Angular Distribution of Photoelectrons in Three Photon Ionisation of Sodium

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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

Feasibility of free space quantum key distribution with coherent polarization states

We demonstrate for the first time the feasibility of free space quantum key distribution with continuous variables under real atmospheric conditions. More specifically, we transmit coherent polarization states over a 100m free space channel on the roof of our institute's building. In our scheme, signal and local oscillator are combined in a single spatial mode which auto-compensates atmospheric fluctuations and results in an excellent interference. Furthermore, the local oscillator acts as spatial and spectral filter thus allowing unrestrained daylight operation.Comment: 12 pages, 8 figures, extensions in sections 2, 3.1, 3.2 and 4. This is an author-created, un-copyedited version of an article accepted for publication in New Journal of Physics (Special Issue on Quantum Cryptography: Theory and Practice). IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from i

Device calibration impacts security of quantum key distribution

Characterizing the physical channel and calibrating the cryptosystem hardware are prerequisites for establishing a quantum channel for quantum key distribution (QKD). Moreover, an inappropriately implemented calibration routine can open a fatal security loophole. We propose and experimentally demonstrate a method to induce a large temporal detector efficiency mismatch in a commercial QKD system by deceiving a channel length calibration routine. We then devise an optimal and realistic strategy using faked states to break the security of the cryptosystem. A fix for this loophole is also suggested.Comment: 4 pages + 1 page of supplementary information. Considerable modification of Eve's attack strategy and QBER minimization technique. All figures have also been improve

Generation and Direct Detection of Broadband Mesoscopic Polarization-Squeezed Vacuum

Using a traveling-wave OPA with two orthogonally oriented type-I BBO crystals pumped by picosecond pulses, we generate vertically and horizontally polarized squeezed vacuum states within a broad range of wavelengths and angles. Depending on the phase between these states, fluctuations in one or another Stokes parameters are suppressed below the shot-noise limit. Due to the large number of photon pairs produced, no local oscillator is required, and 3dB squeezing is observed by means of direct detection.Comment: 4 pages, 4 figures, submitted to PR

The focus of light - linear polarization breaks the rotational symmetry of the focal spot

We experimentally demonstrate for the first time that a linearly polarized beam is focussed to an asymmetric spot when using a high-numerical aperture focussing system. This asymmetry was predicted by Richards and Wolf [Proc.R.Soc.London A, 253, 358 (1959)] and can only be measured when a polarization insensitive sensor is placed in the focal region. We used a specially modified photodiode in a knife edge type set up to obtain highly resolved images of the total electric energy density distribution at the focus. The results are in good agreement with the predictions of a vectorial focussing theory.Comment: to be published in "Journal of Modern Optics

Universal optical amplification without nonlinearity

We propose and experimentally realize a new scheme for universal phase-insensitive optical amplification. The presented scheme relies only on linear optics and homodyne detection, thus circumventing the need for nonlinear interaction between a pump field and the signal field. The amplifier demonstrates near optimal quantum noise limited performance for a wide range of amplification factors.Comment: 5 pages, 4 figure

Lost and found: the radial quantum number of Laguerre-Gauss modes

We introduce an operator linked with the radial index in the Laguerre-Gauss modes of a two-dimensional harmonic oscillator in cylindrical coordinates. We discuss ladder operators for this variable, and confirm that they obey the commutation relations of the su(1,1) algebra. Using this fact, we examine how basic quantum optical concepts can be recast in terms of radial modes.Comment: Some minor typos fixed

Demonstration of the spatial separation of the entangled quantum side-bands of an optical field

Quantum optics experiments on "bright" beams typically probe correlations between side-band modes. However the extra degree of freedom represented by this dual mode picture is generally ignored. We demonstrate the experimental operation of a device which can be used to separate the quantum side-bands of an optical field. We use this device to explicitly demonstrate the quantum entanglement between the side-bands of a squeezed beam