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

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.

Methodology for the identification of promising integrated biorefineries

Ayse Dilan Celebi

Steady increase in global energy consumption, greenhouse gas emissions, and depletion of fossil energy resources, together with increased attention towards sustainable development has prompted researchers to discover economical and environmentally competitive non-petroleum alternatives and biomass is considered to be one of the most promising renewable sources of energy and carbon of this matter to address the aforementioned issues within a biorefinery platform. A biorefinery is an integrated processing facility that converts biomass into transportation fuels, value-added chemicals, heat, and electricity via biochemical and thermochemical conversion routes. Integrated biorefineries are capable of mimicking petroleum refineries via application of advanced process synthesis methods including modeling, simulation, integration and optimization techniques. This thesis presents a comprehensive synthesis methodology for the integration of bioprocessing technologies in biorefineries by addressing techno-economic and environmental sustainability analysis. The proposed systematic design approach combines advanced process modeling approaches, process integration techniques, and multi-objective optimization algorithms to assess the performance of the overall system with respect to economic, environmental, and energetic indicators. The design strategy is applied based on different case studies. Results indicate that multi-product processes can yield significant cost and environmental benefits. Additionally, the integration of biochemical and catalytic processes with thermochemical conversion pathways results in increased carbon efficiency and economic and environmental competitiveness. Synergies between biorefineries and energy system are assessed by integrating industrial plants with a cogeneration system producing biofuels and process heat. In doing so, system efficiency is increased by coupling the proposed cogeneration system with carbon capture and sequestration (CCS) and power-to-gas technologies to store the renewable intermittent electricity in the form of biofuels. The results exhibit that through system expansion, integrated biorefinery systems allow us to imitate fossil refineries with a large spectrum of bio-based products. This further increases the resource efficiency while offering a promising solution to mitigate CO2 emissions and hence reaching the longer-term decarbonization target set by the Paris Agreement.

EPFL2019

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

Nanostructured Electrocatalysts for Water Splitting Reactions

Lucas-Alexandre Stern

At the dawn of the 21st century, mankind is facing an important energy challenge. Future energy demand can only be met by large scale exploitation of renewable energy resources. Solar energy is abundant, with a sufficient capacity for the growing energy demand. However, it is necessary to implement renewable energy storage means. Hydrogen is considered as the energy carrier of the future. An energy economy based on hydrogen is viable only if hydrogen is produced from sustainable means. Water electrolysis is the most promising technique to produce hydrogen directly from water. Yet, the efficiency is limited and electrocatalysts are required to drive both the hydrogen evolution reaction and oxygen evolution reaction. Scarce and expensive materials are currently used to drive these reactions. It is, thus, imperative that efficient Earth-abundant catalysts are developed. Nanostructuring enhances the performance of inexpensive materials for water splitting and several catalysts were studied for this goal. Chapter 2 describes the application of nanostructuring technique to the archetypical catalysts that are nickel oxides for oxygen evolution. The prepared nanoparticles show superior activity towards oxygen evolution than that of their bulk counterpart. The ultrafine size of nanoparticles synthesized allowed the exposure of a higher number of active sites. The activity for oxygen evolution was, thus, significantly enhanced. We also detailed that short conditioning of the electrode improved the performance of the evaluated materials. In chapter 3 we carefully studied nanoparticles and nanowires of nickel phosphide. The catalysts is known to be really active for hydrogen evolution. Our group suspected that this material was, also, a potential oxygen evolution catalyst. We proved, for the first time, that nickel phosphide is a remarkable oxygen evolution catalyst. Under alkaline conditions, used for oxygen evolution, we observed an in-situ formation of a core-shell heterostructure, a typical nanostructure architecture. The surface oxidation of this material allowed high oxygen evolution capabilities. We concluded that careful oxidation of nanostructured materials, as observed for nickel phosphide, is essential for the preparation of future outstanding oxygen evolution catalysts. Chapter 4 details the fabrication of direct solar-to-fuel electrode using cobalt phosphide as hydrogen evolving catalyst. Instead of using the electrical energy provided by solar energy, solar irradiation on the developed assembly allows direct hydrogen production. The careful design of the light-sensitive electrode (photocathode) is detailed. Simple incorporation of cobalt phosphide by means of photodeposition alleviates the cost of the electrode fabrication. The assembled electrode is active for hydrogen evolution under visible light irradiation. In the chapter 5 we sought to fabricate a 3-dimensional hydrogen evolving catalyst. This nanostructure is based on polymer brushes on a flat conducting substrate. Once the brushes are grown on the substrate, a molybdenum sulfide catalyst is then incorporated by simple soaking technique. We were able to tune the loading of the catalyst and the corresponding activity by changing the polymer properties. The height of the polymer was modified as well as its packing density. The resulting activity proved superior to similar approaches and to previous reports on carefully engineered molybdenum sulfide catalysts.

EPFL2017