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  • The Electrochemical Society  (5)
  • 1
    In: ECS Transactions, The Electrochemical Society, Vol. 75, No. 14 ( 2016-08-22), p. 45-53
    Abstract: In this study, Distribution of Relaxation Times (DRT) analysis is applied for identification of polarization losses in High Temperature Polymer Electrolyte Membrane Fuel Cells (HT-PEMFCs). Electrochemical impedance spectra recorded for different air stoichiometries and current densities are analyzed. While basic impedance analysis broadly recognizes the presence of three features, DRT reveals at least six distinct processes occurring on different time scales. By varying the stoichiometry and current bias, three of those processes are attributed to mass transport and cathodic kinetics. Furthermore, the DRT analysis suggests that the cathode kinetics may involve two different processes, as opposed to a single-feature process that is often assumed. These results have improved our understanding of the loss mechanisms in HT-PEMFCs and provide valuable guidance for fuel cell optimization.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2016
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  • 2
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  ECS Meeting Abstracts Vol. MA2015-01, No. 2 ( 2015-04-29), p. 644-644
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2015-01, No. 2 ( 2015-04-29), p. 644-644
    Abstract: Graphite is the most commonly used anode material in Lithium-ion batteries. It allows high energy and power densities (depending on material parameters). Lithium intercalation losses can be reduced by fine-tuning anode design. In previous literature, several electrochemical models (1-4) were proposed to better understand and simulate this process. The challenge is to parameterize and unambiguously validate these models. This would require electrochemical investigations e.g. electrochemical impedance spectroscopy (EIS) in half cell setups under a variation of boundary conditions, namely state of charge (SOC) or temperature (1,5). However, it can be difficult to get sufficient information for parameterization. Some parameters, e.g. electrical and ionic conductivity, show similar dependencies in their physical equations. Lithium intercalation decreases the electrode potential and changes the diffusive reflectance. This is due to SOC dependent photo-molecular interactions, e.g. intraband transitions (6). In this work we present a new optical cell setup with a Lithium ring reference electrode. This innovation allows simultaneous in-situ optical and electrical measurements. We can now observe the dynamic behavior of the macroscopic anode surface reflectance. We demonstrate the excitation by using a modulated voltage signal to measure the reflectance as a response signal. With this new measurement method, we mapped an optical impedance spectrum (OIS), revealing further information about the Lithium intercalation process. Conventional electrochemical models usually only contain electrical measurement figures. The most appropriate model assumption for porous graphite electrodes is based on a transmission line (1,7). In this study, the transmission line model is extended so that it reproduces both the EIS and OIS measurements. It is thereby possible to investigate different model assumptions using a combined electro-optical parameterization (Fig. 1). It becomes apparent that combined electro-optical parameterization can reduce ambiguities in the electrochemical model. It will be demonstrated that the OIS is highly sensitive to changes in ionic and electronic conductivities; ergo, these parameters can be reliably determined. Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
    detail.hit.zdb_id: 2438749-6
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  • 3
    Online Resource
    Online Resource
    The Electrochemical Society ; 2017
    In:  ECS Meeting Abstracts Vol. MA2017-02, No. 32 ( 2017-09-01), p. 1352-1352
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2017-02, No. 32 ( 2017-09-01), p. 1352-1352
    Abstract: High temperature proton exchange membrane fuel cells (HT-PEMFCs) based on phosphoric acid doped polybenzimidazole operate at a temperature range between 140°C and 200°C. Due to their high operating temperature, HT-PEMFCs can tolerate a relatively high concentration of impurities in the anodic fuel stream. This makes HT-PEMFCs suitable for stationary applications where hydrogen is generated on site by steam reforming of hydrocarbons such as methane or oil derivatives. In particular, the preferential oxidation stage (PROX), which is typically required to reduce the CO concentration to ≈10 ppm after the reforming and water gas shift (WGS) reactors, is no longer necessary. Thus, fuel treatment units are simpler and cheaper with HT-PEMFCs [1] . The proven robustness of HT-PEMFCs against fuel impurities has recently attracted interest to operate the HT-PEMFC as a ‘hydrogen pump’ for hydrogen purification applications. In this configuration, a hydrogen rich gas stream is supplied to the cell’s anode compartment and a current is externally applied through the cell. Different from a typical fuel cell, no oxygen is supplied on the cathode side. During this process, hydrogen is electrochemically ‘pumped’ from the anode to the cathode in the form of protons through the electrolyte membrane. The ‘pump effect’ is highly selective and a pure hydrogen stream is obtained at the cathode outlet of the cell (≈10 ppm). Compared with low temperature Nafion based fuel cells, HT-PEMFCs are much more promising for purification of hydrogen streams that contain considerable amounts of impurities, as proven by preliminary studies [2, 3]. In this work, an investigation of the HT-PEMFC operated as an electrochemical hydrogen pump is carried out. The impact of hydrogen dilution and CO poisoning is studied as well as the effects of hydrogen stoichiometry, gas humidification, and electrolyte resistance. The cell is characterized with various techniques including polarization curves, electrochemical impedance spectra (EIS), and distribution of relaxation times (DRT) analysis (Fig. 1). Complementary to the equivalent circuit approach, DRT maps the EIS data to a function that contains the characteristic time scales of the system [4]. These results are important for the assessment of the HT-PEMFC’s potential for hydrogen purification. Although this application is distinctly different from that of a typical fuel cell, the electrochemical process at the anode is actually the same as in a normal HT-PEMFC. Therefore, the study also helps us gain valuable insight into the hydrogen oxidation reaction process in the presence of impurities. References [1] R. Zeis, Beilstein Journal of Nanotechnology, 6 (2015) 68-83. [2] S.J. Kim, B.-S. Lee, S.H. Ahn, J.Y. Han, H.Y. Park, S.H. Kim, S.J. Yoo, H.-J. Kim, E. Cho, D. Henkensmeier, S.W. Nam, T.-H. Lim, S.-K. Kim, W. Huh, J.H. Jang, International Journal of Hydrogen Energy, 38 (2013) 14816-14823. [3] K.A. Perry, G.A. Eisman, B.C. Benicewicz, Journal of Power Sources, 177 (2008) 478-484. [4] A. Weiß, S. Schindler, S. Galbiati, M.A. Danzer, R. Zeis, Electrochimica Acta, 230 (2017) 391-398. Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2017
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  • 4
    Online Resource
    Online Resource
    The Electrochemical Society ; 2016
    In:  ECS Meeting Abstracts Vol. MA2016-02, No. 23 ( 2016-09-01), p. 1717-1717
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2016-02, No. 23 ( 2016-09-01), p. 1717-1717
    Abstract: Impedance spectroscopy is a powerful tool for rating the performance and degradation of battery cells [1]. With regard to commercial cell formats, impedance acquisition and analysis is limited to the full cell impedance due to absence of an appropriate lithium reference potential to separate the shares of both half-cells. In consideration of this limitation, the equivalent electrodes are usually examined separately in symmetrical or three electrode arrangements [2, 3] . While this approach is generally suitable for qualitative estimations of the half-cell ratios, a quantitative reconstruction requires detailed knowledge of impedance contributions from the cell geometry and electrical contacts as well as an appropriate model approach to subtract the latter from the actual half-cell data. In this study, we introduce a model-based reconstruction methodology based on a mathematical treatment of measurement data recorded on experimental full cells with suitable reference electrode. The methodology includes impedance scaling equivalent to the ratio of electrochemically active areas of experimental and commercial cell, a modulation of the geometrical contribution to the cell impedance and a correction of the purely ohmic impedance ratio to compensate the deviation of electrolyte volumes. It is shown that the subsequent application of these modification steps already yields an excellent reconstruction which can even be further refined by increasing the model discretization. The validity of the proposed methodology is cross-checked by application of distribution of relaxation times (DRT) analysis, which is a powerful mathematical tool to separate polarization contributions by their characteristic time constants [4]. Here, DRT is utilized to demonstrate the reproduction fidelity of the impedance modulation. The presented methodology opens the door for a great bandwidth of new applications, for instance to develop iterative half-cell degradation models which can be parametrized from impedance data recorded on the (commercial) full cell at any state of degradation. Thus, it constitutes a completely refined opportunity for online applicable, non-invasive diagnosis of lithium-ion cells. References [1] Osaka, T.; Daikichi, M.; Hiroki, N.; J. Electrochem. Soc. 162 (2015) A2529-A2537 [2] Song, J.; Lee, H.; Wang, Y.; Wan, C.; J. Power Sources 111(2002) 255-267 [3] Chen, C.; Liu, J.; Amine, K.; J. Power Sources 96 (2001) 321-328 [4] Illig, J.; Schmidt, J.P.; Weiss, M.; Weber, A., Ivers-Tiffée, E.; J. Power Sources 239 (2013) 670-679 Figure Captions Fig. 1: a) Exemplary nyquist plot recorded for commercial and experimental full cell ( T = 25°C, SOC = 50 %). Simplified equivalent circuit structures used in the reconstruction for b) experimental full cell c) commercial cell. A reference electrode is implemented in the experimental cell to separate half-cell impedances. Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2016
    detail.hit.zdb_id: 2438749-6
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  • 5
    Online Resource
    Online Resource
    The Electrochemical Society ; 2016
    In:  ECS Meeting Abstracts Vol. MA2016-02, No. 38 ( 2016-09-01), p. 2353-2353
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2016-02, No. 38 ( 2016-09-01), p. 2353-2353
    Abstract: In recent years phosphoric acid doped PBI-type fuel cells have drawn much attention as a promising candidate for energy storage and conversion applications at relatively high temperatures (100 – 200 °C). The elevated operating temperature of HT-PEMFCs (high-temperature polymer electrolyte membrane fuel cells) simplifies water and thermal management. In addition, it greatly enhances the fuel cell’s tolerance against impurities (e.g. CO) in hydrogen, which is critical for operation with reformate hydrogen. However, durability and stability of high-temperature PEM-MEAs still need to improve for widespread commercialization [1], and better tools for identifying performance-loss related mechanisms are desirable. A very useful in-situ technique for performance analysis of HT-PEMFCs is electrochemical impedance spectroscopy (EIS). As previously reported, EIS can be used to characterize the impact of different parameters (e.g. stoichiometry, temperature, etc.) on cell kinetics [2, 3] . Equivalent circuit models are usually used to analyze the EIS data and identify the performance-loss related mechanisms. A major drawback of this approach is that the assumptions for the model equivalent circuits are sometimes ambiguous or even misleading due to the lack of priori knowledge about the electrochemical system under study. Furthermore, a clear separation of various physiochemical processes is difficult if the time constants of these processes overlap significantly in the frequency domain. To overcome these drawbacks, advanced mathematical methods such as Distribution of Relaxation Times (DRT) can be applied. DRT relies on the representation of the polarization impedance by its characteristic time constants and is numerically approximated by a discrete distribution function. This method has been successfully demonstrated for process identification and separation in solid oxide fuel cells (SOFC) [4]. In this study, we applied this technique on high temperature PEM-MEAs for the first time. Electrochemical processes were identified and analyzed by varying cell parameters such as temperature and stoichiometry. The results offer a refined understanding of loss mechanisms and provide valuable guidance for fuel cell improvement and optimization. [1] A. Chandan, M. Hattenberger, A. El-kharouf, S. Du, A. Dhir, V. Self, B.G. Pollet, A. Ingram, W. Bujalski, J. Power Sources 231 (2013) 264 [2] J. L. Jesperesen, E. Schaltz, S.K. Kær, J. of Power Sources 191 (2009) 289-296 [3] F. Mack, R. Laukenmann, S. Galbiati, J. A. Kerres, R. Zeis, ECS Transactions 69 (17), 1075-1087 (2015) [4] A. Leonide, V. Sonn, A. Weber, and E. Ivers-Tiffée, Journal of the Electrochemical Society 155 (1) B36-B41 (2008) Figure 1 Typical Nyquist plot of a phosphoric acid doped PBI-type HT-PEMFC at different current densities (a) and the corresponding distribution function (b). Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2016
    detail.hit.zdb_id: 2438749-6
    Location Call Number Limitation Availability
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