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 batteries are widely used for portable electronics due to high energy density, mature processing technology and reduced cost. However, their applications are somewhat limited by safety concerns. The lithium-ion battery users will take risks in burn or explosion which results from some internal components failure. So, a practical method is required urgently to find out the failures in early time. In this thesis, a new method based on temperature difference between internal point and surface (TDIS) of the battery is developed to detect the thermal failure especially the thermal runaway in early time. A lumped simple thermal model of a lithium-ion battery is developed based on TDIS. Heat transfer coefficients and heat capacity are determined from simultaneous measurements of the surface temperature and the internal temperature in cyclic constant current charging/discharging test. A look-up table of heating power in lithium ion battery is developed based on the lumped model and cyclic charging/discharging experimental results in normal operating condition. A failure detector is also built based on TDIS and reference heating power curve from the look-up table to detect aberrant heating power and bad parameters in transfer function of the lumped model. The TDIS method and TDIS detector is validated to be effective in thermal runaway detection in a thermal runway experiment. In the validation of thermal runway test, the system can find the abnormal heat generation before thermal runaway happens by detecting both abnormal heating power generation and parameter change in transfer function of thermal model of lithium ion batteries. The result of validation is compatible with the expectation of detector design. A simple and applicable detector is developed for lithium ion battery catastrophic failure detection.

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.