In Situ Formation of Micron-Scale Li-Metal Anodes with High Cyclability

Scanning probe microscopy methods have been used to electrodeposit and cycle micron-scale Li anodes deposited electrochemically under nanofabricated Au current collectors. An average Li volume of 5 x 10(8) nm(3) was deposited and cycled with 100% coulombic efficiency for similar to 160 cycles. Integrated charge/discharge values agree with before/after topography, as well as in situ dilatometry, suggesting this is a reliable method to study solid-state electrochemical processes. In this work we illustrate the possibility to deposit highly cyclable nanometer thick Li electrodes by mature SPM and nanofab techniques which can pave the way for inexpensive nanoscale battery arrays. 

In-situ Monitoring of Solid Oxide Electrolysis Cells

High temperature co-electrolysis of steam and carbon dioxide using a solid oxide cell (SOC) has been shown to be an efficient route to produce syngas (CO + H-2), which can then be converted to synthetic fuel. Optimization of co-electrolysis requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the SOC during operation. Thermal imaging, Raman spectroscopy and Diffuse Reflectance Infrared Fourier Transform Spectroscopy are being developed to probe in-situ both the reactions occurring during operation and any associated changes within the structure of the electrodes and electrolyte. Here we discuss the challenges in designing experimental apparatus suitable for high temperature operation with optical spectroscopic access to the areas of the SOC that are of interest. In particular, issues with sealing, temperature gradients, signal strength and cell configuration are discussed and final designs are presented. Preliminary results obtained during co-electrolysis operation are also presented.

Development of a Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) Cell for the In Situ Analysis of Co-Electrolysis in a Solid Oxide Cell

Co-electrolysis of carbon dioxide and steam has been shown to be an efficient way to produce syngas, however further optimisation requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the solid oxide cell (SOC) during operation. Whilst electrochemical measurements are currently conducted in situ, many analytical techniques can only be used ex situ and may even be destructive to the cell (e.g. SEM imaging of microstructure). In order to fully understand and characterise co-electrolysis, in situ monitoring of the reactants, products and SOC is necessary. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) is ideal for in situ monitoring of co-electrolysis as both gaseous and adsorbed CO and CO2 species can be detected, however it has previously not been used for this purpose. The challenges of designing an experimental rig which allows optical access alongside electrochemical measurements at high temperature and operates in a dual atmosphere are discussed. The rig developed has thus far been used for symmetric cell testing at temperatures from 450[degree]C to 600[degree]C. Under a CO atmosphere, significant changes in spectra were observed even over a simple Au|10Sc1CeSZ|Au SOC. The changes relate to a combination of CO oxidation, the water gas shift reaction and carbonate formation and decomposition processes, with the dominant process being both potential and temperature dependent.

The use of a novel compact fluorosensor for in situ monitoring of the photocatalytic destruction of methylene blue dye effluents

The use of TiO 2 photocatalysis for the destruction of dyes such as methylene blue has been extensively reported. One of the challenges faced in both the laboratory and large scale water treatment plants is the fact that the samples have to be removed from the reactor vessel and the catalyst separated prior to analysis being undertaken. In this paper we report the development of a simple fluorimeter instrument and its use in monitoring the photocatalytic destruction of methylene blue dyes in the presence of catalyst suspensions. The results reported show that the instrument provides an effective method for in situ monitoring of the photocatalytic destruction of fluorescent dyes hence allowing more accurate measurement due to the minimisation of sample loss and cross contamination. Furthermore it also provides a method for real time monitoring of the dye pollutant destruction in large scale photocatalytic reactors.

Voltammetric in situ measurements of heavy metals in soil using a portable electrochemical instrument

This paper presents a portable electrochemical instrument capable of detecting and identifying heavy metals in soil, in situ. The instrument has been developed for use in a variety of situations to facilitate contaminated land surveys, avoiding expensive and time-consuming procedures. The system uses differential pulse anodic stripping voltammetry which is a precise and sensitive analytical method with excellent limits of detection. The identification of metals is based on a statistical microprocessor-based method. The instrument is capable of detecting six different toxic metals (lead, cadmium, zinc, nickel, mercury and copper) with good sensitivity

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm^-1 (A1g), 197 cm^-1 (Eg), 398 cm^-1 (B1g), 515 cm^-1 (A1g), and 640 cm^-1 (Eg) assigned to anatase which were replaced by bands at 143 cm^-1 (B1g), 235 cm^-1 (2 phonon process), 448 cm^-1 (Eg) and 612 cm^-1 (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process

In situ preparation of 3D graphene aerogels@hierarchical Fe3O4 nanoclusters as high rate and long cycle anode materials for lithium ion batteries

We describe a novel strategy for in situ fabrication of hierarchical Fe₃O₄ nanoclusters-GAs. Fe₃O₄ NCs-GAs deliver excellent rate capability (the reversible capacities obtained were 1442, 392 and 118 mA h g^-1 at 0.1C, 12C and 35C rates), and a high reversible capacity of 577 mA h g^-1 over 300 cycles at the current density of 5.2 A g^-1 (6C).

In situ synthesis of LiV3O8 nanorods on graphene as high rate-performance cathode materials for rechargeable lithium batteries

We developed a facile two-step hydrothermal procedure to prepare hybrid materials of LiV₃O₈ nanorods on graphene sheets. The special structure endows them with the high-rate transportation of electrolyte ions and electrons throughout the electrode matrix, resulting in remarkable electrochemical performance when they were used as cathodes in rechargeable lithium batteries. © 2013 The Royal Society of Chemistry.

In-situ formation of solidified hydrogen thin-membrane targets using a pulse tube cryocooler

An account is given of the Central Laser Facility's work to produce a cryogenic hydrogen targetry system using a pulse tube cryocooler. Due to the increasing demand for low Z thin laser targets, CLF (in collaboration with TUD) have been developing a system which allows the production of solid hydrogen membranes by engineering a design which can achieve this remotely; enabling the gas injection, condensation and solidification of hydrogen without compromising the vacuum of the target chamber. A dynamic sealing mechanism was integrated which allows targets to be grown and then remotely exposed to open vacuum for laser interaction. Further research was conducted on the survivability of the cryogenic targets which concluded that a warm gas effect causes temperature spiking when exposing the solidified hydrogen to the outer vacuum. This effect was shown to be mitigated by improving the pumping capacity of the environment and reducing the minimum temperature obtainable on the target mount. This was achieved by developing a two-stage radiation shield encased with superinsulating blanketing; reducing the base temperature from 14 0.5 K to 7.2 0.2 K about the coldhead as well as improving temperature control stability following the installation of a high-performance temperature controller and sensor apparatus. The system was delivered experimentally and in July 2014 the first laser shots were taken upon hydrogen targets in the Vulcan TAP facility.

Characterisation of fluidised bed granulation processes using in situ Raman spectroscopy

Previous work by the authors Walker et al. [2007b. Fluidised bed characterisation using Raman spectroscopy: applications to pharmaceutical processing. Chemical Engineering Science 62, 3832–3838] illustrated that Raman spectroscopy could be used to provide 3-D maps of the concentration and chemical structure of particles in motion in a fluidised bed, within a relatively short (120 s) time window. Moreover, we reported that the technique, as outlined, has the potential to give detailed in-situ information on how the structure and composition of granules/powders within the fluidised bed (dryer or granulator) vary with the position and evolve with time. In this study we extended the original work by shortening the time window of the Raman spectroscopic analysis to 10 s, which has allowed the in-situ real-time characterisation of a fluidised bed granulation process. Here we show an important new use of the technique which allows in-situ measurement of the composition of the material within the fluidised bed in three spatial dimensions and as a function of time. This is achieved by recording Raman spectra using a probe positioned within the fluidised bed on a long-travel x–y–z stage. In these experiments the absolute Raman intensity is used to provide a direct measure of the amount of any given material in the probed volume, i.e. a particle density. Particle density profiles have been calculated over the granulation time and show how the volume of the fluidised bed decreases with an increase mean granule size. The Raman spectroscopy analysis indicated that nucleation/coalescence in this co-melt fluidised hot melt granulation system occurred over a relatively short time frame (t<30 s). The Raman spectroscopic technique demonstrated accurate correlation with independent granulation experiments which provided particle size distribution analysis. The similarity of the data indicates that the Raman spectra accurately represent solids ratios within the bed, and thus the techniques quantitative capabilities for future use in the pharmaceutical industry.

In situ catalyst activity control in a novel membrane reactor-Reaction driven wireless electrochemical promotion of catalysis

A dual chamber membrane reactor was used in order to study the effect of macroscopically applied oxygen chemical potential differences to a platinum catalyst supported on a mixed oxygen ion and electronic conducting membrane. It is believed that the oxygen chemical potential difference imposed by the use of an oxygen sweep in one of the reactor chambers causes the back-spillover of oxygen species from the support onto the catalyst surface, resulting in the modification of the catalytic activity. The use of different sweep gases, such as ethylene and hydrogen was investigated as the means to reverse the rate modification by removing the spilt over species from the catalyst surface and returning the system to its initial state. Oxygen sweep in general had a positive effect on the reaction rate with rate increases up to 20% measured. Experimental results showed that hydrogen is a more potent sweep gas than ethylene in terms of the ability to reverse rate modification. A 10% rate loss was observed when using an ethylene sweep as compared with an almost 60% rate decrease when hydrogen was used as the sweep gas. © 2009 Elsevier Ltd. All rights reserved.

In situ cross-calibration of in-fibre Bragg Grating and Electrical Resistance Strain Gauges for structural monitoring using an extensometer

Special issue on Sensor Systems for Structural Health Monitoring Abstract—This study addresses the direct calibration of optical fiber strain sensors used for structural monitoring and is carried out in situ. The behavior of fiber-Bragg-grating-based sensor systems when attached to metal bars, in a manner representative of their use as reinforcement bars in structures, was examined and their response calibrated. To ensure the validity of the measurements,this was done using an extensometer with a further calibrationagainst the response of electrical resistance strain gauges, often conventionally used, for comparison. The results show a repeatable calibration generating a suitable geometric factor of extension to strain for these sensors, to enable accurate strain data to be obtained when the fiber-optic sensor system is in use in structural monitoring applications.

Monitoring of Corrosion in Structural Reinforcing Bars: performance comparison using in-situ fibre optic and electric wire strain gauge systems

Abstract This work addresses the problems of effective in situ measurement of the initiation or the rate of steel corrosion in reinforced concrete structures through the use of optical fiber sensor systems. By undertaking a series of tests over prolonged periods, coupled with acceleration of corrosion, the performance of fiber Bragg grating-based sensor systems attached to high-tensile steel reinforcement bars (ldquorebarsrdquo), and cast into concrete blocks was determined, and the results compared with those from conventional strain gauges where appropriate. The results show the benefits in the use of optical fiber networks under these circumstances and their ability to deliver data when conventional sensors failed.