@phdthesis{Macher2021,
  author    = {Macher, Sven},
  title     = {On the Effects of Moisture on Polymer-Based Electrochromic Devices},
  doi       = {10.25972/OPUS-24240},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-242407},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2021},
  abstract  = {The present work builds on a conjugated electrochromic polymer with a highly transmissive and colorless bright state and its application in electrochromic devices. The main body of this work focuses on the investigation of the influence of moisture on electrochromic devices and solutions to overcome possible degradation of these devices due to moisture ingress. Firstly, a series of EDOT derivatives with a terminal double bond in the lateral sidechain to potentially achieve a highly transmissive and fully colorless bright state was investigated. All of the EDOT derivatives were electrochemically polymerized and characterized by means of (in-situ) spectroelectrochemistry. The results highlight the dramatic influence of the terminal double bond on the improved visible light transmittance and color neutrality in the bright state. After detailed evaluation and comparison, the best performing compound, which contains a hexenyl sidechain (PEDOT-EthC6), was scaled-up by changing the deposition technique from an electrochemical to a chemical in-situ polymerization process on a R2R-pilot line in an industrially relevant environment. The R2R-processed PEDOTEthC6 half-cells were characterized in detail and provide enhanced electrochromic properties in terms of visible light transmittance and color neutrality in the bright state as well as short response times, improved contrast ratio, coloration efficiency and cycling stability (10 000 cycles).[21] In a second step, the novel PEDOT-EthC6 electrochromic polymer was combined with a Prussian Blue counter electrode and a solid polymer electrolyte to form an all-solid-sate ECDs based on complementary switching electrodes and PET-ITO as flexible substrates. The fabricated ECDs were optically and spectroelectrochemically characterized. Excellent functionality of the S2S-processed flexible ECDs was maintained throughout 10 000 switching cycles under laboratory conditions. The ECDs offer enhanced electrochromic properties in terms of visible light transmittance change and color neutrality in the bright state as well as contrast ratio, coloration efficiency, cycling stability and fast response times. Furthermore, the final device assembly was transferred from a S2S-process to a continuous R2R-lamination process.[238] In a third step, the PEDOT-EthC6/PB-based ECDs were submitted to conscious environmental aging tests. The emphasis of the research presented in this work, was mainly put at the influence of moisture and possible failure mechanisms regarding the PEDOT-EthC6/PB based ECDs. An intense brown coloration of the electrodes was observed while cycling the ECDs in humid atmospheres (90\% rH) as a major degradation phenomenon. The brown coloration and a thereby accompanied loss of conductivity of the PET-ITO substrates was related to significant degradation of the ITO layers, inserted as the conductive layers in the flexible ECDs. A dissolution of the ITO thin films and formation of metallic indium particles on the surface of the ITO layers was observed that harmed the cycling stability enormously. The conductive layers of the aged ECDs were investigated by XRD, UV-Vis, SEM and spectroelectrochemical measurements and validated the supposed irreversible reduction of the ITO layers.[279] In the absence of reasonable alternatives to PET-ITO for flexible (R2R-processed) ECDs, it is also important to investigate measures to avoid the degradation of ECDs. This is primarily associated with the avoidance of appropriate electrode potentials necessary for ITO reduction in humid atmospheres. As an intrinsic action point, the electrode potentials were investigated via electrochemical measurements in a three-electrode setup of an all-solid-state ECD. Extensive knowledge on the electrode potentials allowed the voltage-induced degradation of the ITO in flexible ECDs to be avoided through the implementation of an unbalanced electrode configuration (charge density ratio of working and counter electrode). It was possible to narrow the overall operational voltage window to an extent in which irreversible ITO reduction no longer occurs. The unbalanced electrode configuration lead to an improved cycling stability without harming other characteristics such as response time and light transmittance change and allows ECD operation in the presence of humidity.[279] The avoidance of the mentioned degradation phenomena is further associated with appropriate sealing methods and materials as well as appropriate electrode and device fabrication processes. Since a variety of sealing materials is commercially available, due to the commercial launch of organic photovoltaic (OPV) and light emitting diodes (OLEDs), the focus in the present work was put to water-free electrode fabrication. As an extrinsic action point, a novel preparation method of a nanoscale PEDOT-EthC6 dispersion based on organic solvents is presented here in a final step. The water-free processing method gives access to straightforward printing and coating processes on flexible PET-ITO substrates and thus represents a promising and simplified alternative to the established PEDOT:PSS. The resulting nano-PEDOT-EthC6 thin films exhibit enhanced color neutrality and transmissivity in the bright state and are comparable to the properties of the in-situ polymerized PEDOT-EthC6 thin films.[280]},
  subject      = {Elektrochromie},
  language  = {en}
}
@phdthesis{Gold2023,
  author    = {Gold, Lukas},
  title     = {Methods for the state estimation of lithium-ion batteries},
  doi       = {10.25972/OPUS-30618},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-306180},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2023},
  abstract  = {This work introduced the reader to all relevant fields to tap into an ultrasound-based state of charge estimation and provides a blueprint for the procedure to achieve and test the fundamentals of such an approach. It spanned from an in-depth electrochemical characterization of the studied battery cells over establishing the measurement technique, digital processing of ultrasonic transmission signals, and characterization of the SoC dependent property changes of those signals to a proof of concept of an ultrasound-based state of charge estimation. The State of the art \& theoretical background chapter focused on the battery section on the mechanical property changes of lithium-ion batteries during operation. The components and the processes involved to manufacture a battery cell were described to establish the fundamentals for later interrogation. A comprehensive summary of methods for state estimation was given and an emphasis was laid on mechanical methods, including a critical review of the most recent research on ultrasound-based state estimation. Afterward, the fundamentals of ultrasonic non-destructive evaluation were introduced, starting with the sound propagation modes in isotropic boundary-free media, followed by the introduction of boundaries and non-isotropic structure to finally approach the class of fluid-saturated porous media, which batteries can be counted to. As the processing of the ultrasonic signals transmitted through lithium-ion battery cells with the aim of feature extraction was one of the main goals of this work, the fundamentals of digital signal processing and methods for the time of flight estimation were reviewed and compared in a separate section. All available information on the interrogated battery cell and the instrumentation was collected in the Experimental methods \& instrumentation chapter, including a detailed step-by-step manual of the process developed in this work to create and attach a sensor stack for ultrasonic interrogation based on low-cost off-the-shelf piezo elements. The Results \& discussion chapter opened with an in-depth electrochemical and post-mortem interrogation to reverse engineer the battery cell design and its internal structure. The combination of inductively coupled plasma-optical emission spectrometry and incremental capacity analysis applied to three-electrode lab cells, constructed from the studied battery cell's materials, allowed to identify the SoC ranges in which phase transitions and staging occur and thereby directly links changes in the ultrasonic signal properties with the state of the active materials, which makes this work stand out among other studies on ultrasound-based state estimation. Additional dilatometer experiments were able to prove that the measured effect in ultrasonic time of flight cannot originate from the thickness increase of the battery cells alone, as this thickness increase is smaller and in opposite direction to the change in time of flight. Therefore, changes in elastic modulus and density have to be responsible for the observed effect. The construction of the sensor stack from off-the-shelf piezo elements, its electromagnetic shielding, and attachment to both sides of the battery cells was treated in a subsequent section. Experiments verified the necessity of shielding and its negligible influence on the ultrasonic signals. A hypothesis describing the metal layer in the pouch foil to be the transport medium of an electrical coupling/distortion between sending and receiving sensor was formulated and tested. Impedance spectroscopy was shown to be a useful tool to characterize the resonant behavior of piezo elements and ensure the mechanical coupling of such to the surface of the battery cells. The excitation of the piezo elements by a raised cosine (RCn) waveform with varied center frequency in the range of 50 kHz to 250 kHz was studied in the frequency domain and the influence of the resonant behavior, as identified prior by impedance spectroscopy, on waveform and frequency content was evaluated to be uncritical. Therefore, the forced oscillation produced by this excitation was assumed to be mechanically coupled as ultrasonic waves into the battery cells. The ultrasonic waves transmitted through the battery cell were recorded by piezo elements on the opposing side. A first inspection of the raw, unprocessed signals identified the transmission of two main wave packages and allowed the identification of two major trends: the time of flight of ultrasonic wave packages decreases with the center frequency of the RCn waveform, and with state of charge. These trends were to be assessed further in the subsequent sections. Therefore, methods for the extraction of features (properties) from the ultrasonic signals were established, compared, and tested in a dedicated section. Several simple and advanced thresholding methods were compared with envelope-based and cross-correlation methods to estimate the time of flight (ToF). It was demonstrated that the envelope-based method yields the most robust estimate for the first and second wave package. This finding is in accordance with the literature stating that an envelope-based method is best suited for dispersive, absorptive media [204], to which lithium-ion batteries are counted. Respective trends were already suggested by the heatmap plots of the raw signals vs. RCn frequency and SoC. To enable such a robust estimate, an FIR filter had to be designed to preprocess the transmitted signals and thereby attenuate frequency components that verifiably lead to a distorted shape of the envelope. With a robust ToF estimation method selected, the characterization of the signal properties ToF and transmitted energy content (EC) was performed in-depth. A study of cycle-to-cycle variations unveiled that the signal properties are affected by a long rest period and the associated relaxation of the multi-particle system "battery cell" to equilibrium. In detail, during cycling, the signal properties don't reach the same value at a given SoC in two subsequent cycles if the first of the two cycles follows a long rest period. In accordance with the literature, a break-in period, making up for more than ten cycles post-formation, was observed. During this break-in period, the mechanical properties of the system are said to change until a steady state is reached [25]. Experiments at different C-rate showed that ultrasonic signal properties can sense the non-equilibrium state of a battery cell, characterized by an increasing area between charge and discharge curve of the respective signal property vs. SoC plot. This non-equilibrium state relaxes in the rest period following the discharge after the cut-off voltage is reached. The relaxation in the rest period following the charge is much smaller and shows little C-rate dependency as the state is prepared by constant voltage charging at the end of charge voltage. For a purely statistical SoC estimation approach, as employed in this work, where only instantaneous measurements are taken into account and the historic course of the measurement is not utilized as a source of information, the presence of hysteresis and relaxation leads to a reduced estimation accuracy. Future research should address this issue or even utilize the relaxation to improve the estimation accuracy, by incorporating historic information, e.g., by using the derivative of a signal property as an additional feature. The signal properties were then tested for their correlation with SoC as a function of RCn frequency. This allowed identifying trends in the behavior of the signal properties as a function of RCn frequency and C-rate in a condensed fashion and thereby enabled to predict the frequency range, about 50 kHz to 125 kHz, in which the course of the signal properties is best suited for SoC estimation. The final section provided a proof of concept of the ultrasound-based SoC estimation, by applying a support vector regression (SVR) to before thoroughly studied ultrasonic signal properties, as well as current and battery cell voltage. The included case study was split into different parts that assessed the ability of an SVR to estimate the SoC in a variety of scenarios. Seven battery cells, prepared with sensor stacks attached to both faces, were used to generate 14 datasets. First, a comparison of self-tests, where a portion of a dataset is used for training and another for testing, and cross-tests, which use the dataset of one cell for training and the dataset of another for testing, was performed. A root mean square error (RMSE) of 3.9\% to 4.8\% SoC and 3.6\% to 10.0\% SoC was achieved, respectively. In general, it was observed that the SVR is prone to overestimation at low SoCs and underestimation at high SoCs, which was attributed to the pronounced hysteresis and relaxation of the ultrasonic signal properties in this SoC ranges. The fact that higher accuracy is achieved, if the exact cell is known to the model, indicates that a variation between cells exists. This variation between cells can originate from differences in mechanical properties as a result of production variations or from differences in manual sensor placement, mechanical coupling, or resonant behavior of the ultrasonic sensors. To mitigate the effect of the cell-to-cell variations, a test was performed, where the datasets of six out of the seven cells were combined as training data, and the dataset of the seventh cell was used for testing. This reduced the spread of the RMSE from (3.6 - 10.0)\% SoC to (5.9 - 8.5)\% SoC, respectively, once again stating that a databased approach for state estimation becomes more reliable with a large data basis. Utilizing self-tests on seven datasets, the effect of additional features on the state estimation result was tested. The involvement of an additional feature did not necessarily improve the estimation accuracy, but it was shown that a combination of ultrasonic and electrical features is superior to the training with these features alone. To test the ability of the model to estimate the SoC in unknown cycling conditions, a test was performed where the C-rate of the test dataset was not included in the training data. The result suggests that for practical applications it might be sufficient to perform training with the boundary of the use cases in a controlled laboratory environment to handle the estimation in a broad spectrum of use cases. In comparison with literature, this study stands out by utilizing and modifying off-the-shelf piezo elements to equip state-of-the-art lithium-ion battery cells with ultrasonic sensors, employing a range of center frequencies for the waveform, transmitted through the battery cell, instead of a fixed frequency and by allowing the SVR to choose the frequency that yields the best result. The characterization of the ultrasonic signal properties as a function of RCn frequency and SoC and the assignment of characteristic changes in the signal properties to electrochemical processes, such as phase transitions and staging, makes this work unique. By studying a range of use cases, it was demonstrated that an improved SoC estimation accuracy can be achieved with the aid of ultrasonic measurements - thanks to the correlation of the mechanical properties of the battery cells with the SoC.},
  subject      = {Lithium-Ionen-Akkumulator},
  language  = {en}
}