High voltage cathodes for Na-ion batteries: Na3V2O2x(PO4)2F3-2x system

254 p : il, graf. col.

Dendrites Inhibition in Rechargeable Lithium Metal Batteries

The specific high energy and power capacities of rechargeable lithium metal (Li⁰) batteries are ideally suited to portable devices and are valuable as storage units for intermittent renewable energy sources. Lithium, the lightest and most electropositive metal, would be the optimal anode material for rechargeable batteries if it were not for the fact that such devices fail unexpectedly by short-circuiting via the dendrites that grow across electrodes upon recharging. This phenomenon poses a major safety issue because it triggers a series of adverse events that start with overheating, potentially followed by the thermal decomposition and ultimately the ignition of the organic solvents used in such devices.

In this thesis, we developed experimental platform for monitoring and quantifying the dendrite populations grown in a Li battery prototype upon charging under various conditions. We explored the effects of pulse charging in the kHz range and temperature on dendrite growth, and also on loss capacity into detached “dead” lithium particles.

Simultaneously, we developed a computational framework for understanding the dynamics of dendrite propagation. The coarse-grained Monte Carlo model assisted us in the interpretation of pulsing experiments, whereas MD calculations provided insights into the mechanism of dendrites thermal relaxation. We also developed a computational framework for measuring the dead lithium crystals from the experimental images.

Wide Field-of-view Microscopes and Endoscopes for Time-lapse Imaging and High-throughput Screening

Wide field-of-view (FOV) microscopy is of high importance to biological research and clinical diagnosis where a high-throughput screening of samples is needed. This thesis presents the development of several novel wide FOV imaging technologies and demonstrates their capabilities in longitudinal imaging of living organisms, on the scale of viral plaques to live cells and tissues.

The ePetri Dish is a wide FOV on-chip bright-field microscope. Here we applied an ePetri platform for plaque analysis of murine norovirus 1 (MNV-1). The ePetri offers the ability to dynamically track plaques at the individual cell death event level over a wide FOV of 6 mm × 4 mm at 30 min intervals. A density-based clustering algorithm is used to analyze the spatial-temporal distribution of cell death events to identify plaques at their earliest stages. We also demonstrate the capabilities of the ePetri in viral titer count and dynamically monitoring plaque formation, growth, and the influence of antiviral drugs.

We developed another wide FOV imaging technique, the Talbot microscope, for the fluorescence imaging of live cells. The Talbot microscope takes advantage of the Talbot effect and can generate a focal spot array to scan the fluorescence samples directly on-chip. It has a resolution of 1.2 μm and a FOV of ~13 mm². We further upgraded the Talbot microscope for the long-term time-lapse fluorescence imaging of live cell cultures, and analyzed the cells’ dynamic response to an anticancer drug.

We present two wide FOV endoscopes for tissue imaging, named the AnCam and the PanCam. The AnCam is based on the contact image sensor (CIS) technology, and can scan the whole anal canal within 10 seconds with a resolution of 89 μm, a maximum FOV of 100 mm × 120 mm, and a depth-of-field (DOF) of 0.65 mm. We also demonstrate the performance of the AnCam in whole anal canal imaging in both animal models and real patients. In addition to this, the PanCam is based on a smartphone platform integrated with a panoramic annular lens (PAL), and can capture a FOV of 18 mm × 120 mm in a single shot with a resolution of 100─140 μm. In this work we demonstrate the PanCam’s performance in imaging a stained tissue sample.

Stability of Electrode-Electrolyte Interfaces during Charging in Lithium Batteries

In this thesis we study the growth of a Li electrode-electrolyte interface in the presence of an elastic prestress. In particular, we focus our interest on Li-air batteries with a solid electrolyte, LIPON, which is a new type of secondary or rechargeable battery. Theoretical studies and experimental evidence show that during the process of charging the battery the replated lithium adds unevenly to the electrode surface. This phenomenon eventually leads to dendrite formation as the battery is charged and discharged numerous times. In order to suppress or alleviate this deleterious effect of dendrite growth, we put forth a study based on a linear stability analysis. Taking into account all the mechanisms of mass transport and interfacial kinetics, we model the evolution of the interface. We find that, in the absence of stress, the stability of a planar interface depends on interfacial diffusion properties and interfacial energy. Specifically, if Herring-Mullins capillarity-driven interfacial diffusion is accounted for, interfaces are unstable against all perturbations of wavenumber larger than a critical value. We find that the effect of an elastic prestress is always to stabilize planar interfacial growth by increasing the critical wavenumber for instability. A parametric study results in quantifying the extent of the prestress stabilization in a manner that can potentially be used in the design of Li-air batteries. Moreover, employing the theory of finite differences we numerically solve the equation that describes the evolution of the surface profile and present visualization results of the surface evolution by time. Lastly, numerical simulations performed in a commercial finite element software validate the theoretical formulation of the interfacial elastic energy change with respect to the planar interface.

PCR-SSCP and Isoelectric Focusing as Screening Methods for Identification of (Sub-) Tropical Fish Species

To ensure the authentication of fishery products lacking biological characters, rapid species identification methods are required. Two DNA- and protein-based methods, PCR-SSCP (polymerase chain reaction - single strand conformation polymorphism) of a 464 bp segment of the cytochrome b – gene and isoelectric focusing (IEF) of water-soluble proteins from fish fillets, were applied to identify fillets of (sub-) tropical fish species available on the European market. Among the samples analysed were two taxonomically identified species from the family Sciaenidae and one from Sphyraenidae. By comparison of DNA- and protein patterns of different samples, information about intra-species variability of patterns, and homogeneity of batches (e.g. fillet blocks or bags) can be obtained. PCR-SSCP and IEF may be useful for pre-checking of a large number of samples by food control laboratories. Zusammenfassung Zur Sicherstellung der Authentizität von Fischerei-Erzeugnissen ohne biologische Merkmale sind schnelle Verfahren zur Speziesidentifizierung hilfreich. Zwei Methoden der DNA- bzw. Protein-Analyse wurden eingesetzt, um Filets (sub-) tropischer Fischarten, die auf dem europäischen Markt angeboten werden, zu identifizieren. Bei diesen Methoden handelt es sich um die PCR-SSCP (Polymerase-Kettenreaktion – Einzelstrang-Konformationspolymorphismus) – Analyse der PCR-Produkte und die IEF (isoelektrische Fokussierung) der wasserlöslichen Fischmuskelproteine. Unter den untersuchten Proben waren zwei taxonomisch bestimmte Arten aus der Familie Sciaenidae und eine Spezies aus der Familie Sphyraenidae. Durch Vergleich der DNA- bzw. Proteinmuster lassen sich Informationen über die intra-spezifische Variabilität solcher Muster und die Einheitlichkeit von Partien (beispielsweise Filetblöcke oder Filetbeutel) gewinnen. PCR-SSCP und IEF können in Laboratorien der Lebensmittelüberwachung als Vortest gerade bei hohen Probenzahlen sinnvoll eingesetzt werden.

Phosphate treatment of frozen prawns. Pt. 1. Screening of various phosphates for prevention of drip loss

Various phosphates and their mixtures were screened for their efficiency of preventing drip loss in frozen prawns. The effectiveness of the phosphates decreased in the following order: Sodium tripolyphosphate — Sodium pyrophosphate — Sodium hexametaphosphate Sodium metaphosphate — Sodium dihydrogen phosphate; the last two being ineffective. Even though thaw drip loss was reduced by the above treatments the organoleptic quality of the thawed as well as cooked products was unsatisfactory, discoloration being the major defect. A solution of a mixture of 12% sodium tripolyphosphate and 8.6% sodium dihydrogen phosphate or 2% citric acid in water when used as dip prevented thaw drip loss, improved cooked yield and organoleptic quality without adversely affecting the biochemical characteristics. Commercial scale trials showed that the results are highly reproducible.

Screening of healthcare workers for tuberculosis: development and validation of a new health economic model to inform practice

Methods for determining cost-effectiveness of different treatments are well established, unlike appraisal of non-drug interventions, including novel diagnostics and biomarkers.

Evaluating the impact of V2G services on the degradation of batteries in PHEV and EV

Many researchers and industry observers claim that electric vehicles (EV) and plug-in hybrid electric vehicles (PHEV) could provide vehicle-to-grid (V2G) bulk energy and ancillary services to an electricity network. This work quantified the impact on various battery characteristics whilst providing such services. The sensitivity of the impact of V2G services on battery degradation was assessed for EV and PHEV for different battery capacities, charging regimes, and battery depth of discharge. Battery degradation was found to be most dependent on energy throughput for both the EV and PHEV powertrains, but was most sensitive to charging regime (for EVs) and battery capacity (for PHEVs). When providing ancillary services, battery degradation in both powertrains was most sensitive to individual vehicle battery depth of discharge. Degradation arising from both bulk energy and ancillary services could be minimised by reducing the battery capacity of the vehicle, restricting the number of hours connected and reducing the depth of discharge of each vehicle for ancillary services. Regardless, best case minimum impacts of providing V2G services are severe such as to require multiple battery pack replacements over the vehicle lifetime. © 2013 Elsevier Ltd.

Nonequilibrium dynamics of photoexcited electrons in graphene: Collinear scattering, Auger processes, and the impact of screening

We present a combined analytical and numerical study of the early stages (sub-100-fs) of the nonequilibrium dynamics of photoexcited electrons in graphene. We employ the semiclassical Boltzmann equation with a collision integral that includes contributions from electron-electron (e-e) and electron-optical phonon interactions. Taking advantage of circular symmetry and employing the massless Dirac fermion (MDF) Hamiltonian, we are able to perform an essentially analytical study of the e-e contribution to the collision integral. This allows us to take particular care of subtle collinear scattering processes - processes in which incoming and outgoing momenta of the scattering particles lie on the same line - including carrier multiplication (CM) and Auger recombination (AR). These processes have a vanishing phase space for two-dimensional MDF bare bands. However, we argue that electron-lifetime effects, seen in experiments based on angle-resolved photoemission spectroscopy, provide a natural pathway to regularize this pathology, yielding a finite contribution due to CM and AR to the Coulomb collision integral. Finally, we discuss in detail the role of physics beyond the Fermi golden rule by including screening in the matrix element of the Coulomb interaction at the level of the random phase approximation (RPA), focusing in particular on the consequences of various approximations including static RPA screening, which maximizes the impact of CM and AR processes, and dynamical RPA screening, which completely suppresses them. © 2013 American Physical Society.

Hierarchically structured nanocarbon electrodes for flexible solid lithium batteries

The ever increasing demand for storage of electrical energy in portable electronic devices and electric vehicles is driving technological improvements in rechargeable batteries. Lithium (Li) batteries have many advantages over other rechargeable battery technologies, including high specific energy and energy density, operation over a wide range of temperatures (-40 to 70. °C) and a low self-discharge rate, which translates into a long shelf-life (~10 years) [1]. However, upon release of the first generation of rechargeable Li batteries, explosions related to the shorting of the circuit through Li dendrites bridging the anode and cathode were observed. As a result, Li metal batteries today are generally relegated to non-rechargeable primary battery applications, because the dendritic growth of Li is associated with the charging and discharging process. However, there still remain significant advantages in realizing rechargeable secondary batteries based on Li metal anodes because they possess superior electrical conductivity, higher specific energy and lower heat generation due to lower internal resistance. One of the most practical solutions is to use a solid polymer electrolyte to act as a physical barrier against dendrite growth. This may enable the use of Li metal once again in rechargeable secondary batteries [2]. Here we report a flexible and solid Li battery using a polymer electrolyte with a hierarchical and highly porous nanocarbon electrode comprising aligned multiwalled carbon nanotubes (CNTs) and carbon nanohorns (CNHs). Electrodes with high specific surface area are realized through the combination of CNHs with CNTs and provide a significant performance enhancement to the solid Li battery performance. © 2013 Elsevier Ltd.