No description available.

No description available.

Four topics are presented in this thesis. Firstly, a new design for a combinatorial electrochemical cell plate based on circuit board technology is described. The new combinatorial cell plate was tested using sputtered silicon and capacity as a function of mass was determined. The measured specific capacity was 3580 mAh/g, which corresponds to Li15Si4 stoichiometry. The irreversible capacity was measured to be less than 2% of the reversible capacity. This design reduced the spurious capacity that came from the lead pattern of the old plate. Second, the role of oxygen content on the electrochemical properties of sputtered Si1-xOx was investigated. All the prepared thin film samples had an amorphous or nanostructured nature. The measured specific capacity (first charge) suggests that Si1-xOx is made up of amorphous silicon that reacts reversibly with lithium, and SiO2 that forms inactive Li4SiO4 after the first lithiation. The current study shows that the irreversible capacity is directly proportional to the oxygen content. This study indicates clearly that in order to produce material with high capacity, oxygen should be minimized to reduce Li consumption during Li4SiO4 formation. However, the Si:O ratio should be optimized to get a reasonable active: inactive ratio. Third, a systematic study to investigate the effect of the addition of carbon on the electrochemical performance of the Sn-Si binary is reported. This study involved the preparation and investigation of three pseudobinary libraries. The addition of carbon was found to inhibit the aggregation of tin and reduce the two-phase coexistence regions as evidenced by smooth differential capacity plots. This was reflected in the improved electrochemical performance such as reversible capacity and cycleability. Fourth, an investigation of carbon-rich alloys of Fe1-xCx is reported. Both x-ray diffraction and 57Fe Mössbauer spectroscopy were employed to get insight into the structural properties of this system. X-ray diffraction revealed the amorphous or nanostructured nature of all samples with different Fe:C ratios. The distribution of hyperfine parameters extracted from the Mössbauer analysis shows the existence of two components suggesting that Fe exists in two distinct sites: (1) Fe surrounded with Fe neighbors and (2) Fe surrounded with C neighbors. The asymmetric environment was found more pronounced as carbon content increases in the films. This was reflected by high quadrupole splitting in excess of 1.0 mm/s.

Düsseldorf, Universiẗat, Diss., 2004.

Battery research has been going full steam and with that the search for alternative anodes. Among many proposed electrode materials, little attention has been given to phosphorus. Phosphorus boasts the third highest gravimetric charge capacity and the highest volumetric charge capacity of all elements. Because of that, it would be an attractive battery anode material were it not for its poor cyclability with significant capacity loss immediately after the first cycle. This is known to be the consequence of considerable volume changes of phosphorus during charge/discharge cycles. In this work, we propose circumventing this issue by mixing amorphous red phosphorus with carbon nanotubes. By employing a non-destructive sublimation-deposition method, we have synthesized composites where the synergetic effect between phosphorus and carbon nanotubes allow for an improvement in the electrochemical performance of battery anodes. In fact, it has been shown that carbon nanotubes can act as an effective buffer to phosphorus volumetric expansions and contractions during charging and discharging of the half-cells [1]. By modifying the synthesis parameters, we have also been able to change the degree of crystallinity of the phosphorus matrix in the composites. In fact, the less common phase of red phosphorus, named fibrous phosphorus, was obtained, and that explains some of the varying electrochemical performances observed in the composites. Overall, it is found that a higher surface area of amorphous phosphorus allows for a better anode material when using single-walled carbon nanotubes as fillers.

No description available.

A laboratory scale delayed coking process was used to produce petrol precursors, diesel precursors, methane rich gas, green and calcined coke from five previously untested South African heavy petroleum residues. The ash content of the heavy petroleum residues was found to be detrimental to the microstructure of the green coke and Coefficient of Thermal Expansion (CTE) of the calcined coke. The sulphur content of the calcined cokes produced was found to be in-line with typical global anode grade cokes. De-ashing of the feedstock would be necessary to produce anode grade fillers for the aluminium industry. The local production of anode grade coke would serve to reduce imports and supply the aluminium smelters on the east coast of South Africa. The heavy petroleum residues (also known as heavy fuel oil) are currently used as bunker fuel in the shipping industry and are responsible for substantial air pollution. Delayed coking of these residues could extend the production of petrol and diesel per barrel of imported crude oil and reduce the effect on South Africa’s balance of payments deficit and impact the environment in a beneficial manner with respect to carbon dioxide and sulphur emissions. The research also evaluated the replacement of heavy fuel oil with marine diesel produced by delayed coking of the former. Marine diesel was found to emit less sulphur oxides and have a higher energy density per unit of carbon dioxide emitted. While seawater scrubbing of the heavy fuel oil would be more cost effective in reducing the sulphur oxide emissions, it would not contribute to carbon dioxide reductions. The research created a hypothetical scenario to determine the required value of Clean Development Mechanism credits for a marine diesel replacement, were shipping to be incorporated under the Kyoto Protocol in future

The demand for high performance Lithium-ion batteries (LIBs) is increasing due to widespread use of portable devices and electric vehicles. Silicon (Si) is one of the most attractive candidate anode materials for the next generation LIBs because of its high theoretical capacity (3,578 mAh/g) and low operation potential (~0.4 V vs Li+/Li). However, the high volume change (>300%) during Lithium ion insertion/extraction leads to poor cycle life. The goal of this work is to improve the electrochemical performance of Si/C composite anode in LIBs. Two strategies have been employed: to explore spatial arrangement in micro-sized Si and to use Si/graphene nanocomposites. A unique branched microsized Si with carbon coating was made and demonstrated promising electrochemical performance with a high active material loading ratio of 2 mg/cm2, large initial discharge capacity of 3,153 mAh/g and good capacity retention of 1,133 mAh/g at the 100th cycle at 1/4C current rate. Exploring the spatial structure of microsized Si with its advantages of low cost, easy dispersion, and immediate compatibility with the prevailing electrode manufacturing technology, may indicate a practical approach for high energy density, large-scale Si anode manufacturing. For Si/Graphene nanocomposites, the impact of particle size, surface treatment and graphene quality were investigated. It was found that the electrochemical performance of Si/Graphene anode was improved by surface treatment and use of graphene with large surface area and high defect density. The 100 nm Si/Graphene nanocomposites presented the initial capacity of 2,737 mAh/g and good cycling performance with a capacity of 1,563 mAh/g after 100 cycles at 1/2C current rate. The findings provided helpful insights for design of different types of graphene nanocomposite anodes.

Over the last decades, lithium-ion batteries have grown more important and substituted other energy storage systems. Due to advantages such as high energy density and low self-discharge, the lithium-ion battery has taken its part in the rechargeable energy storage market, and it is now found in most laptops, cameras and mobile phones. With the increasing demands for electrical vehicles and stationary energy storage systems, there is a necessity for improved lithium-ion battery materials. In this thesis several alternative electrode materials have been examined with a main focus on the electrochemical characterisation. As an alternative to the commercial cathode LiCoO2, the LiMn2O4 cathode has been suggested due to its reduced toxicity, material abundance, reduced costs and increased specific capacity. On the anode side, several Sn-containing anodes have been investigated and steps to overcome the main challenge, the great volume expansion upon cycling, have been taken. In addition, a novel anode material group was synthesised at the University of Marburg and two substances of the lithium chalcogenidometalate networks were successfully characterised. The cathode material, LiMn2O4, was synthesised via the sol-gel technique and several coating methods such as dip-coating, electrophoretics and infiltration were investigated. The LiMn2O4 material was initially coated on a porous metal foam as a current collector, thus providing new possibilities as the porosity of the substrate increased, mechanical stability and adhesion improved and a 3-dimensional network was obtained. In order to compare the results of the LiMn2O4 cathode material on the novel current collector, the material was also coated on a standard metallic foil and characterised. The analysis followed via X-ray diffraction, electron microscopy, thermogravimetrical analysis and several electrochemical techniques. Tin containing anode materials were chosen due to the doubling of the theoretical capacity compared with the commercially used graphite. However, a great challenge lies with using tin or tin-containing anode materials. Upon lithiation of Sn, the material can expand up to 300 %, therefore a stabilising effect is necessary to avoid a collapse of the material. This work shows several new concepts and attempts to overcome this challenge, including SnO2 nanowires deposited via chemical vapour deposition on both metallic foam and standard current collectors. A new improvement consisted of the tin - carbon nanofibers where the nanofibers form a stabilising matrix that can partially buffer the volume change of the Sn particles. The synthesis of the Sn-containing anodes took place at the University of Cologne, while characterisation, cell preparation and optimising the electrode system were features of this thesis. In addition, a lithium chalcogenidometalate network proved to be an interesting, new anode material group. Both Li4MnSn2Se7 and Li4MnGe2S7 (synthesised at Philipps-Universität Marburg) were electrochemically examined to better understand the lithiation processes. Both materials obtained very high specific capacities and were found to be possible alternatives to the state-of-the art anodes. All the examined electrode materials were found to have some advantage over the commercially used LiCoO2 and graphite electrodes, and a thorough characterization of the materials was performed to understand the processes that took place. / Lithium-Ionen Batterien sind in den letzten Jahrzehnten immer wichtiger geworden und haben mittlerweile andere Energiespeichersysteme in weiten Bereichen ersetzt. Ihre hohe Energiedichte und niedrige Selbstentladung sind Gründe dafür, dass die Lithium-Ionen Batterie einen großen Teil des Marktes für wiederaufladbare Energiespeicher einnimmt und ist in Laptops, Kameras und Handys zu finden. Mit dem zunehmenden Interesse an Elektrofahrzeugen und stationären Energiespeichersystemen entstand der Bedarf an verbesserten Lithium-Ionen Batteriematerialien. Verschiedene alternative Elektrodenmaterialien mit einem Hauptfokus auf ihrer elektrochemischen Charakterisierung wurden in dieser Dissertation untersucht. Als eine Alternative zum kommerziellen LiCoO2 wurde LiMn2O4 als Kathode vorgeschlagen, hauptsächlich aufgrund der niedrigeren Toxizität, der Materialverfügbarkeit und der erhöhten spezifischen Ladung. Auf der Anodenseite wurden verschiedene Sn-haltige Anoden untersucht um das vorangige Problem der Volumenausdehnung beim Laden/Entladen zu lösen. Außerdem wurde mit den Lithium-Chalkogenidometallaten ein neuartiges Anodenmaterial synthetisiert und erfolgreich charakterisiert. Das LiMn2O4-Kathodenmaterial wurde mittels einer Sol-Gel-Methode hergestellt und verschiedene Beschichtungsmethoden wie, Tauchbeschichtung, Elektrophorese und Infiltration, untersucht. Zunächst wurde ein hochporöser metallischer Stromableiter mit dem LiMn2O4-Material beschichtet, was neue Elektrodenbauformen ermöglicht. Die Porosität des Substrats kann erhöht und die mechanische Stabilität und Haftung verbessert werden. Außerdem ist ein 3-D Netzwerk vorhanden. Ein Vergleich mit LiMn2O4 auf einer metallischen Standardfolie wurde durchgeführt und eine allgemeine Charakterisierung mittels Röntgenbeugungsanalyse, Elektronenmikroskopie, Thermogravimetrie und elektrochemischen Methoden folgte. Aufgrund ihrer im Vergleich zu kommerziellem Graphit verdoppelten theoretisch speicherbaren Ladung wurden zinnhaltige Anodenmaterialien gewählt. Es besteht jedoch eine große Herausforderung bei Sn-haltigen Anoden, da sich das Material bei Lithierung des Sn um bis zu 300 % ausdehnt. Ein stabilisierender Effekt ist nötig, um einen Zusammenbruch des Materials zu vermeiden. In dieser Arbeit werden neue Konzepte und Bestrebungen zur Lösung aufgezeigt. Dies umfasst die Abscheidung von SnO2-Nanodrähten auf metallische Schäume und auf glatte Stromableiter. Eine weitere Verbesserung besteht aus Sn-Kohlenstoffnanofasern, bei denen die Nanofasern ein stabilisierendes Gerüst darstellen, so dass die Volumenausdehnung der Sn-Partikel teilweise aufgenommen wird. Die Synthese der Sn-Anoden wurde an der Universität zu Köln durchgeführt, die weitere Charakterisierung, Zellpräperation und Optimierung des Elektrodensystems waren Schwerpunkte dieser Dissertation. Weiterhin hat sich das Lithium-Chalkogenidometallat Netzwerk als ein interessantes Anodenmaterial erwiesen. Beide Materialien, Li4MnSn2Se7 und Li4MnGe2S7 (hergestellt an der Philipps-Universität Marburg), wurden elektrochemisch analysiert, um die Lithierungsprozesse im Detail zu verstehen. Beide Materialien erreichen sehr hohe spezifische Ladungen und können als denkbare Alternativen zum Stand der Technik betrachten werden. Alle untersuchten neuen Elektrodenmaterialien zeigen Vorteile gegenüber der kommerziellen LiCoO2- und Graphit-Elektroden. Zum besseren Verständnis der grundlegenden Prozesse wurde eine umfassende Charakterisierung der Materialien durchgeführt.

This research is to synthesize polyaniline (PANI) thin film on the Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) by using potentiostatic deposition of electrochemical method. The hybrid film composed of PEDOT:PSS and PANI was fabricated to replace the ITO layer for polymer solar cells as an anode. In the future, the hybrid film can develop the flexible polymer solar cells. In this study, we fixed the total thickness of the hybrid film, and we investigated optical transmittance, conductivity, Highest Occupied Molecular Orbital (HOMO), surface roughness, and surface morphology of hybrid films by changing the ratio of PEDOT:PSS and PANI, and to discuss the factors on device efficiency. Then, we compared the device structures with anode made by PEDOT: PSS. We found the hybrid films fabricated with different ratio of PEDOT:PSS and PANI, and the HOMO results were similar. In addition, we found optical transmittance, conductivity, surface roughness, and surface morphology of hybrid films that varies with different ratio of PEDOT:PSS and PANI. The power conversion efficiencies of the device mainly were affected by the surface roughness and morphology of the hybrid film surface. Comparing to other parameters, the hybrid film fabricated by PEDOOT:PSS(280nm) and PANI(30nm) owns the most appropriate surface roughness and surface morphology. The power conversion efficiency(PCE) was up to 0.68%, and then via post-annealing of 90¢J 10 minutes the PCE was increase to 1.06% under AM 1.5G illumination based on PEDOT:PSS (280 nm) / PANI (30 nm) / P3HT: PCBM (100 nm) / Al (200 nm), and the device area of 0.16 cm2.