This project aims to create transition metal perovskite/Nitrogen-doped Carbon electrospun nanofibres as alternative cost-efficient bifunctional electrocatalysts to replace noble metals for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in energy conversion (PEM fuel cells and water electrolysers) and storage (metal-air batteries) devices. At the same time, I will develop new in situ studies that will allow a deeper understanding of the structure-property relationships allowing for further optimisation. The search for green alternative sources of energy is of great importance for our current society. In order to battle increasing greenhouse gases and global warming created by the use of fossil fuels, and to meet the UK's 2050 climate change targets, we need to develop new technologies that allow researchers to tackle this problem. Some of these alternatives include fuel cells, solar cells, batteries, supercapacitors and water electrolysers. OER and ORR are key processes taking place in most of these technologies and will be the focus of this project. The high cost of the noble metal catalysts employed in energy conversion and storage devices is one of the major drawbacks to their full development and exploitation. There are many reports new materials that can overcome state-of-the-art limitations at an acceptable cost. However, not much research has been done to understand the effect of nanostructuring, hybridisation between various electrochemically active materials and understanding the structure-property relationships to allow an improved performance. In this project, I will design hybrid materials combining already known transition metal perovskite electrocatalysts with nitrogen-doped carbons electrocatalysts using the electrospinning technique. These new hybrid nanostructures will be characterised using state-of-the-art techniques. I will also design in operando studies combining structural and property coupled measurements. The electrocatalytic activity of perovskites is thought to be due to the presence of oxygen vacancies in their structure. By combining Raman spectroscopy and OER and ORR measurements, we will be able to monitor the changes in the oxygen vacancies of the perovskites (detected by Raman spectroscopy) as their electrochemical performance is evaluated. A similar approach will be developed using X-ray computed tomography, which will provide invaluable information about the complex structures and interactions involved in the catalytic process at the different structural levels of organisation and integrated within real devices. This will be correlated with the electrocatalytic activity of N-doped carbon materials studied by X-Ray Adsorption studies and the synergy between these two electrocatalysts understood. This will lead to a better understanding of the parameters influencing the activity of these materials in relation to their structure and also to the device environment and will facilitate a better electrode engineering. This project will be conducted at the Materials Research Institute (MRI), Queen Mary University of London (QMUL). The MRI brings together a range of expertise with different schools including Engineering and Materials, Physics and Astronomy, Biological and Chemical Sciences, and Dentistry, providing a platform to support interdisciplinary materials research. I maintain a close collaboration with the Electrochemical Innovation Lab (Chemical Engineering Department, UCL) which will provide access to X-ray computed tomography and industrial links to test the new materials at scaled-up dimensions. Coupled structure-property studies will be carried out in collaboration with Dr. Ozlem Sel and Dr. Ivan Lucas, from Laboratoire Interfaces Systemes Electrochimiques (LISE, CNRS, Paris, Sorbonne Universites). An internal collaboration with Prof. Titirici group at MRI-QMUL working on N-doped carbon electrocatalysis will complement these collaborations.

The project aims to develop innovative polymer electrolyte based electrolysers with lower life cycle costs (achieved by enhanced efficiency) utilising enhanced materials and components. This proposal is based on adopting alkaline anion-exchange membrane (AEM) and ionomer (AEI) technology to open up the opportunity for low cost electrolysers systems with: i) low cost polymer electrolytes, catalysts (sustainable i.e. non-Pt), and bipolar plate materials; ii) higher energy efficiency; iii) durable long life operation; and iv) flexibility to respond to dynamic load operation. We target electrolysers involving hydrogen production from water electrolysis and involving carbon dioxide reduction for low overpotential (high value) organic chemical synthesis. A major aim is to produce the next generation of AAEMs and AEIs that can be supplied to (current and future) project partners in bulk quantities (including AEIs in a solubilised form). Hydrogen is an excellent storage medium for renewable and sustainable energy systems. Hydrogen has several advantages as an energy carrier including highly efficient reversible conversion between hydrogen and electricity, good gravimetric energy density of compressed gas compared to most batteries and scalability of hydrogen technologies for grid scale applications. Water electrolysis is a safe option for production of pure hydrogen at point of use as it does not require substantial storage requirements. Currently, the cost of hydrogen produced by electrolysis is greater than that of other methods such as steam reforming. Two major reasons for this is the capital cost of the cells and the electrical energy consumption. Commercial hydrogen production by water electrolysis is based on one of two technologies: aqueous alkaline (potassium hydroxide) electrolytes and proton exchange membrane electrolytes. Alkaline cells use lower cost electrode materials than acid polymer systems but current densities (and efficiency) are typically lower. The capital cost of proton exchange membrane electrolysers is higher (largely dictated by the high material costs of membranes [perfluorinated polymers] and precious metal [Pt, Ir, Ru] based catalysts) but their production rates (per unit electrode area) are higher based on the higher current densities. We thus seek to transform the latter technology by combing the advantages of alkaline and polymer electrolytes using low cost materials with the aim of improving energy efficiencies. Realistically there is a minimum energy consumption that can be achieved by electrolysis (based on thermodynamic potentials and voltage losses in the cell) and thus we set our target at a voltage of 1.75 V at 1 A cm-2 (based on geometric electrode area). To maximise the potential impact of the materials being developed, carbon dioxide reducing electrolysers will also be studied (involving the field of carbon dioxide utilisation). The reduction of carbon dioxide into useful chemicals is of great potential value from a sustainability, environmental and societal context. Such syntheses require a significant energy use and thus using renewable electrical energy in such applications could play a major part in their development. Consequently we seek to develop electrochemical technology whereby we synthesis small molecules (formate, synthesis gas, and/or methanol) based on anion exchange membrane electrolyser materials and architectures (including the involvement of carbonate anion conducting electrolytes - which inherently yield higher chemical stabilities compared to hydroxide conducting analogues). The project aims to deliver a step change in uptake of ultra-low carbon, green-hydrogen production and carbon dioxide reduction systems. This will be based upon the application of the applicants previous technology breakthroughs of alkaline polymer electrolyte materials and non-precious metal catalyst for galvanic and electrolytic electrochemical energy conversion and storage technologies.

The first viable large scale fuel cell systems were the liquid electrolyte alkaline fuel cells developed by Francis Bacon. Until recently the entire space shuttle fleet was powered by such fuel cells. The main difficulties with these fuel cells surrounded the liquid electrolyte, which was difficult to immobilise and suffers from problems due to the formation of low solubility carbonate species. Subsequent material developments led to the introduction of proton-exchange membranes (PEMs e.g. Nafion(r)) and the development of the well-known PEMFC. Cost is a major inhibitor to commercial uptake of PEMFCs and is localised on 3 critical components: (1) Pt catalysts (loadings still high despite considerable R&D); (2) the PEMs; and (3) bipolar plate materials (there are few inexpensive materials which survive contact with Nafion, a superacid). Water balance within PEMFCs is difficult to optimise due to electro-osmotic drag. Finally, PEM-based direct methanol fuel cells (DMFCs) exhibit reduced performances due to migration of methanol to the cathode (voltage losses and wasted fuel).Recent advances in materials science and chemistry has allowed the production of membrane materials and ionomers which would allow the development of the alkaline-equivalent to PEMs. The application of these alkaline anion-exchange membranes (AAEMs) promises a quantum leap in fuel cell viability. The applicant team contains the world-leaders in the development of this innovative technology. Such fuel cells (conduction of OH- anions rather than protons) offer a number of significant advantages:(1) Catalysis of fuel cell reactions is faster under alkaline conditions than acidic conditions - indeed non-platinum catalysts perform very favourably in this environment e.g. Ag for oxygen reduction.(2) Many more materials show corrosion resistance in alkaline than in acid environments. This increases the number and chemistry of materials which can be used (including cheap, easy stamped and thin metal bipolar plate materials).(3) Non-fluorinated ionomers are feasible and promise significant membrane cost reductions.(4) Water and ionic transport within the OH-anion conducting electrolytes is favourable electroosmotic drag transports water away from the cathode (preventing flooding on the cathode, a major issue with PEMFCs and DMFCs). This process also mitigates the 'crossover' problem in DMFCs.This research programme involves the development of a suite of materials and technology necessary to implement the alkaline polymer electrolyte membrane fuel cells (APEMFC). This research will be performed by a consortium of world leading materials scientists, chemists and engineers, based at Imperial College London, Cranfield University, University of Newcastle and the University of Surrey. This team, which represents one of the best that can be assembled to undertake such research, embodies a multiscale understanding on experimental and theoretical levels of all aspects of fuel cell systems, from fundamental electrocatalysis to the stack level, including diagnostic approaches to assess those systems. The research groups have already explored some aspects of APEMFCs and this project will undertake the development of each aspect of the new technology in an integrated, multi-pronged approach whilst communicating their ongoing results to the members of a club of relevant industrial partners. The extensive opportunities for discipline hopping and international-level collaborations will be fully embraced. The overall aim is to develop membrane materials, catalysts and ionomers for APEMFCs and to construct and operate such fuel cells utilising platinum-free electrocatalysts. The proposed programme of work is adventurous: however, risks have been carefully assessed alongside suitable mitigation strategies (the high risk components promise high returns but have few dependencies). Success will lead to the U.K. pioneering a new class of clean energy conversion technology.

The first viable large scale fuel cell systems were the liquid electrolyte alkaline fuel cells developed by Francis Bacon. Until recently the entire space shuttle fleet was powered by such fuel cells. The main difficulties with these fuel cells surrounded the liquid electrolyte, which was difficult to immobilise and suffers from problems due to the formation of low solubility carbonate species. Subsequent material developments led to the introduction of proton-exchange membranes (PEMs e.g. Nafion(r)) and the development of the well-known PEMFC. Cost is a major inhibitor to commercial uptake of PEMFCs and is localised on 3 critical components: (1) Pt catalysts (loadings still high despite considerable R&D); (2) the PEMs; and (3) bipolar plate materials (there are few inexpensive materials which survive contact with Nafion, a superacid). Water balance within PEMFCs is difficult to optimise due to electro-osmotic drag. Finally, PEM-based direct methanol fuel cells (DMFCs) exhibit reduced performances due to migration of methanol to the cathode (voltage losses and wasted fuel).Recent advances in materials science and chemistry has allowed the production of membrane materials and ionomers which would allow the development of the alkaline-equivalent to PEMs. The application of these alkaline anion-exchange membranes (AAEMs) promises a quantum leap in fuel cell viability. The applicant team contains the world-leaders in the development of this innovative technology. Such fuel cells (conduction of OH- anions rather than protons) offer a number of significant advantages:(1) Catalysis of fuel cell reactions is faster under alkaline conditions than acidic conditions - indeed non-platinum catalysts perform very favourably in this environment e.g. Ag for oxygen reduction.(2) Many more materials show corrosion resistance in alkaline than in acid environments. This increases the number and chemistry of materials which can be used (including cheap, easy stamped and thin metal bipolar plate materials).(3) Non-fluorinated ionomers are feasible and promise significant membrane cost reductions.(4) Water and ionic transport within the OH-anion conducting electrolytes is favourable electroosmotic drag transports water away from the cathode (preventing flooding on the cathode, a major issue with PEMFCs and DMFCs). This process also mitigates the 'crossover' problem in DMFCs.This research programme involves the development of a suite of materials and technology necessary to implement the alkaline polymer electrolyte membrane fuel cells (APEMFC). This research will be performed by a consortium of world leading materials scientists, chemists and engineers, based at Imperial College London, Cranfield University, University of Newcastle and the University of Surrey. This team, which represents one of the best that can be assembled to undertake such research, embodies a multiscale understanding on experimental and theoretical levels of all aspects of fuel cell systems, from fundamental electrocatalysis to the stack level, including diagnostic approaches to assess those systems. The research groups have already explored some aspects of APEMFCs and this project will undertake the development of each aspect of the new technology in an integrated, multi-pronged approach whilst communicating their ongoing results to the members of a club of relevant industrial partners. The extensive opportunities for discipline hopping and international-level collaborations will be fully embraced. The overall aim is to develop membrane materials, catalysts and ionomers for APEMFCs and to construct and operate such fuel cells utilising platinum-free electrocatalysts. The proposed programme of work is adventurous: however, risks have been carefully assessed alongside suitable mitigation strategies (the high risk components promise high returns but have few dependencies). Success will lead to the U.K. pioneering a new class of clean energy conversion technology.

The first viable large scale fuel cell systems were the liquid electrolyte alkaline fuel cells developed by Francis Bacon. Until recently the entire space shuttle fleet was powered by such fuel cells. The main difficulties with these fuel cells surrounded the liquid electrolyte, which was difficult to immobilise and suffers from problems due to the formation of low solubility carbonate species. Subsequent material developments led to the introduction of proton-exchange membranes (PEMs e.g. Nafion(r)) and the development of the well-known PEMFC. Cost is a major inhibitor to commercial uptake of PEMFCs and is localised on 3 critical components: (1) Pt catalysts (loadings still high despite considerable R&D); (2) the PEMs; and (3) bipolar plate materials (there are few cheap materials which survive contact with Nafion, a superacid). Water balance within PEMFCs is difficult to optimise due to electro-osmotic drag. Finally, PEM-based direct methanol fuel cells (DMFCs) exhibit reduced performances due to migration of methanol to the cathode (voltage losses and wasted fuel).Recent advances in materials science and chemistry has allowed the production of membrane materials and ionomers which would allow the development of the alkaline-equivalent to PEMs. The application of these alkaline anion-exchange membranes (AAEMs) promises a quantum leap in fuel cell viability. The applicant team contains the world-leaders in the development of this innovative technology. Such fuel cells (conduction of OH- anions rather than protons) offer a number of significant advantages:(1) Catalysis of fuel cell reactions is faster under alkaline conditions than acidic conditions - indeed non-platinum catalysts perform very favourably in this environment e.g. Ag for oxygen reduction.(2) Many more materials show corrosion resistance in alkaline than in acid environments. This increases the number and chemistry of materials which can be used (including cheap, easy stamped and thin metal bipolar plate materials).(3) Non-fluorinated ionomers are feasible and promise significant membrane cost reductions.(4) Water and ionic transport within the OH-anion conducting electrolytes is favourable electroosmotic drag transports water away from the cathode (preventing flooding on the cathode, a major issue with PEMFCs and DMFCs). This process also mitigates the 'crossover' problem in DMFCs.This research programme involves the development of a suite of materials and technology necessary to implement the alkaline polymer electrolyte membrane fuel cells (APEMFC). This research will be performed by a consortium of world leading materials scientists, chemists and engineers, based at Imperial College London, Cranfield university, University of Newcastle and the University of Surrey. This team, which represents one of the best that can be assembled to undertake such research, embodies a multiscale understanding on experimental and theoretical levels of all aspects of fuel cell systems, from fundamental electrocatalysis to the stack level, including diagnostic approaches to assess those systems. The research groups have already explored some aspects of APEMFCs and this project will undertake the development of each aspect of the new technology in an integrated, multi-pronged approach whilst communicating their ongoing results to the members of a club of relevant industrial partners. The extensive opportunities for discipline hopping and international-level collaborations will be fully embraced. The overall aim is to develop membrane materials, catalysts and ionomers for APEMFCs and to construct and operate such fuel cells utilising platinum-free electrocatalysts. The proposed programme of work is adventurous: however, risks have been carefully assessed alongside suitable mitigation strategies (the high risk components promise high returns but have few dependencies). Success will lead to the U.K. pioneering a new class of clean energy conversion technology.