Declining fossil fuel reserves and ever-increasing demands for energy make developments in energy storage capabilities vital. Battery usage is becoming increasingly widespread, but this is presenting new challenges due to materials scarcity and limitations in battery performance. It is vital that the increased exploitation of existing battery materials and the development of next generation batteries proceeds through sustainable approaches. We propose to deliver a continuous, scaled-up route for the preparation of next generation battery materials. We will exploit the efficiency of microwave reactors with a high throughput approach to deliver a 'greener' route to existing battery materials. In parallel to this we will explore the opportunities of integration of battery components into polymeric matrices to allow rapid, high accuracy materials deposition to deliver exceptionally high quality devices capable of safely integrating the higher energy density materials of the future. We have targeted specific materials that have known function as cathodes, anodes or electrolytes and will deliver bulk quantities of these whilst investigating related materials designed with optimised properties. State-of-the art computational approaches to materials exploration in silico will run in close collaboration with the synthetic teams in order to give a fast, iterative process of materials discovery, investigation and exploitation. The multiple electrochemical, structural and compositional changes that occur during battery operation must be understood in order to exploit these materials in a safe, reliable manner so that devices can be delivered to end users. The team will bring their extensive experience to bear on these problems to carry out the full structural, compositional and electrochemical analysis of these materials, vital in delivering reliable performance. Expertise in probing the local structure will allow us to generate insights into the nature of the electrochemical interfaces between anode/electrode/cathode. These are the regions where materials are at the limits of their (electro)chemical stability and so this understanding will allow us to find and then improve the limits of materials' performance in operando.

Many inherent problems need to be overcome if we are to approach an energy framework that is both clean and sustainable. Although progress is being made, it is likely that solutions will rely on new concepts in the design of materials rather than improvements to existing materials. This view provides the rationale behind the proposed research: based on preliminary exciting findings, we will extend our studies of a class of materials with unique structural features that have never been fully exploited - nor even fully explored. The research focuses on a mineral, schafarzikite, and our preliminary studies have been directed towards introducing functionality to provide useful properties. This proposal emanates from two highly exciting findings: 1) we have been able to insert anions into channels within the schafarzikite framework; 2) we have discovered a schafarzikite material that contains a low-dimensional copper oxide framework that is ferromagnetic. The first discovery suggests that this structure could make an important contribution to aspects of energy storage, both for new electrode materials and new electrolytes. It is our objective to characterise fully these new materials and screen them for use as advanced materials in these areas. This programme, and possible subsequent commercialisation, will be assisted by a collaboration with Johnson Matthey. The second research finding is of academic interest because ferromagnetic oxides are quite rare. However, added interest attaches to the fact that low dimensional copper oxides provided the basis for the High-Tc superoconducting materials that superconduct at temperatures up to 133 K. However, all these materials have antiferromagnetic parent phases, and this antiferromagnetism is likely to be inportant in the superconductivity mechanism. The chemical manipulation of this particular material to introduce electronic conductivity is therefore a major objective of the programme. We are not aware of any studies that relate to elecronic conduction in copper oxide materials with an inherent ferromagnetic ground state. Materials with the perovskite structure have been studied extensively and their properties have resulted in applications in many areas, including electrodes and electrolytes in electrochemical devices. Although structurally very different from perovskites, functionalising their properties is conceptually similar to that which can be achieved for the perovskite system: cation substitutions at one site can be used to tune the functional properties at the other. However, there has been very little previous research that has focused on this structure. We will therefore be vigilant to recognise other new features that are likely to become apparent during the programme but are not included in the specific targets above. The synthetic aspects of the programme of work will be informed by predictions of suitable chemical targets that have been determined by theoretical calculations relating to the stabilities of possible chemical compositions.

Since the commercial introduction of lithium-ion batteries (LIBs) by Sony in the early 1990s, LIBs become preferred power sources in portable electronics due to their high energy density. LIBs are being slowly introduced in the electric vehicles (EVs) and for grid storage applications. These high energy density LIBs use cobalt or nickel-rich layered cathode materials, which pose several issues. To meet the growing demands, high energy, sustainable, and safe battery technologies that are beyond LIBs are urgently required. Fluoride-ion batteries (FIBs) offer a potential next-generation electrochemical energy storage device that has a higher energy density and safety when compared with state-of-the-art LIBs. Upon realization of its full potential, FIBs would transform the automotive sector and other energy storage sectors beyond LIBs. Currently, FIBs are operated at high temperatures limited by the use of low fluoride-ion conducting solid electrolytes. The development of suitable liquid electrolytes has the potential to bring out the hidden potential of rechargeable fluoride-ion batteries. Controlling the reactivity of fluoride in solution is vital to develop non-aqueous liquid electrolytes. Earlier electron-deficient boron complexes were used to bind the fluoride ions and control its reactivity. However, boron-based molecules bind fluoride ions too strongly and will not release the fluoride ions to the electrodes in electrochemical cells; therefore, these complexes are not suitable for electrolytic applications. A series of organic molecules have identified that control the reactivity of the fluoride ions in solution, and at the same time, they would release the fluoride ions to the electrode in electrochemical cells (predicted based on the binding energy). Such molecules will enable the development of advanced liquid electrolytes for FIBs. In an alternative approach, the PI has also proposed to develop new 'quasi non-aqueous' fluoride transporting liquid electrolytes. These two types of liquid electrolytes will be used to build and investigate FIBs with various metal/metal fluoride combinations. The main objectives of the project are to develop suitable fluoride-ion-transporting non-aqueous and quasi-non-aqueous liquid electrolytes and to ensure that fluoride ion batteries perform under room temperature with high energy and safety. Potential applications and benefit: The primary outcome of the project will enable the rapid development of room temperature FIBs and will pave the way for the realisation of high energy rechargeable FIBs with applications in portable electronics, grid, and EVs.

High End Computing (HEC), or supercomputers, provides exciting opportunities in understanding and increasingly predicting the properties of complex materials through atomistic and electronic structure modelling. The scope and power of our simulations rely on the software we create to match the expanding capabilities provided by the latest development in hardware. Our project will build on the expertise in the UK HEC Materials Chemistry Consortium, to exploit the UK's world-leading supercomputer in a wide-ranging programme of research in the chemistry and physics of functional materials that are used in applications and devices including solar cells, light powerful eco batteries, large flexible electronic displays, self-cleaning and smart windows, improved mobile phones, cheaper and more efficient production of bulk and fine chemicals from detergents to medicines; and thus transforming lives of people and society. The project will develop five themes in applications and three on fundamental aspects of materials, bringing together the best minds of the UK academic community who represent over 25 universities. Close collaboration and scientific interactions between our themes will promote rapid progress and advancement of novel solutions benefiting both applied and fundamental developments. Tuning properties of materials forms the backbone of research in Energy Generation, Storage and Transport, which is a key application theme for UK's economy, which relies heavily on power consumption. We will target the performance of materials used in both batteries and fuel cells; and novel types of solar cells. In Reactivity and Catalysis, we will develop realistic models of several key catalytic systems. Targets include increasing efficiency in industrial processes and more efficient reduction in pollution, including exhaust fumes of petrol or diesel vehicles. New Environmental and Smart Materials will safely store radioactive waste, capture greenhouse gases for long-term storage, filter toxins and pollutants from water, thus improving our environment. This theme will also focus on smart materials used in self cleaning windows, and windows that allow heat from sunlight to enter or be reflected depending on the current temperature of the glass. Research in Soft Matter and Biomaterials will reveal the fundamental processes of biomineralisation, which drives bone repair and bone grafting; with a focus on synthetic bone replacement materials. Soft matter also poses novel and fascinating problems, particularly relating to the properties of colloids, polymers and gels. Materials Discovery will support both screening and global optimisation based approaches to a broad range of materials. Applications include, for example, screening different chemical dopants, which directly affects a targeted physical property of the material, to improve the desired property of a device, and searching the phase diagram for solid phases of a pharmaceutical drug molecule. As different solid phases of a molecule will typical dissolve at different rates, it is extremely important to administer the correct form or a higher/lower dose will result. Fundamental themes cover research in physics and chemistry of matter organised at all scales from Bulk to Surfaces and Interfaces to Low Dimensional Materials (e.g. nanotubes and particles). The challenges are in addressing the morphology, atomic structure and stability of different phases; defects and their effects; material growth, corrosion and dissolution; the structure and behaviour of interfaces. Example applications of nanomaterials include: in suntan lotions, smart windows and pigments, drug delivery, etc. To undertake these difficult and challenging simulations we will need computer software that can accurately model, both reproduce and predict, the materials of interest at the atomic and electronic scale. It is essential that our software is optimised for performance on the latest supercomputers.

The goal of this proposal is to develop and validate an in-situ Nuclear Magnetic Resonance (NMR)-based screening and optimisation methodology for heterogenised organocatalytic systems, able to monitor and evaluate catalyst activity, transport and surface interactions at a pore-scale level in such functionalised materials. Batch reaction studies combined with in-situ 1H and 13C NMR spectroscopy, diffusion and relaxation techniques will give new and exclusive insights into these systems by providing quantitative data on intra-pore kinetics, diffusion and adsorption, which will be able to direct catalyst formulation and reaction design by evaluating the controlling interactions and mass transport phenomena of the various reactant/solvent/product species within the pores of the heterogenised catalytic system, hence aid selection of optimal reaction parameters such as choice of suitable solvents, solid supports, pore size and type of linker to immobilise the organocatalyst on support. The validation of this methodology in heterogenised organocatalysis will be a significant step forward towards effective screening and development of these materials, which can be expanded to other related technologies using functionalised porous materials.