Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

Spectral analysis of four 'hypervariable' AGN: a micro-needle in the haystack?

We analyze four extreme AGN transients to explore the possibility that they are caused by rare, high-amplitude microlensing events. These previously unknown type-I AGN are located in the redshift range 0.6-1.1 and show changes of > 1.5 magnitudes in the g-band on a timescale of ~years. Multi-epoch optical spectroscopy, from the William Herschel Telescope, shows clear differential variability in the broad line fluxes with respect to the continuum changes and also evolution in the line profiles. In two cases a simple point-source, point-lens microlensing model provides an excellent match to the long-term variability seen in these objects. For both models the parameter constraints are consistent with the microlensing being due to an intervening stellar mass object but as yet there is no confirmation of the presence of an intervening galaxy. The models predict a peak amplification of 10.3/13.5 and an Einstein timescale of 7.5/10.8 years respectively. In one case the data also allow constraints on the size of the CIII] emitting region, with some simplifying assumptions, to to be ~1.0-6.5 light-days and a lower limit on the size of the MgII emitting region to be > 9 light-days (half-light radii). This CIII] radius is perhaps surprisingly small. In the remaining two objects there is spectroscopic evidence for an intervening absorber but the extra structure seen in the lightcurves requires a more complex lensing scenario to adequately explain.

Studies on Quasinormal Modes and Late-time Tails in Black Hole Spacetimes

Black hole's response to external perturbations will carry significant information about these exotic objects. Its response, shortly after the initial `kick', is known to be ruled by the damped oscillation of the perturbating eld, called quasinormal modes(QNMs), followed by the tails of decay and is the characteristic of the background black hole spacetime. In the last three decades, several shortcomings came out in the Einstein's General Theory of Relativity(GTR). Such issues come, especially, from observational cosmology and quantum eld theory. In the rst case, for example, the observed accelerated expansion of the universe and the hypothesized mysterious dark energy still lack a satisfactory explanation. Secondly, GTR is a classical theory which does not work as a fundamental theory, when one wants to achieve a full quantum description of gravity. Due to these facts modi cation to GTR or alternative theories for gravity have been considered. Two potential approaches towards these problems are the quintessence model for dark energy and Ho rava-Lifshitz(HL) gravity. Quintessence is a dynamical model of dark energy which is often realized by scalar eld mechanism. HL gravity is the recently proposed theory of gravity, which is renormalizable in power counting arguments. The two models are considered as a potential candidate in explaining these issues.

Righe spettrali: formazione, shift ed allargamento

In questo breve elaborato si vuole spiegare l’importanza dello studio di un corpo celeste mediante l’osservazione del suo spettro ovvero un grafico del flusso emesso in funzione della frequenza o della lunghezza d’onda nel quale sono presenti righe spettrali, formate dall’interazione tra materia e radiazione, a causa dell’assorbimento od emissione di fotoni a seguito di transizioni elettroniche, ma anche vibrazionali e rotazionali per le molecole. In particolare, dall’analisi delle righe spettrali si traggono diverse informazioni sull’oggetto, quali, la composizione e l’abbondanza delle specie chimiche che lo compongono in base al tipo di righe presenti e alla loro intensità, si deduce la temperatura e la pressione dell’oggetto studiato dalla larghezza di queste, ancora, informazioni sul moto relativo e la distanza dall’osservatore misurando lo shift delle righe; infine densità e campi magnetici del mezzo interstellare. Per molti oggetti astronomici, troppo distanti, lo studio dello spettro è l’unico modo per trarre conclusioni sulla loro natura. Per questo, nel primo capitolo si ricava l’equazione del trasporto radiativo, soffermandosi sui processi che regolano l’assorbimento e l’emissione di energia. Il secondo capitolo invece, tratta il caso particolare delle atmosfere stellari, nel quale si ricava, con una serie di approssimazioni fatte sull’equazione del trasporto radiativo, quale parte osserviamo di una stella e dove si formano le righe spettrali. Successivamente ci si è concentrati sui meccanismi che portano alla formazione delle righe spettrali, analizzando sia le transizioni radiative con i coefficienti di Einstein, sia quelle collisionali, e distinguendo tra transizioni permesse o proibite con le regole di selezione. Infine si sono esaminate le informazioni che si possono ricavare dalle righe spettrali, approfondendo sui fenomeni di shift e modifica di queste, descrivendo più nel dettaglio la riga a 21 cm dell’atomo di idrogeno, fondamentale in astrofisica.

I Wormholes ed il loro impiego per il viaggio interstellare

Viaggiare da un punto all'altro dell'universo muovendosi in uno spazio-tempo piatto richiede tempi talmente colossali da risultare impossibile per la nostra razza; pertanto, un viaggio interstellare potrebbe essere realizzato solo per mezzo di topologie relativistiche in grado di accorciare la distanza fra i punti dell'universo. Dopo aver dato una serie di motivazioni per cui i buchi neri ed il ponte di Einstein-Rosen non sono adatti ad essere impiegati viene introdotta una particolare classe di soluzioni, presentata per la prima volta da Michael S. Morris e Kip S. Thorne, delle equazioni di Einstein: essa descrive wormholes i quali, almeno in linea di principio, risultano attraversabili dagli esseri umani in quanto non presentano un orizzonte degli eventi sulla gola. Quest'ultima proprietà, insieme alle equazioni di campo di Einstein, pone dei vincoli piuttosto estremi sul tipo di materiale in grado di dar luogo alla curvatura spazio-temporale del wormhole: nella gola del wormhole la materia deve possedere una tensione radiale di enorme intensità, dell'ordine di quella presente nel centro delle stelle di neutroni più massive per gole con un raggio di appena qualche kilometro. Inoltre, questa tensione dev'essere maggiore della densità di energia del materiale: ad oggi non si conosce alcun materiale con quest'ultima proprietà, la quale viola entrambe le "condizioni sull'energia" alla base di teoremi molto importanti e verificati della relatività generale. L'esistenza di questa materia non può essere esclusa a priori, visto che non esiste prova sperimentale o matematica della sua irrealisticità fisica, ma non essendo mai stata osservata è importante assicurarsi di impiegarne il meno possibile nel wormhole: questo ci porterà a mostrare che i wormholes in cui il materiale esotico presenta una densità di energia negativa per gli osservatori statici sono i più adatti al viaggio interstellare.

Cornered Asymptotically Hyperbolic Metrics

Thesis (Ph.D.)--University of Washington, 2016-08

The asymptotics of an amplitude for the 4-simplex

An expression for the oscillatory part of an asymptotic formula for the relativistic spin network amplitude for a 4-simplex is given. The amplitude depends on specified areas for each two-dimensional face in the 4-simplex. The asymptotic formula has a contribution from each flat Euclidean metric on the 4-simplex which agrees with the given areas. The oscillatory part of each contribution is determined by the Regge calculus Einstein action for that geometry.

Sasakian quiver gauge theories and instantons on cones over lens 5-spaces

We consider SU(3)-equivariant dimensional reduction of Yang Mills theory over certain cyclic orbifolds of the 5-sphere which are Sasaki-Einstein manifolds. We obtain new quiver gauge theories extending those induced via reduction over the leaf spaces of the characteristic foliation of the Sasaki-Einstein structure, which are projective planes. We describe the Higgs branches of these quiver gauge theories as moduli spaces of spherically symmetric instantons which are SU(3)-equivariant solutions to the Hermitian Yang-Mills equations on the associated Calabi-Yau cones, and further compare them to moduli spaces of translationally-invariant instantons on the cones. We provide an explicit unified construction of these moduli spaces as Kahler quotients and show that they have the same cyclic orbifold singularities as the cones over the lens 5-spaces. (C) 2015 The Authors. Published by Elsevier B.V.

Degenerate mixtures of rubidium and ytterbium for engineering open quantum systems

In the last two decades, experimental progress in controlling cold atoms and ions now allows us to manipulate fragile quantum systems with an unprecedented degree of precision. This has been made possible by the ability to isolate small ensembles of atoms and ions from noisy environments, creating truly closed quantum systems which decouple from dissipative channels. However in recent years, several proposals have considered the possibility of harnessing dissipation in open systems, not only to cool degenerate gases to currently unattainable temperatures, but also to engineer a variety of interesting many-body states. This thesis will describe progress made towards building a degenerate gas apparatus that will soon be capable of realizing these proposals. An ultracold gas of ytterbium atoms, trapped by a species-selective lattice will be immersed into a Bose-Einstein condensate (BEC) of rubidium atoms which will act as a bath. Here we describe the challenges encountered in making a degenerate mixture of rubidium and ytterbium atoms and present two experiments performed on the path to creating a controllable open quantum system. The first experiment will describe the measurement of a tune-out wavelength where the light shift of $\Rb{87}$ vanishes. This wavelength was used to create a species-selective trap for ytterbium atoms. Furthermore, the measurement of this wavelength allowed us to extract the dipole matrix element of the $5s \rightarrow 6p$ transition in $\Rb{87}$ with an extraordinary degree of precision. Our method to extract matrix elements has found use in atomic clocks where precise knowledge of transition strengths is necessary to account for minute blackbody radiation shifts. The second experiment will present the first realization of a degenerate Bose-Fermi mixture of rubidium and ytterbium atoms. Using a three-color optical dipole trap (ODT), we were able to create a highly-tunable, species-selective potential for rubidium and ytterbium atoms which allowed us to use $\Rb{87}$ to sympathetically cool $\Yb{171}$ to degeneracy with minimal loss. This mixture is the first milestone creating the lattice-bath system and will soon be used to implement novel cooling schemes and explore the rich physics of dissipation.

Phase Transitions in Engineered Ultracold Quantum Systems

The study of quantum degenerate gases has many applications in topics such as condensed matter dynamics, precision measurements and quantum phase transitions. We built an apparatus to create 87Rb Bose-Einstein condensates (BECs) and generated, via optical and magnetic interactions, novel quantum systems in which we studied the contained phase transitions. For our first experiment we quenched multi-spin component BECs from a miscible to dynamically unstable immiscible state. The transition rapidly drives any spin fluctuations with a coherent growth process driving the formation of numerous spin polarized domains. At much longer times these domains coarsen as the system approaches equilibrium. For our second experiment we explored the magnetic phases present in a spin-1 spin-orbit coupled BEC and the contained quantum phase transitions. We observed ferromagnetic and unpolarized phases which are stabilized by the spin-orbit coupling’s explicit locking between spin and motion. These two phases are separated by a critical curve containing both first-order and second-order transitions joined at a critical point. The narrow first-order transition gives rise to long-lived metastable states. For our third experiment we prepared independent BECs in a double-well potential, with an artificial magnetic field between the BECs. We transitioned to a single BEC by lowering the barrier while expanding the region of artificial field to cover the resulting single BEC. We compared the vortex distribution nucleated via conventional dynamics to those produced by our procedure, showing our dynamical process populates vortices much more rapidly and in larger number than conventional nucleation.

N=4 supersymmetric AdS(5) vacua and their moduli spaces

We classify the N = 4 supersymmetric AdS(5) backgrounds that arise as solutions of five-dimensional N = 4 gauged supergravity. We express our results in terms of the allowed embedding tensor components and identify the structure of the associated gauge groups. We show that the moduli space of these AdS vacua is of the form SU(1, m)/ (U(1) x SU(m)) and discuss our results regarding holographically dual N = 2 SCFTs and their conformal manifolds.

A high-flux BEC source for mobile atom interferometers (vol 17, 065001, 2015)

Erratum to: A high-flux BEC source for mobile atom interferometers in: New Journal of Physics 17 (2015) 065001

A high-flux BEC source for mobile atom interferometers

Quantum sensors based on coherent matter-waves are precise measurement devices whose ultimate accuracy is achieved with Bose-Einstein condensates (BECs) in extended free fall. This is ideally realized in microgravity environments such as drop towers, ballistic rockets and space platforms. However, the transition from lab-based BEC machines to robust and mobile sources with comparable performance is a challenging endeavor. Here we report on the realization of a miniaturized setup, generating a flux of 4x10(5) quantum degenerate Rb-87 atoms every 1.6 s. Ensembles of 1 x 10(5) atoms can be produced at a 1 Hz rate. This is achieved by loading a cold atomic beam directly into a multi-layer atom chip that is designed for efficient transfer from laser-cooled to magnetically trapped clouds. The attained flux of degenerate atoms is on par with current lab-based BEC experiments while offering significantly higher repetition rates. Additionally, the flux is approaching those of current interferometers employing Raman-type velocity selection of laser-cooled atoms. The compact and robust design allows for mobile operation in a variety of demanding environments and paves the way for transportable high-precision quantum sensors.

Position-dependent spin-orbit coupling for ultracold atoms

We theoretically explore atomic Bose-Einstein condensates (BECs) subject to position-dependent spin-orbit coupling (SOC). This SOC can be produced by cyclically laser coupling four internal atomic ground (or metastable) states in an environment where the detuning from resonance depends on position. The resulting spin-orbit coupled BEC (SOBEC) phase separates into domains, each of which contain density modulations-stripes-aligned either along the x or y direction. In each domain, the stripe orientation is determined by the sign of the local detuning. When these stripes have mismatched spatial periods along domain boundaries, non-trivial topological spin textures form at the interface, including skyrmions-like spin vortices and anti-vortices. In contrast to vortices present in conventional rotating BECs, these spin-vortices are stable topological defects that are not present in the corresponding homogenous stripe-phase SOBECs.