Combined hydrogen production and electricity storage using a vanadium-manganese redox dual-flow battery

A redox dual-flow battery is distinct from a traditional redox flow battery (RFB) in that the former includes a secondary energy platform, in which the pre-charged electrolytes can be discharged in external catalytic reactors through decoupled redox-mediated hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The concept offers several advantages over conventional electrolysis in terms of safety, durability, modularity, and purity. In this work, we demonstrate a vanadium-manganese redox-flow battery, in which Mn3+/Mn2+ and V3+/V2+ respectively mediate the OER and the HER in Mo2C-based and RuO2-based catalysts. The flow battery demonstrates an average energy efficiency of 68% at a current density of 50 mA . cm(-2) (cell voltage = 1.92 V) and a relative energy density 45% higher than the conventional all-vanadium RFB. Both electrolytes are spontaneously discharged through redox-mediated HER and OER with a faradic efficiency close to 100%.

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.

EPFL2022

Redox flow battery and indirect water electrolysis

Véronique Amstutz

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 VâCe 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.

EPFL2015

Renewable hydrogen generation from a dual-circuit redox flow battery

Véronique Amstutz, Christos Comninellis, Hubert Girault, Xile Hu, Francis Powlesland, Kathryn Ellen Toghill, Heron Vrubel

Redox flow batteries (RFBs) are particularly well suited for storing the intermittent excess supply of renewable electricity; so-called “junk” electricity. Conventional RFBs are charged and discharged electrochemically, with electricity stored as chemical energy in the electrolytes. In the RFB system reported here, the electrolytes are conventionally charged but are then chemically discharged over catalytic beds in separate external circuits. The catalytic reaction of particular interest generates hydrogen gas as secondary energy storage. For demonstration, indirect water electrolysis was performed generating hydrogen and oxygen in separated catalytic reactions. The electrolyte containing V(II) was chemically discharged through proton reduction to hydrogen on a molybdenum carbide catalyst, whereas the electrolyte comprising Ce(IV) was similarly discharged in the oxidation of water to oxygen on a ruthenium dioxide catalyst. This approach is designed to complement electrochemical energy storage and may circumvent the low energy density of RFBs especially as hydrogen can be produced continuously whilst the RFB is charging.