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) / The prevalent applications of energy storage devices have incited wide-spread efforts on production of thin, flexible, and light-weight lithium-ion batteries. In this work, lithium-ion batteries using novel flexible paper-based current collectors have been developed. The paper-based current collectors were fabricated from carbon nanotube (CNT)-coated wood microfibers (CNT-microfiber paper). This thesis presents the fabrication of the CNT-microfiber paper using wood microfibers, coating electrode materials, design and assemblies of battery, testing methodologies, and experimental results and analyses. Wood microfibers were coated with carbon nanotubes and poly(3,4-ethylenedioxythiophene) (PEDOT) through an electrostatic layer-by-layer nanoassembely process and formed into a sheet, CNT-microfiber paper. The CNT loading of the fabricated paper was measured 10.1 μg/cm2 subsequently considered. Electrode material solutions were spray-coated on the CNT-microfiber paper to produce electrodes for the half and full-cell devices. The CNT current collector consists of a network structure of cellulose microfibers at the micro-scale, with micro-pores filled with the applied conductive electrode materials reducing the overall internal resistance for the cell. A bending test revealed that the paper-based electrodes, compared to metal ones, incurred fewer damages after 20 bends at an angle of 300o. The surface fractures on the paper-based electrodes were shallow and contained than metallic-based electrodes. The micro-pores in CNT-microfiber paper structure provides better adherence to the active material layer to the substrate and inhibits detachment while bending. Half-cells and full-cells using lithium cobalt oxide (LCO), lithium titanium oxide (LTO), and lithium magnesium oxide (LMO) were fabricated and tested. Coin cell assembly and liquid electrolyte was used. The capacities of half-cells were measured 150 mAh/g with LCO, 158 mAh/g with LTO, and 130 mAh/g with LMO. The capacity of the LTO/LCO full-cell also was measured 126 mAh/g at C/5 rate. The columbic efficiency of the LTO/LCO full-cell was measured 84% for the first charging cycle that increased to 96% after second cycle. The self-discharge test of the full-cell after charging to 2.7 V at C/5 current rate is showed a stable 2 V after 90 hours. The capacities of the developed batteries at lower currents are comparable to the metallic electrode-based devices, however, the capacities were observed to drop at higher currents. This makes the developed paper-based batteries more suitable for low current applications, such as, RFID tags, flexible electronics, bioassays, and displays. The capacities of the batteries at higher current can be improved by enhancing the conductivity of the fibers, which is identified as the future work. Furthermore, fabrication of an all solid state battery using solid electrolyte is also identified as the future work of this project.

Indiana University-Purdue University Indianapolis (IUPUI) / Since 1990s, rechargeable Li-ion batteries have been widely used in consumer electronics such as cell phones, global positioning systems (GPS), personnel digital assistants (PDA), digital cameras, and laptop computers. Recently Li-ion batteries received considerable attention as a major power source for electric vehicles. However, significant technical challenges still exist for widely deploying Li-ion batteries in electric vehicles. For instance, the energy density of Li-ion batteries is not high enough to support a long-distance commute. The Li-ion batteries used for the Nissan Leaf and Chevy Volt only can support 50 – 100 miles per charge. The cost of Li-ion battery packs in electric vehicles is still high. The battery pack for the Chevy Volt costs about $8,000, and the larger one in the Nissan Leaf costs about $12,000. To address these problems, new Li-ion battery electrode materials with high energy density and low cost should be developed. Among Li-ion battery cathode materials, vanadium pentoxide, V2O5, is one of the earliest oxides studied as a cathode for Li-ion batteries because of its low cost, abundance, easy synthesis, and high energy density. However, its practical reversible capacity has been limited due to its irreversible structural change when Li insertion is more than x = 1. Tremendous efforts have been made over the last twenty years to improve the phase reversibility of LixV2O5 (e.g., 0 ≤ x ≤ 2) because of vanadium pentoxides’ potential use as high capacity cathodes in Li-ion batteries. In this thesis, a new strategy was studied to develop vanadium pentoxide cathode materials with improved phase reversibility. The first study is to synthesize vanadium oxide cathodes via a new chemical route – creating a phase transformation from the vanadium sulfide to oxide. The β-Na0.33V2O5 was prepared via a new method of chemical synthesis, involving the chemical transformation of NaVS2 via heat-treatment at 600 °C in atmospheric air. The β-Na0.33V2O5 particles were well crystalized and rod-shaped, measuring 7–15 μm long and 1–3 μm wide with the formation of the crystal defects on the surface of the particles. In contrast to previous reports contained in the literature, Na ions were extracted, without any structural collapse, from the β -Na0.33V2O5 structure and replaced with Li ions during cycling of the cell in the voltage range, 1.5 V to 4.5 V. This eventually resulted in a fully reversible Li intercalation into the LixV2O5 structure when 0.0 ≤ x ≤ 2.0. The second study is to apply the synthesis method to LiVS2 for the synthesis of β׳-LixV2O5 for use as a high performance cathode. The synthesis method is based on the heat treatment of the pure LiVS2 in atmospheric air. By employing this method of synthesis, well-crystalized, rod-shaped β׳-LixV2O5 particles 20 – 30 μm in length and 3 – 6 μm in width were obtained. Moreover, the surface of β׳-LixV2O5 particles was found to be coated by an amorphous vanadium oxysulfide film (~20 nm in thickness). In contrast to a low temperature vanadium pentoxide phase (LixV2O5), the electrochemical intercalation of lithium into the β׳-LixV2O5 was fully reversible where 0.0 < x < 2.0, and it delivered a capacity of 310 mAh/g at a current rate of 0.07 C between 1.5 V and 4 V. Good capacity retention of more than 88% was also observed after 50 cycles even at a higher current rate of 2 C. The third study is the investigation of NaVS2 as a cathode intercalation material for sodium ion batteries. We have shown that reversible electrochemical deintercalation of x ~ 1.0 Na per formula unit of NaxVS2, corresponding to a capacity of ~200 mAh/g, is possible. And a stable capacity of ~120 mAh/g after 30 cycles was observed. These studies show that the new chemical synthesis route for creating a phase transformation from the vanadium sulfide to oxide by heat treatment in air is a promising method for preparing vanadium oxide cathode material with high reversibility. Although this sample shows a relatively low voltage range compared with other cathodes such as LiCoO2 (3.8 V) and LiFePO4 (3.4 V), the large capacity of this sample is quite attractive in terms of increasing energy density in Li-ion batteries. Also, NaVS2 could be a promising cathode material for sodium ion batteries.

Indiana University-Purdue University Indianapolis (IUPUI) / Lithium ion (Li-ion) batteries have become integral parts of our lives; they are widely used in applications like handheld consumer products, automotive systems, and power tools among others. To extract maximum output from a Li-ion battery under optimal conditions it is imperative to have access to the state of the battery under every operating condition. Faults occurring in the battery when left unchecked can lead to irreversible, and under extreme conditions, catastrophic damage. In this thesis, an adaptive fault diagnosis technique is developed for Li-ion batteries. For the purpose of fault diagnosis the battery is modeled by using lumped electrical elements under the equivalent circuit paradigm. The model takes into account much of the electro-chemical phenomenon while keeping the computational effort at the minimum. The diagnosis process consists of multiple models representing the various conditions of the battery. A bank of observers is used to estimate the output of each model; the estimated output is compared with the measurement for generating residual signals. These residuals are then used in the multiple model adaptive estimation (MMAE) technique for generating probabilities and for detecting the signature faults. The effectiveness of the fault detection and identification process is also dependent on the model uncertainties caused by the battery modeling process. The diagnosis performance is compared for both the linear and nonlinear battery models. The non-linear battery model better captures the actual system dynamics and results in considerable improvement and hence robust battery fault diagnosis in real time. Furthermore, it is shown that the non-linear battery model enables precise battery condition monitoring in different degrees of over-discharge.

Indiana University-Purdue University Indianapolis (IUPUI) / There is a strong urge for advanced diagnosis method, especially in high power battery packs and high energy density cell design applications, such as electric vehicle (EV) and hybrid electric vehicle segment, due to safety concerns. Accurate and robust diagnosis methods are required in order to optimize battery charge utilization and improve EV range. Battery faults cause significant model parameter variation affecting battery internal states and output. This work is focused on developing diagnosis method to reliably detect various faults inside lithium-ion cell using electrochemical model based observer and fuzzy logic algorithm, which is implementable in real-time. The internal states and outputs from battery plant model were compared against those from the electrochemical model based observer to generate the residuals. These residuals and states were further used in a fuzzy logic based residual evaluation algorithm in order to detect the battery faults. Simulation results show that the proposed methodology is able to detect various fault types including overcharge, over-discharge and aged battery quickly and reliably, thus providing an effective and accurate way of diagnosing li-ion battery faults.