Analysis and comparison of hydrogen routes for automotive use

The goal of this project would be to analyze and compare systematically the different existing and emerging processes producing hydrogen from fossil and renewable resources. As the perspective would be the replacement of fossil fuels with hydrogen in the transportation sector, the comparison of the different processes will essentially be based on the environmental impacts.

Coupling of electrocatalysts to photoabsorbers for solar fuels production

Carlos Gilberto Morales Guio

The direct transformation of sunlight into fuels and chemicals has attracted considerable attention for the potential impact on the storage of solar energies at large scales and the reduction of CO2 emissions. More than 80% of our current global energy consumption comes from the burning of non-renewable fossil fuels which produces enormous quantities of CO2 and contributes to global warming. We believe today that the key to reduce our dependence on exhaustible natural resources and limit the emission of greenhouse gases is the transition to CO2-free renewable energy sources. However, harvesting of energy from renewable sources (i.e. solar, wind, tidal) is intermittent and the deployment of devices for their transformation into useful forms of energy (i.e. electricity, chemicals, fuels, biomass) in a global scale is conditioned upon the improvement in efficiency of the energy storage mechanisms. A promising approach to store energy is the use of sunlight to drive the production of hydrogen fuel from water. Hydrogen produced from water and sunlight can be transformed back to electricity on demand or be used to generate mechanical energy in cars to power the transportation industry. The oxidation of hydrogen generates useable energy and at the same time exhaust clean, carbon-free water as the only product. Therefore, the production of hydrogen using a renewable energy source in an efficient and inexpensive device has the potential to discourage the continued use of fossil fuels and improve our environment. The viability of any mechanism for the storage of sunlight as fuel will depend on the reduction of energy penalties during the transformation process. Electrocatalysts are advanced materials that bring into one active site electrons and molecules in the appropriate orientation to lower activation energy barriers, accelerate rate of transformations and improve overall efficiencies for chemical reactions. The best catalysts for water splitting are precious metals such as Pt, Ir and Ru, which show superior rates of reaction at low overpotentials. However, these noble metals are too expensive and scarce for large scale applications. This thesis summarizes our recent research in the preparation, characterization, and application of Earth-abundant electrocatalysts for solar water splitting. Although in the last decade a great number of efficient and inexpensive electrocatalysts have been reported, methods for the deposition of these materials on the surface of photoabsorbers are rarely reported. This work shows various simple and scalable techniques for the deposition of hydrogen and oxygen evolving electrocatalysts on the surface of photocathodes and photoanodes, respectively. Surface-protected photocahodes were activated for solar hydrogen production in alkaline conditions with MoS2+x, Ni-Mo and Mo2C. A novel method for the deposition of an optically transparent amorphous iron nickel oxide oxygen evolution electrocatalyst is also reported. The catalyst was deposited on both thin film and high-aspect ratio nanostructured hematite photoanodes. The low catalyst loading combined with its high activity at low overpotential results in significant improvement on the onset potential for photoelectrochemical water oxidation. This transparent catalyst further enables the preparation of a stable hematite/perovskite solar cell tandem device, which performs unassisted water splitting.

EPFL2016

Performance evolution and modeling of PEM fuel cell systems

Nicolas Roggo

In the context of climate change mitigation, different alternatives to reduce the atmospheric CO2 emissions are; increasing the efficiency, switching to renewable resource and reduce emissions from fossil resources by CO2 capture and storage (CCS) . Hydrogen is considered as potential alternative to cover the energy needs by using it as a fuel in internal combustion engines or fuel cells, or as chemical source. In proton exchange membrane (PEM) fuel cells, also known as polymer exchange membrane fuel cells, pure hydrogen fuelis combined with the oxygen from the atmosphere to produce water, heat and electricity. Many research has been done in recent years on fuel cell systems leading to higher efficiencies. The performance is influenced by the membrane properties, the catalysts, the number of cells and the operating conditions. For studying the performance of fuel cell systems process modeling is a well-known approach. Here the evolution of fuel cell efficiency, especially of PEMFC is studied within the aim of updating previously developed PEMFC process models to integrate them with different hydrogen production processes using fossil and renewable resources in order to assess the competitiveness on the energy market.

2012

Redox dual-flow battery for combined electricity storage and hydrogen production

Danick Reynard

The energy transition towards a carbon-neutral and sustainable economy is one of the greatest challenges of the 21st century to combat global warming and pollution. The decarbonization process is affecting every sector of the economy (electricity, transportation, industrialâŠ). For power generation, renewable energy resources are realistic alternatives to replace fossil resources such as gas and coal. However, the intermittent nature of wind and solar power limits their penetration into the conventional grid and increases the need for energy storage (battery, hydrogen storageâŠ) for smoothing out fluctuations between electric supply and demand. In this context, the concept of the redox dual-flow battery was introduced to propose a hybrid storage solution that can store electrical energy both electrochemically and in the form of hydrogen fuel. The system differs from a traditional redox flow battery by including a secondary energy platform, in which the electrolytes can be discharged chemically in external catalytic reactors through redox-mediated water electrolysis to produce clean hydrogen. The dual storage feature improves the flexibility and enhances significantly the capacity of the system by storing energy beyond the capacity of the electrolytes in the form of hydrogen. Additionally, the redox-mediated water electrolysis offers several advantages over conventional electrolysis in terms of safety, durability and purity. In this thesis, the proof-of-concept of a dual-flow circuit using a vanadium-manganese redox flow battery for combined electricity storage and hydrogen production is demonstrated. The redox flow battery employs vanadium sulfate (V3+/V2+) and manganese sulfate (Mn3+/Mn2+) dissolved in concentrated sulfuric aqueous solution as negative and positive electrolyte, respectively. The galvanic cell achieves energy efficiency of 68% at a current density of 50 mAÂ·cmâ2 (cell voltage =1.92 V) and a relative battery energy density 45% higher than the conventional all-vanadium RFB in the same conditions. Once charged, the electrolytes can be spontaneously discharged through redox-mediated oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in RuO2 and Mo2C catalytic reactors, resulting in an energy consumption for hydrogen production of ca. 50 kWh/kg H2. The system provides a competitive alternative for large-scale energy storage in renewable energy and transport applications.