Plusieurs processus photo-induits d'énergie et de transfert d'énergie ont été étudiés en solution et dans le film par spectroscopie d'absorption transitoire et de fluorescence pour deux types de cellules solaires. Combinés avec d'autres expériences et par une analyse globale, ces phénomènes ultrarapides avec leur durée de vie ont été observés et les scénarios photo-induits ont été déterminés. La compréhension approfondie des matériaux moléculaires pourrait aider les chimistes à concevoir des cellules solaires efficaces. La première étude sur l'influence des conceptions chimiques sur la formation et la séparation des charges implique différentes fractions donneuses et différents solvants et les résultats ont été expliqués par la théorie de Marcus-Jortner combinée avec le calcul quantique. La deuxième étude porte sur les complexes Fe (II) comme photosensibilisateurs pour les cellules solaires sensibilisées aux colorants. On a étudié une série de complexes de Fe (II) homo et hétérotéptiques avec des ligands de carbène et de terpyridine en solution et dans le film. La durée de vie de l'état de transfert de la charge métal-ligand du triplet d'enregistrement du complexe Fe (II) est obtenue en solution. La compréhension du film est en cours. / Various photo-induced energy and energy transfer processes were investigated in solution and in the film by transient absorption and fluorescence spectroscopies for two types of solar cells. Combined with other experiments and through a global analysis, those ultrafast phenomena with their lifetimes were observed and the photo-induced scenarios were determined. The insight understanding of molecular materials could help chemists to design efficient solar cells.The first study about the influence of chemical designs on charge formation and separation involves different donor moieties and different solvents and the results were explained by Marcus-Jortner theory combined with quantum calculationThe second investigation is about Fe(II) complexes as photosensitizers for dye-sensitized solar cells. A series of homo- and heteroleptic Fe(II) complexes with carbene and terpyridine ligands have been studied in solution and in the film. The record triplet metal-to-ligand charge transfer state lifetime of Fe(II) complex is achieved in solution. The further understanding in the film is in progress.

The globally increasing energy demand that results from the rapid development of modern society has created intensive attention towards the importance of energy efficiency. The areas of energy storage and energy conversion have become one of the most important topics in scientific community at present. As new generation energy storage elements, supercapacitors have exhibited promising practical prospects in the information, transportation, electronics and other sectors due to their charge and discharge performance at high rate, high power density as well as long cycle life. Energy density, including gravimetric energy density, areal energy density and volumetric energy density, is one of the most critical indicator evaluating the performance of supercapacitors. The electrochemical performance of supercapacitors depends mainly on the electrochemical activities and kinetic properties of electrode materials. Carbonaceous materials are deemed to be highly promising, and therefore are extensively investigated energy storage materials for supercapacitors because of their environmental friendliness, low-cost production and outstanding chemical inertness during charging-discharging processes. The specific surface area has been long thought to be the main factor influencing the capacitance of carbonaceous materials. However, the pore structure is of similar importance. High specific surface areas are always arising from a high content of micropores. However, pore radii in the sub-nanometer range impede the ionic charge transfer ability significantly and thus cause a damping of capacitance. In this thesis, hierarchical porous carbons and their composite materials were fabricated by using polyacrylonitrile as carbon precursor for a tailored step-by-step pore forming method, including phase inversion, CaCO3 activation and KOH activation. The materials were thoroughly characterized by XRD, SEM, TEM, BET, XPS and Raman spectroscopy to ascertain the chemical and structural features. The electrochemical properties were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) in detail to analyze the pore effect, which strongly influence their electrochemical properties. Porous carbons with high specific surface areas up to 2315 m2 g-1 and high pore volume of 1.9 cm3·g-1 were prepared. A step-wise pore forming method was employed to ensure a high specific surface area and high content of macro/mesopore at the same time. The relationship between pore structure, electrochemical capacitance and rate capability was investigated by changing the content of micropores. For a same specific surface area, a higher micropore content led to a lower capacitance and poorer rate capability. Based on these results, the capacitance was optimized to be 286.8 F g-1. The areal energy density of the supercapacitors can be improved by increasing the mass loading in a certain area directly. However, insufficient electrochemical reaction may be caused by a lack of unhindered electrical and ionic charge transfer routes, resulting in inefficient material utilization. This problem is addressed by designing hierarchical pore structures with embedded conductive additives. Thus, hierarchical porous carbons were modified by embedding carbon nanotubes (CNTs), followed by coverage with thin layers of birnessite. Owing to the hierarchical pore design and the very high pore volume, the birnessite coverage did not cause pore blocking. At the same time, an intimate contact between carbon and birnessite was established. A high area energy density of 627.8 μWh·cm-2 was obtained based on an optimized mass loading of 13.9 mg cm-2. The volumetric energy density of supercapacitors was determined by the density and porosity of active materials. Similarly, the dense active materials not always generate high specific capacitance because of an increased dead mass. However, too porous active materials do not provide sufficient volumetric capacitance due to a waste of space. Thus, density and porosity must be balanced by hierarchical pore structure design so that all pores are interconnected and can be accessed by ions. At the same time, the content of these pores should be as low as possible to save space. Based on the results, highly hierarchical porous carbons were synthesized and embedded into conductive carbon foam to combine electronic conductivity with ionic transfer. In that way, a volumetric energy density as high as 19.44 µWh cm-3 at a volumetric power density of 500 mW cm-3 was generated.