Charakterisierung der Leistungsfähigkeit von PEM-Wasser-Elektrolysezellen, die mit und ohne Strömungskanäle arbeiten, basierend auf experimentell validierten semi-empirischen gekoppelten physikalischen Modellen

PEM water electrolysis is a clean technology for hydrogen production. In spite of its many advantages, the costs of the conventional PEM electrolysis cell makes it commercially less competitive vis-à-vis its peers. An alternative cell design has been proposed which has up to a 25 % costs advantage over the conventional cell. In this alternative cell design, the flow channel plate which bears the most costs in the conventional cell design has been replaced with a 3-D Porous Transport Layer (PTL) structure. It has however, been observed that the conventional cell by far out performs the low cost cell at high current density operations, due to increased mass transport limitation in the later. Industrial and commercial hydrogen production efforts are focused towards high current density operation (> 3 A/cm²), so the alternative cell design must be optimized for mass transport limitation. PEM water electrolysis is a clean technology for hydrogen production. In spite of its many advantages, the costs of the conventional PEM electrolysis cell makes it commercially less competitive vis-à-vis its peers. An alternative cell design has been proposed which has up to a 25 % costs advantage over the conventional cell. In this alternative cell design, the flow channel plate which bears the most costs in the conventional cell design has been replaced with a 3-D Porous Transport Layer (PTL) structure. It has however, been observed that the conventional cell by far out performs the low cost cell at high current density operations, due to increased mass transport limitation in the later. Industrial and commercial hydrogen production efforts are focused towards high current density operation (> 3 A/cm²), so the alternative cell design must be optimized for mass transport limitation. This work seeks to understand the source of, and to eliminate the mass transport losses in the alternative cell design to get it performing at least as good as the conventional cell at current densities up to 5 A/cm². A 2-D non-isothermal semi-empirical fully-coupled models of both cell designs have been developed and experimentally validated. The developed validated models were then used as tools to simulate and predict the best operating conditions, design parameters and micro-structural properties of the PTL at which the mass transport issues in the alternate cell will be at its minimum, at high current densities. The models are based on a multi-physics approach in which thermodynamic, electrochemical, thermal and mass transport sub-models are coupled and solved numerically, to predict the cell polarization and individual overpotentials, as well as address heat and water management issues. The most unique aspect of this work however, is the development of own semi-empirical equations for predicting the mass transport overpotential imposed by the gas phase (bubbles) at high current densities. For the very first time, calculated polarization curves up to 5 A/cm² have been validated by own experimental data. The results show that, the temperature and pressure, water flowrate and thickness of the PTL are the critical parameters for mitigating mass transport limitation. It was found that, for the size of the cells studied (25 cm² active area each), when both cells are operating at the same temperature of 60 °C, alternative design will have a comparable performance to the conventional designed cell even at 5 A/cm² current density when; the operating pressure is ≥ 5 bar, the feed water flowrate is ≥ 0.024l/min∙cm², PTL porosity is 50 %, PTL pore size is ≥ 11 µm and PTL thickness is 0.5 mm. At these operating, design and micro-structural conditions, the predicted difference between the polarizations of both cells will be only ~10 mV at 5 A/cm² operating current density.Die PEM Wasser Elektrolyse gilt als effiziente Technologie zur Herstellung von sauberem Wasserstoff zur Energiespeicherung. Trotz der vielen Vorteile führen hohe Kosten für die Produktion konventioneller Komponenten und Stacks zu einer nicht konkurrenzfähigen Technologie. Ein alternatives und kostengünstiges Zelldesign wurde vorgestellt, das, verglichen mit einem konventionellen Design, einen Kostenvorteil von bis zu 25 % hervorbringt. Bei diesem alternativen Zelldesign wird die Platte mit Strömungskanälen, die den größten Kostenanteil birgt, durch eine 3-D poröse Struktur (PTL) ersetzt. Bei hohen Stromdichten zeigt aber ein Design ohne Strömungskanäle niedrigere Leistungsdaten, was durch eine gesteigerte Limitierung des Massentransportes erklärt werden kann. Da sich die industrielle und kommerzielle Wasserstoffproduktion in Richtung hoher Stromdichten (> 3 A/cm²) entwickelt, scheint das erforderliche Verständnis von Massentransporteffekten offensichtlich das kosteneffiziente Design gegenüber dem konventionellen Design voran zu treiben. Diese Arbeit versucht den Ursprung von Massentransportlimitierung des kostengünstigen Zelldesigns zu verstehen und zu eliminieren. Um diese Zielvorgabe zu erreichen, wurden 2-D nicht-isotherme, semi-empirische, vollständig gekoppelte Modelle beider Zelldesigns entwickelt und experimentell validiert. Die entwickelten und validierten Modelle wurden als Werkzeug zur Simulation und Vorhersage der am besten geeigneten Betriebs- und Designparameter, sowie Eigenschaften der Mikrostrukur der PTL verwendet. Die hierin entwickelten Modelle basieren auf einem multiphysikalischen Ansatz, worin thermodynamische, elektrische und thermische Effekte sowie Massentransportuntermodelle gekoppelt und gelöst wurden, um sowohl die Zellpolarisation und individuelle Überpotentiale vorherzusagen, als auch Wärme- und Wassermanagement zu adressieren. Das Alleinstellungsmerkmal dieser Arbeit ist jedoch die Entwicklung von semi-empirischen Gleichungen, um die Überpotentiale der Massentransporthemmung, ausgehend von Gasblasen, vorhersagen zu können. Ebenso wurden zum ersten Mal berechnete PEM Wasser Elektrolyse Polarisationskurven bis zu einer Stromdichte von 5 A/cm² mit eigenen Daten validiert. Die Ergebnisse zeigen, dass Temperatur und Druck, sowie Wasserflußrate und Dicke der PTL die kritischen Parameter sind, um Massentransportlimitierung zu vermeiden. Es wurde sogar gezeigt, dass bei der verwendeten Zellgröße (aktive Fläche = 25 cm²) vergleichbare Leistungsdaten bei 60 °C und 5 A/cm² erreicht werden können, sofern der Betriebsdruck 5 bar übersteigt, die Wasserflussrate größer als 0.024 l/min ist, die Porosität der PTL 50 % übersteigt, die Porendurchmesser größer als 11 µm sind und die PTL Dicke bei 0.5 mm liegt. Bei diesen Parametern wurden Unterschiede zwischen den beiden Zelldesigns von etwa 10 mV bei 5 A/cm² vorhergesagt

Legislative History: An Act to Preserve Public Ownership of Historic Fort Gorges in Casco Bay (HP696)(LD 1000)

https://digitalmaine.com/legishist115/1999/thumbnail.jp

Sub-kHz lasing of a CaF_2 Whispering Gallery Mode Resonator Stabilized Fiber Ring Laser

We utilize a high quality calcium fluoride whispering-gallery-mode resonator to stabilize a simple erbium doped fiber ring laser with an emission frequency of 196 THz (wavelenght 1530 nm) to a linewidth below 650 Hz. This corresponds to a relative stability of 3.3 x 10^(-12) over 16 \mus. In order to characterize the linewidth we use two identical self-built lasers and a commercial laser to determine the individual lasing linewidth via the three-cornered hat method.Comment: 4 pages, 3 figure

Maximization of the optical intra-cavity power of whispering-gallery mode resonators via coupling prism

In this paper, a detailed description of the optical coupling into a Whispering Gallery Mode (WGM) resonator through a prism via frustrated total internal reflection (FTIR) is presented. The problem is modeled as three media with planar interfaces and closed expressions for FTIR are given. Then, the curvature of the resonator is taken into account and the mode overlap is theoretically studied. A new analytical expression giving the optimal geometry of a disc-shaped or ring-shaped resonator for maximizing the intra-cavity circulating power is presented. Such expression takes into consideration the spatial distribution of the WGM at the surface of the resonator, thus being more accurate than the currently used expressions. It also takes into account the geometry of the prism. It is shown an improvement in the geometry values used with the current expressions of about 30%. The reason why the pump laser signal can be seen in experiments under critical coupling is explained on this basis. Then, the conditions required for exciting the highest possible optical power inside the resonator are obtained. The aim is to achieve a highly-efficient up-conversion of a THz signal into the optical domain via the second-order nonlinearity of the resonator material.This work has been financially supported by "DiDaCTIC: Desarrollo de un sistema de comunicaciones inalámbrico en rango THz integrado de alta tasa de datos", TEC2013-47753-C3, CAM S2013/ICE-3004 "DIFRAGEOS" projects, "Proyecto realizado con la Ayuda Fundación BBVA a Investigadores y Creadores Culturales 2016" and "Estancias de movilidad de profesores PRX16/00021"

Crystalline MgF2 whispering gallery mode resonators for enhanced bulk index sensitivity

We report on experiments on refractrometric sensing with crystalline Whispering Gallery Mode (WGM) resonators made of magnesium fluoride, which has a refractive index that is only slightly larger than that of water (Delta n approximate to 0.05). The resulting evanescent field of a WGM resonator placed in an aqueous environment penetrates therefore deep into the surrounding medium, which makes it a promising candidate for sensing applications. We measured a bulk index sensitivity of 1.09 nm/RIU (refractive index unit) in a resonator with a radius of R = 2.91mm and intrinsic Q-factors of more than 10(8) in aqueous environments. Furthermore, we describe the fabrication process of crystalline WGM resonators

Selective Coupling Enhances Harmonic Generation of Whispering-Gallery Modes

We demonstrate second-harmonic generation (SHG) in an x-cut congruent lithium niobate (LN) whispering-gallery mode (WGM) resonator. First, we show theoretically that independent control of the coupling of the pump and signal modes is optimal for high conversion rates. A coupling scheme based on our earlier work [F. Sedlmeir et al., Phys. Rev. Applied 7, 024029 (2017)] is then implemented experimentally to verify this improvement. Thereby, we are able to improve on the efficiency of SHG by more than an order of magnitude by selectively outcoupling using a LN prism, utilizing the birefringence of it and the resonator in kind. This method is also applicable to other nonlinear processes in WGM resonators

Whispering gallery modes at the rim of an axisymmetric optical resonator: Analytical versus numerical description and comparison with experiment

Optical whispering gallery modes (WGMs) of mm-sized axisymmetric resonators are well localized at the equator. Employing this distinctive feature, we obtain simple analytical relations for the frequencies and eigenfunctions of WGMs which include the major radius of the resonator and the curvature radius of the rim. Being compared with results of finite-element simulations, these relations show a high accuracy and practicability. High-precision free-spectral-range measurements with a millimeter-sized disc resonator made of MgF2 allow us to identify the WGMs and confirm the applicability of our analytical description. (C) 2013 Optical Society of Americ

Towards terahertz detection and calibration through spontaneous parametric down-conversion in the terahertz idler-frequency range generated by a 795 nm diode laser system

We study a calibration scheme for terahertz wave nonlinear-optical detectors based on spontaneous parametric down-conversion. Contrary to the usual low wavelength pump in the green, we report here on the observation of spontaneous parametric down-conversion originating from an in-growth poled lithium niobate crystal pumped with a continuous wave 50 mW, 795 nm diode laser system, phase-matched to a terahertz frequency idler wave. Such a system is more compact and allows for longer poling periods as well as lower losses in the crystal. Filtering the pump radiation by a rubidium-87 vapor cell allowed the frequency-angular spectra to be obtained down to similar to 0.5 THz or similar to 1 nm shift from the pump radiation line. The presence of an amplified spontaneous emission "pedestal" in the diode laser radiation spectrum significantly hampers the observation of spontaneous parametric down-conversion spectra, in contrast to conventional narrowband gas lasers. Benefits of switching to longer pump wavelengths are pointed out, such as collinear optical-terahertz phase-matching in bulk crystals. (c) 2018 Author(s)

Directional emission of dielectric disks with a finite scatterer in the THz regime

In the Terahertz (THz) domain, we investigate both numerically and experimentally the directional emission of whispering gallery mode resonators that are perturbed by a small scatterer in the vicinity of the resonators rim. We determine quality factor degradation, the modal structure and the emission direction for various geometries. We find that scatterers do allow for directional emission without destroying the resonator's quality factor. This finding allows for new geometries and outcoupling scenarios for active whispering gallery mode structures such as quantum cascade lasers and passive resonators such as evanescent sensors. The experimental results agree well with finite difference time domain simulations. (C) 2013 Optical Society of Americ