Exploration of VACNTs in Anode-less Batteries: Mechanism and Cell Optimization
Anode-less or anode-free batteries are getting increasing attention owing to their excellent energy density, cost efficiency, and ease of process upscaling. Exploring anode-less battery will offer a breakthrough in energy storage devices by using the lithium reserve already present in the NMC cathode to reversibly cycle after an initial formation process, which will reduce the overall thickness, processing steps, and cost of materials, and provide excellent energy density. Vertically aligned CNTs (VACNTs) on metal substrates can be an interesting choice for this application due to their low thickness, reproducible synthesis process, and uniform surface properties, which have already proven their applicability in supercapacitors. In this PhD project, we will investigate their newer avenue of applications- anode-less batteries, where VACNTs act as the lithium or sodium plating substrate. We will study the electrochemistry of VACNT in lithium anode-less batteries (in liquid and solid electrolytes) and in sodium anode-less batteries in a liquid electrolyte. The PhD student will work on the synthesis optimizations of VACNT to tune the thickness and density to match their electrochemistry. Post-cycling studies (Raman and SEM) will be carried out to study the effect of cycling and the electrolytes on the VACNT layers. The project aims to explore the possibility of the application of VACNTs in various energy storage systems, which can open up new application possibilities and valorization
Photo- and thermocatalytic cross-coupling of esters for the synthesis of biosourced alkenes
The easy access to energy and carbon-based raw materials offered by the fossil feedstock allowed a rapid growth of our society. Nevertheless, the expected depletion of fossil resources and climate change, require changing for a more sustainable model. Bio-based feedstock is a promising source of carbon to substitute petrochemicals but require a drastic change of the actual model. While the current paradigm relies on the production of energy and high-value molecules through oxidation steps, a model based on Carbon Circular Economy, i.e. the transformation of CO2 and biomass feedstock that are already highly oxidized materials demands the development of new methodologies for reduction, deoxygenation, and the direct use of oxygenated bonds to access functionalized and useful organic molecules.
In organic chemistry, cross-coupling reactions represent one of the major tools to create C–C bonds. However, they are still based mainly on the use of organic halides as electrophiles. In this project, the PhD candidate will demonstrate that readily available and abundant alkyl esters can serve as electrophilic coupling partners in catalyzed cross-coupling reactions with alkenes. Esters can indeed be directly biosourced or easily synthesized from alkyl carboxylic acids and alcohols, thereby diminishing the environmental impact of the carbon-carbon bond formation.
Synthetic methodologies towards functionalized azaheterocycles and application to energetic molecules
The objective of the PhD is to develop new synthesis and/or functionalization methods to obtain functionalized heterocyclic molecules. These molecules are based on 5- or 6-member azaheteroaromatic rings (diazines, triazines, triazoles, tetrazoles, etc.). The targeted structures make it possible to envisage high densities and enthalpies of formation, while maintaining low sensitivity (thermal, mechanical, etc.). They find applications in the energy field, notably propulsion, explosives and gas generators (airbags). In addition, these heterocyclic compounds as well as the intermediates are also structurally close to families of biologically active products and/or likely to exhibit fluorescence properties, as already shown in a previous PhD in the laboratory.
Chemical recycling of oxygenated and nitrogenated plastic waste by reductive catalytic routes
Since the 1950s, the use of petroleum-based plastics has encouraged the emergence of a consumption model focused on the use of disposable products. Global plastic production has almost doubled over the last 20 years, currently reaching 468 million tons per year. These non-biodegradable plastic are the source of numerous forms of environmental pollution. Since the 1950s, only 9% of the wastes have been recycled. The majority have been incinerated or sent to landfill. In the current context of this linear economy, health, climate and societal issues make it essential to transition to a circular approach to materials. This evolution requires the development of recycling methods that are both effective and robust. While the most common recycling methods currently in use are mainly mechanical processes that apply to specific types of waste, such as PET plastic bottles, the development of chemical recycling methods appears promising for treating waste for which no recycling channels exist. These innovative chemical processes make it possible to recover the carbonaceous material from plastics to produce new ones.
Within this objective of material circularity, this doctoral project aims to develop new chemical recycling routes for mixed oxygen/nitrogen plastic waste such as polyurethanes (insulation foam, mattresses, etc.) and polyamides (textile fibres, circuit breaker boxes, etc.), for which recycling routes are virtually non-existent. This project is based on a strategy of depolymerizing these plastics by the selective cleavage of the carbon-oxygen and/or carbon-nitrogen bonds to form the corresponding monomers or their derivatives. To do that, catalytic systems involving metal catalysts coupled with abundant and inexpensive reducing agents will be developed. In order to optimize these catalytic systems, we will seek to understand how they proceed and the mechanisms involved.
Synthesis and optical properties of quantum dots
Graphene as a constituent of graphite was close to us for almost 500 years. However, it is only in 2005 that A. Geim and K. Novoselov (Nobel Prize in 2010) reported for the first time the obtaining of a nanostructure composed by a single layer of carbon atom. The exceptional electronic properties of graphene make it a very promising material for applications in electronic and renewable energies.
For many applications, one should be able to modify and control precisely the electronic properties of graphene. In this context, we propose to synthesize chemically graphene nanoparticles and study their absorption and photoluminescence properties. We will focus on families of elongated nanoparticles, with the aim of studying how size can enable us to observe and control multiexcitonic processes in these materials. This project will be developed in collaboration with Physicists so the candidate will work in a multidisciplinary environment.