Caractéristiques d’antennes térahertz photoconductrices de type micro-ruban coplanaire

Ce projet de recherche a permis d'étudier l'émission d'un rayonnement térahertz (THz) par des antennes photoconductrices (PC) émettrices de type micro-ruban coplanaire. Ces antennes sont fabriquées sur substrats d'arséniure de gallium semi-isolant (GaAs-SI) ou sur ce même substrat ayant subit un traitement d'implantation ionique aux protons suivi d'un recuit thermique (GaAs:H). L'influence de ce procédé de fabrication sur les propriétés du matériau photoconducteur et sur les caractéristiques de l'antenne émettrice a été étudiée. Des mesures de photoconductivité résolue en temps effectuées sur les deux types de substrat montrent que le procédé d'implantation/recuit a eu pour effet de diminuer le temps de vie des photoporteurs de 630 ps à environ 4 ps, tandis que la mobilité n'est réduite que d'un facteur maximum de 1,6. Cette valeur de la mobilité des photoporteurs a par ailleurs été estimée à environ 100 cm$^2$/(V.s) pour le substrat GaAs:H. Les mesures électriques effectuées sur les antennes fabriquées sur les deux types de substrat montrent que le procédé d'implantation/recuit permet d'augmenter la résistivité de la couche active du dispositif d'un facteur 10 (elle passerait de 10$^{8}$ $\Omega$.cm pour le GaAs-SI à 10$^9$ $\Omega$.cm pour le GaAs:H). Les courbes courant-tension, en obscurité et sous illumination, de ces antennes suggèrent également que la densité de pièges profonds est fortement augmentée suite au traitement d'implantation/recuit. L'étude des caractéristiques des diverses antennes a permis de montrer l'intérêt de ce procédé de fabrication. Pour les antennes fabriquées sur GaAs:H, la largeur de bande est améliorée (elle atteint environ 3 THz) et l'amplitude du champ THz émis est augmentée par un facteur 1,4 (dans les mêmes conditions expérimentales). Le rapport signal/bruit des traces THz mesurées sur les antennes les plus performantes est $>$ 200. Une plus grande résistivité et une densité de pièges profonds plus élevée, permet d'appliquer de plus fortes tensions de polarisation sur ces antennes GaAs:H. Finalement, nos résultats ont montré que les améliorations des caractéristiques d'émission de ces antennes THz sont corrélées à la présence d'un champ électrique local plus élevé du coté de l'anode du dispositif.

Newly developed electrosynthesis of Layered Double Hydroxides: application to sensing, energy storage and conversion

Layered Double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, it does not usually allow for a fine control of the M(II)/M(III) ratio in the synthesized material and it is not suitable for large anions intercalation. Therefore, in this work a novel protocol has been proposed with the aim to overcome all these constraints using a method based on potentiodynamic synthesis. LDHs of controlled composition were prepared using different molar ratios of the trivalent to bivalent cations in the electrolytic solution ranging from 1:1 to 1:4. Moreover, we were able to produce electrochemically LDHs intercalated with carbon nanomaterials for the first time. A one-step procedure which contemporaneously allows for the Ni/Al-LDH synthesis, the reduction of graphene oxide (GO) and its intercalation inside the structure has been developed. The synthesised materials have been applied in several fields of interest. First of all, LDHs with a ratio 3:1 were exploited, and displayed good performances as catalysts for 5-(hydroxymethyl)furfural electro-oxidation, thus suggesting to carry out further investigation for applications in the field of industrial catalysis. The same materials, but with different metals ratios, were tested as catalysts for Oxygen Evolution Reaction, obtaining results comparable to LDHs synthesised by the classical co-precipitation method and also a better activity with respect to LDHs obtained by the potentiostatic approach. The composite material based on LDH and reduced graphene oxide was employed to fabricate a cathode of a hybrid supercapacitor coupled with an activated carbon anode. We can thus conclude that, to date, the potentiodynamic method has the greatest potential for the rapid synthesis of reproducible films of Co and Ni-based LDHs with controlled composition.

Towards eco-friendly batteries: concepts for lithium and sodium ion batteries

Several possibilities are arising aiming the development of “greener”, more sustainable energy storage systems. One point is the completely water-based processing of battery electrodes, thus being able to renounce the use of toxic solvents in the preparation process. Despite its advantage of lower cost and eco-friendlyness, there is the need of similar mechanical and electrochemichal behavior for boosting this preparation mode. Another point – accompanying the water-based processing - is the replacement of solvent-based polymer binders by water-based ones. These binders can be based on fluorinated, crude-oil based polymers on the one side, but also on naturally abundant and economic friendly biopolymers. The most common anode materials, graphite and lithium titanate (LTO), have been subjected a water-based preparation route with different binder systems. LTO is a promising anode material for lithium ion batteries (LIBs), as it shows excellent safety characteristics, does not form a significant SEI and its volume change upon intercalation of lithium ions is negligible. Unfortunately, this material suffers from a rather low electric conductivity - that is why an intensive study on improved current collector surfaces for LTO electrodes was performed. In order to go one step ahead towards sustainable energy storage, anode and cathode active materials for a sodium ion battery were synthesized. Anode active material resulted in a successful product which was then subjected to further electrochemical tests. In this PhD work the development of “greener” energy storage possibilities is tested under several aspects. The ecological impact of raw materials and required battery components is examined in detail.

Synthesis and characterization of prussian blue analogue materials for post-Li ion batteries

Energy issues have always been a subject of concern to people. During the past 30 years, rechargeable Li-ion batteries (LIBs) have been widely used in portable electronic devices and power tools because of their high energy density and efficiency among practical secondary batteries. While the unevenly distribution of Lithium sources and the increasing cost of lithium-raw material can not satisfy the requirement for further cost reduction, especially for the grid-scale energy storage. Post-lithium ion batteries as promising replacement for LIBs have attracted wide attention, owing to their high abundant resources and adequate insertion potential. Similar with Li-ion batteries, finding a suitable electrode material is the key for the research and application of the post-Li ion batteries. In our project, we focus our study on Prussian blue analogues (PBAs), with formula AxM[M’(CN)6]1-y□y•zH2O (0≤x≤2, 0anode material for both Li-ion and post-Li batteries. The most commonly studied PBAs are metal haxacyanoferrate, with the carbon-sites of -CN- ligands fix connected with Fe. Here, we synthesized three different PBAs: manganese hexacynoferrate (MnHCF), zinc hexacynoferrate (ZnHCF) and titanium hexacynoferrate (TiHCF), using co-precipitation method, and their electrochemical properties were tested in both aqueous Na+, K+, Mg2+, Zn2+ and organic Li+, Na+ electrolytes. Various X-ray techniques were employed to study their electronic and structural properties of electrodes and electrochemical reaction mechanism during cycling.

Graphite for lithium-ion batteries: mineral analysis and global Material Flow Analysis

Graphite is a mineral commodity used as anode for lithium-ion batteries (LIBs), and its global demand is doomed to increase significantly in the future due to the forecasted global market demand of electric vehicles. Currently, the graphite used to produce LIBs is a mix of synthetic and natural graphite. The first one is produced by the crystallization of petroleum by-products and the second comes from mining, which causes threats related to pollution, social acceptance, and health. This MSc work has the objective of determining compositional and textural characteristics of natural, synthetic, and recycled graphite by using SEM-EDS, XRF, XRD, and TEM analytical techniques and couple these data with dynamic Material Flow Analysis (MFA) models, which have the objective of predicting the future global use of graphite in order to test the hypothesis that natural graphite will no longer be used in the LIB market globally. The mineral analyses reveal that the synthetic graphite samples contain less impurities than the natural graphite, which has a rolled internal structure similar to the recycled one. However, recycled graphite shows fractures and discontinuities of the graphene layers caused by the recycling process, but its rolled internal structure can help the Li-ions’ migration through the fractures. Three dynamic MFA studies have been conducted to test distinct scenarios that include graphite recycling in the period 2022-2050 and it emerges that - irrespective of any considered scenario - there will be an increase of synthetic graphite demand, caused by the limited stocks of battery scrap available. Hence, I conclude that both natural and recycled graphite is doomed to be used in the LIB market in the future, at least until the year 2050 when the stock of recycled graphite production will be enough to supersede natural graphite. In addition, some new improvement in the dismantling and recycling processes are necessary to improve the quality of recycled graphite.