RESUMO
Conversion of carbon dioxide into hydrocarbons using solar energy is an attractive strategy for storing such a renewable source of energy into the form of chemical energy (a fuel). This can be achieved in a system coupling a photovoltaic (PV) cell to an electrochemical cell (EC) for CO2 reduction. To be beneficial and applicable, such a system should use low-cost and easily processable photovoltaic cells and display minimal energy losses associated with the catalysts at the anode and cathode and with the electrolyzer device. In this work, we have considered all of these parameters altogether to set up a reference PV-EC system for CO2 reduction to hydrocarbons. By using the same original and efficient Cu-based catalysts at both electrodes of the electrolyzer, and by minimizing all possible energy losses associated with the electrolyzer device, we have achieved CO2 reduction to ethylene and ethane with a 21% energy efficiency. Coupled with a state-of-the-art, low-cost perovskite photovoltaic minimodule, this system reaches a 2.3% solar-to-hydrocarbon efficiency, setting a benchmark for an inexpensive all-earth-abundant PV-EC system.
RESUMO
Solution processing of polycrystalline compound semiconductor thin film using nanocrystals as a precursor is considered one of the most promising and economically viable routes for future large-area manufacturing. However, in polycrystalline compound semiconductor films such as Cu2ZnSnS4 (CZTS), grain size, and the respective grain boundaries play a key role in dictating the optoelectronic properties. Various strategies have been employed previously in tailoring the grain size and boundaries (such as ligand exchange) but most require postdeposition thermal annealing at high temperature in the presence of grain growth directing agents (selenium or sulfur vapor with/without Na, K, etc.) to enlarge the grains through sintering. Here, we show a different strategy of controlling grain size by tuning the kinetics of nucleation and the subsequent grain growth in CZTS nanocrystal thin films during a crystalline phase transition. We demonstrate that the activation energy for the phase transition can be varied by utilizing different shapes (spherical and nanorod) of nanocrystals with similar size, composition, and surface chemistry leading to different densities of nucleation sites and, thereby, different grain sizes in the films. Additionally, exchanging the native organic ligands for inorganic surface ligands changes the activation energy for the phase change and substantially changes the grain growth dynamics, while also compositionally modifying the resulting film. This combined approach of using nucleation and growth dynamics and surface chemistry enables us to tune the grain size of polycrystalline CZTS films and customize their electronic properties by compositional engineering.
RESUMO
Although in sodium-oxygen (Na-O2) batteries show promise as high-energy storage systems, this technology is still the subject of intense fundamental research, owing to the complex reaction by which it operates. To understand the formation mechanism of the discharge product, sodium superoxide (NaO2), advanced experimental tools must be developed. Here we present for the first time the use of a Na-O2 microbattery using a liquid aprotic electrolyte coupled with fast imaging transmission electron microscopy to visualize, in real time, the mechanism of NaO2 nucleation/growth. We observe that the formation of NaO2 cubes during reduction occurs by a solution-mediated nucleation process. Furthermore, we unambiguously demonstrate that the subsequent oxidation of NaO2 of which little is known also proceeds via a solution mechanism. We also provide insight into the cell electrochemistry via the visualization of an outer shell of parasitic reaction product, formed through chemical reaction at the interface between the growing NaO2 cubes and the electrolyte, and suggest that this process is responsible for the poor cyclability of Na-O2 batteries. The assessment of the discharge-charge mechanistic in Na-O2 batteries through operando electrochemical transmission electron microscopy visualization should facilitate the development of this battery technology.
RESUMO
Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (Mn+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate Mn+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of Mn+ on oxygen reduction. A case study on the Na-O2 system is described in detail. Among other things, the Na+ concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided.