Electrical & Computer Engineering
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Item MEMS SENSOR PLATFORMS FOR IN SITU CHARACTERIZATION OF LI-ION BATTERY ELECTRODES(2016) Jung, Hyun; Ghodssi, Reza; Electrical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Lithium-ion batteries provide high energy density while being compact and light-weight and are the most pervasive energy storage technology powering portable electronic devices such as smartphones, laptops, and tablet PCs. Considerable efforts have been made to develop new electrode materials with ever higher capacity, while being able to maintain long cycle life. A key challenge in those efforts has been characterizing and understanding these materials during battery operation. While it is generally accepted that the repeated strain/stress cycles play a role in long-term battery degradation, the detailed mechanisms creating these mechanical effects and the damage they create still remain unclear. Therefore, development of techniques which are capable of capturing in real time the microstructural changes and the associated stress during operation are crucial for unravelling lithium-ion battery degradation mechanisms and further improving lithium-ion battery performance. This dissertation presents the development of two microelectromechanical systems sensor platforms for in situ characterization of stress and microstructural changes in thin film lithium-ion battery electrodes, which can be leveraged as a characterization platform for advancing battery performance. First, a Fabry-Perot microelectromechanical systems sensor based in situ characterization platform is developed which allows simultaneous measurement of microstructural changes using Raman spectroscopy in parallel with qualitative stress changes via optical interferometry. Evolutions in the microstructure creating a Raman shift from 145 cm−1 to 154 cm−1 and stress in the various crystal phases in the LixV2O5 system are observed, including both reversible and irreversible phase transitions. Also, a unique way of controlling electrochemically-driven stress and stress gradient in lithium-ion battery electrodes is demonstrated using the Fabry-Perot microelectromechanical systems sensor integrated with an optical measurement setup. By stacking alternately stressed layers, the average stress in the stacked electrode is greatly reduced by 75% compared to an unmodified electrode. After 2,000 discharge-charge cycles, the stacked electrodes retain only 83% of their maximum capacity while unmodified electrodes retain 91%, illuminating the importance of the stress gradient within the electrode. Second, a buckled membrane microelectromechanical systems sensor is developed to enable in situ characterization of quantitative stress and microstructure evolutions in a V2O5 lithium-ion battery cathode by integrating atomic force microscopy and Raman spectroscopy. Using dual-mode measurements in the voltage range of the voltage range of 2.8V – 3.5V, both the induced stress (~ 40 MPa) and Raman intensity changes due to lithium cycling are observed. Upon lithium insertion, tensile stress in the V2O5 increases gradually until the α- to ε-phase and ε- to δ-phase transitions occur. The Raman intensity change at 148 cm−1 shows that the level of disorder increases during lithium insertion and progressively recovers the V2O5 lattice during lithium extraction. Results are in good agreement with the expected mechanical behavior and disorder change in V2O5, highlighting the potential of microelectromechanical systems as enabling tools for advanced scientific investigations. The work presented here will be eventually utilized for optimization of thin film battery electrode performance by achieving fundamental understanding of how stress and microstructural changes are correlated, which will also provide valuable insight into a battery performance degradation mechanism.Item Characterization of Linear Electro-Optic Effect of Poled Organic Thin Films(2008-02-29) Park, Dong Hun; Lee, Chi H; Herman, Warren N; Electrical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The goal of this thesis is to re-evaluate both Teng-Man and attenuated total reflection (ATR) methods for measuring the linear electro-optic (EO) coefficients of poled organic thin films based on a multilayer structure containing a transparent conducting oxide (TCO) layer. The linear EO properties are often characterized using the Teng-Man reflection method. However, it has been reported that experimental error can result from ignoring multiple reflections and that an accurate determination of the EO effect could be achieved only by a numerical calculation that applies anisotropic Fresnel equations to the multilayer structure. We present new closed-form expressions for analysis of Teng-Man measurements of the EO coefficients of poled polymer thin films. These expressions account for multiple reflection effects using a rigorous analysis of the multilayered structure for varying angles of incidence. The analysis based on plane waves is applicable to both transparent and absorptive films and takes into account the properties of the TCO electrode layer and buffer layers. Methods for fitting data are presented and the error introduced by ignoring the TCO layer and multiple reflections is discussed. We also discuss the effect of Gaussian beam optics and the suitability of a thick z-cut LiNbO3 crystal as a reference to validate the Teng-Man measurement. Simply taking the metal electrode off the Teng-Man sample makes it feasible to use the ATR method using a metal-coated prism. This technique has the capability of measuring anisotropic indices of refraction along with film thicknesses. In addition, it enables measurement of r13 and r33 separately without an assumption for the ratio of r13 to r33 as required in the Teng-Man method. We have found that the ATR analysis based on a three-layer waveguide structure (air/film/substrate) can produce a large error especially when the film supports a single guided mode and the ATR analysis based on a multilayer structure containing a TCO layer gives you a more reliable estimation. We discuss the error introduced by using the three-layer waveguide structure and compare to using the multilayer structure. Finally, we discuss the characterization of the optical property of TCO's using ellipsometeric analysis, which is required for both the rigorous Teng-Man and ATR analysis. Representative experimental results showing that the result from the ATR method based on the multilayer structure shows a good agreement with that from the rigorous Teng-Man analysis are presented. We have measured a very high linear electro-optic coefficient (r33=350 pm/V) from a NLO film (AJ-TTE-II, synthesized by Alex Jen's group at University of Washington) at 1310 nm wavelength, which is ~12 times higher than the best inorganic electro-optic crystal LiNbO3.