Infoscience

Thesis

Redox flow battery and indirect water electrolysis

The progressive integration of renewable energy sources such as wind turbines and photovoltaic pannels in the current electrical network, and the rise of the electrical mobility, provoke a change of paradigm in the sector of energy management. The increasing variability of the electricity production and consumption profiles, together with the requirement for a reliable supply of energy, necessitates the implementation of energy storage means of different scales and for a wide range of applications. Redox flow batteries (RFBs) are well adapted for buffering the fluctuations of solar or wind energy production. They present a fast response time, can withstand a large number of charge-discharge cycles and their ouput power is independant of their energy capacity. The main limitation of RFBs resides in their low energy density. The objective of the present work was to test a mean to overcome this low energy density. A new concept was developed, which rests on the addition of a second pathway to discharge the RFB. This pathway allows to generate hydrogen and oxygen, without affecting the functioning of the RFB. This concept was called dual-circuit RFB and was patented. RFBs are based on two liquids electrolytes, each stored in a reservoir, and flowing through an electrochemical cell for their electrochemical conversion. Each electrolyte contains one redox couple and Ce(IV)/Ce(III) and V(III)/V(II) were selected as positive and negative redox couples in the RFB developed here. Charge-discharge curves of a V–Ce RFB were measured for characterisation purposes and for the preparation of the charged electrolytes. The latter ones can be discharged electrochemically in the RFB to generate electricity (electrochemical discharge mode), or they can be directed in a secondary circuit where they are discharged for the production of hydrogen or oxygen (chemical discharge mode). The chemical discharge of the negative electrolyte consists of the reaction of V(II) with protons to produce hydrogen and V(III). Mo2C was selected as heterogenous catalyst for the characterisation of the reaction. A conversion close to 100% suggested no loss of current. A kinetic analysis provided some insights into the catalytic mechanism of this reaction. The chemical discharge of the positive electrolyte aimed at the conversion of Ce(IV) to Ce(III) by the oxidation of water to oxygen and also necessitates a catalyst. Iridium dioxide (IrO2) and ruthenium dioxide (RuO2) were evaluated in terms of conversion and kinetics. The composition of the positive electrolyte was shown to be of importance for this reaction. To show the feasibility of this concept, a larger-scale demonstrator system was designed based on a 10 kW (40kWh) commercially available vanadium RFB. A characterisation of this RFB was first performed. The design a suitable Mo2C catalyst and its corresponding catalytic bed is also discussed. As a conclusion, the concept developed and experimentally tested in the present work leads to a RFB system which is characterised by two discharge modes, increasing its energy storage capacity and energy density. The dual-circuit RFB also represents a crossing between electrical grid and hydrogen mobility as the hydrogen produced by surplus electricity could be delivered to fuel cell cars. The application of this system in a local distribution electrical network, close to a wind or solar source seems a promising approach.

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