have high energy density and voltage. Ortho olivine lithium transitional metals are known to be abundant and inexpensive; these compounds are less noxious than other cathode materials. Advancement in research is being done in finding iron and manganese compounds as cathode materials for advanced technologies. However, Lithium manganese phosphates are known to suffer with poor electrochemical performances due the manganese dissolution in the organic liquid electrolyte due to Jahn-Teller Lattice distortion. This problem was tried to endorse in this thesis. In the second chapter by synthesizing nano sized cathode particles with good electronic conductivity, good performance was achieved. In the third chapter additive olivine cathode was synthesized my modified sol gel process. A wt. % of TMSP was added as an additive in the organic liquid electrolyte. By comparing the properties between the two kinds of electrolytes it was observed that by the addition of the additive in the organic electrolyte good electrochemical properties could be achieved hindering the Mn dissolution in the electrolyte. In the final chapter, a composite solid electrolyte was fabricated by using NASICON-type glass ceramic of Lithium aluminum titanium phosphate (LATP) with organic binder of Polyethylene oxide. The flexible solid electrolyte exhibited good ionic conductivity. An all solid state cell was fabricated using the composite solid electrolyte using LiMn2O4 as the symmetric electrodes. At different pressures, the performance of the solid state cell was studied.

Indiana University-Purdue University Indianapolis (IUPUI) / Heat generation is a major safety concern in the design and development of Li ion batteries (LIBs) for large scale applications, such as electric vehicles. The total heat generation in LIBs includes entropic heat, enthalpy, reaction heat, and heat of mixing. The main objective of this study is to investigate the influence of heat of mixing on the LIBs and to understand whether it is necessary to consider the heat of mixing during the design and development of LIBs. In the previous research, Thomas and Newman derived methods to compute heat of mixing in LIB cells. Their results show that the heat of mixing cannot be neglected in comparison with the other heat sources at 2 C rate. In this study, the heat of mixing in different materials, porosity, particle sizes, and charging/discharging rate was investigated. A COMSOL mathematical model was built to simulate the heat generation of LIBs. The LIB model was based on Newman’s model. LiMn2O4 and LiCoO2 were applied as the cathode materials, and LiC6 was applied as the anode material. The results of heat of mixing were compared with the other heat sources to investigate the weight of heat of mixing in the total heat generation. The heat of mixing in cathode is smaller than the heat of mixing in anode, because of the diffusivity of LiCoO2 is 1 ×10-13 m2/s, which is larger than LiC6's diffusivity 2.52 × 10-14 m2/s. In the comparison, the heat of mixing is not as much as the irreversible heat and reversible heat, but it still cannot be neglected. Finally, a special situation will be discussed, which is the heat of mixing under the relaxation status. For instance, after the drivers turn off their vehicles, the entropy, ix enthalpy and reaction heat in LIBs will stop generating, but the heat will still be generated due to the release of heat of mixing. Therefore, it is meaningful to investigate to see if this process has significant influence on the safety and cycle life of LIBs.

Indiana University-Purdue University Indianapolis (IUPUI) / Developing alternative cathodes with high capacity is critical for the next generation rechargeable batteries to meet the ever-increasing desires of global energy storage market. This thesis is focused on two sulfur-based cathode materials ranging from inorganic lithium sulfide to organotrisulfide. For lithium sulfide cathode, we developed a nano-Li2S/MWCNT paper electrode through solution filtration method, which involved a low temperature of 100 °C. The Li2S nanocrystals with a size less than 10 nm were formed uniformly in the pores of carbon paper network. These electrodes show an unprecedented low overpotential (0.1 V) in the first charges, also show high discharge capacities, good rate capability, and excellent cycling performance. This superior electrochemical performance makes them promising for use with lithium metal-free anodes in rechargeable Li–S batteries for practical applications. For organotrisulfide cathode, we use a small organotrisulfide compound, e.g. dimethyl trisulfide, to be a high capacity and high specific energy organosulfide cathode material for rechargeable lithium batteries. Based on XRD, XPS, SEM, and GC-MS analysis, we investigated the cell reaction mechanism. The redox reaction of DMTS is a 4e- process and the major discharge products are LiSCH3 and Li2S. The following cell reaction becomes quite complicated, apart from the major product DMTS, the high order organic polysulfide dimethyl tetrasulfide (DMTtS) and low order organic polysulfide dimethyl disulfide (DMDS) are also formed and charged/discharged in the following cycles. With a LiNO3 containing ether-based electrolyte, DMTS cell delivers an initial discharge capacity of 720 mAh g-1 and retains 74% of the initial capacity over 70 cycles with high DMTS loading of 6.7 mg cm-2 at C/10 rate. When the DMTS loading is increased to 11.3 mg cm-2, the specific energy is 1025 Wh kg-1 for the active materials (DMTS and lithium) and the specific energy is 229 Wh kg-1 for the cell including electrolyte. Adjusting on the organic group R in the organotrisulfide can achieve a group of high capacity cathode materials for rechargeable lithium batteries.

West Lafayette; Indiana University-Purdue University Indianapolis (IUPUI) / Lithium-ion batteries (LIBs) are commonly and widely applied in current numerous devices such as smart phones, laptops, electric vehicles and medical devices. The LIBs are considered as a mature technology in todays commercial market bene ted from their uncomplicated lithium intercalation and de-intercalation reactions, stable cycling performance and good working life as energy storage devices and power resources. However, the conventional LIBs with technical limits such as high weight, low lithium utilization and low speci c energy density hit the bottlenecks of further improvements and optimizations for meeting the growing power supply requirements. It is urgent to develop the second generations of rechargeable lithium batteries, which have the bene ts of low cost, high speci c capacity and high energy density with light weight. In this context, lithium-sulfur batteries (LSBs) and lithium-selenium (Li-Se) batteries attract much attention due to the high possibility to meet the requirements of high speci c capacity and high energy density. However, the technical challenges they are facing put some barriers before they can be successfully commercialized. By a brief summary, the challenges to be solved are current low energy density because of requiring large amount of liquid electrolyte, the highly ammability and unsafety of lithium metal, low active material content due to the necessary requirement of carbon and binder, and severe so-called shuttle effect resulting in low Coulombic effciency. Before solving these challenges, Li-S batteries or Li-Se batteries are unlikely to be successfully commercialized in our market. Therefore, numerous research is aimed at solving the challenges and further developing more advanced Li-S and Li-Se battery systems. In the present dissertation, the contributions are mainly focused on sulfur-based and selenium-based materials, which aim to solve the current existing challenges and improve the battery performance, herein obtain a higher potential for application. Four chapters are included in this dissertation, which aim to present the four studied projects. The rst research conducted in this dissertation is developing organo S/Se hybrid materials which require low E/S ratios of liquid electrolyte and show light shuttle effect, therefore indicate promising high energy density and cycling life. Secondly, the tin foil is used as lithium sources instead of metallic lithium anode, then incorporated with sulfur cathode as a full cell. The full cell design provides the potential using a metallic anode other than pure lithium and increase the safety factor of a battery system. In addition, nano-scale selenium/carbon nanotubes composite electrode is synthesized via a chemical reduction method. With the optimization on thickness of the composite electrodes, the Se cathode has an active material content of ~60% and shows stable long cycling life with maximizing the utilization of selenium. The nal research conducted in this dissertation is applying a macro molecule named cyanostar, which has the ability to chemically bind with polysul de species, thereupon to alleviate the shuttle effect in Li-S batteries. With the evidence from chemistry analysis and electrochemical comparison results presented in this dissertation, cyanostar is proven to have the potential for further applications in Li-S batteries.

Indiana University-Purdue University Indianapolis (IUPUI) / Electrospinning has gained immense interests in recent years due to its potential application in various fields, including energy storage application. The V2O5/GO as a layered crystal structure has been demonstrated to fabricate nanofibers with diameters within a range of ~300nm through electrospinning technique. The porous, hollow, and interconnected nanostructures were produced by electrospinning formed by polymers such as Polyvinylpyrrolidone (PVP) and Polyvinyl alcohol (PVA), separately, as solvent polymers with electrospinning technique. In this study, we investigated the synthesis of a graphene-modified nanostructured V2O5 through modified sol-gel method and electrospinning of V2O5/GO hybrid. Electrochemical characterization was performed by utilizing Arbin Battery cycler, Field Emission Scanning Electron Microscopy (FESEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TGA), Mercury Porosimetry, and BET surface area measurement. As compared to the other conventional fabrication methods, our optimized sol-gel method, followed by the electrospinning of the cathode material achieved a high initial capacity of 342 mAh/g at a high current density of 0.5C (171 mA/g) and the capacity retention of 80% after 20 cycles. Also, the prepared sol-gel method outperforms the pure V2O5 cathode material, by obtaining the capacity almost two times higher. The results of this study showed that post-synthesis treatment of cathode material plays a prominent role in electrochemical performance of the nanostructured vanadium oxides. By controlling the annealing and drying steps, and time, a small amount of pyrolysis carbon can be retained, which improves the conductivity of the V2O5 nanorods. Also, controlled post-synthesis helped us to prevent aggregation of electro-spun twisted nanostructured fibers which deteriorates the lithium diffusion process during charge/discharge of batteries.