Developing a sustainable energy infrastructure for the 21st century requires the large scale development of renewable energy resources. Fully exploiting these inherently intermittent supplies will require advanced energy storage technologies, with rechargeable Li-ion and Na-ion batteries considered highly promising for both vehicle electrification and grid storage applications. However, the performance required of battery materials has not been achieved, and significant improvements are needed. Modern computational techniques allow the elucidation of structure-property relationships at the atomic level and are valuable tools in providing fundamental insights into novel materials. Therefore, in this thesis a combination of atomistic simulation and ab initio density functional theory (DFT) techniques have been used to study a number of potential battery cathode materials. Firstly, Na2FePO4F and NaFePO4 are interesting materials that have been reported recently as attractive positive electrodes for Na-ion batteries. Here, we report their Na-ion conduction behaviour and intrinsic defect properties using atomistic simulation methods. Na+ ion conduction in Na2FePO4F is predicted to be two-dimensional (2D) in the interlayer plane. Na ion migration in NaFePO4 is restricted to the [010] direction along a curved trajectory, leading to quasi-1D Na+ diffusion. Furthermore, Na/Fe antisite defects are predicted to have a lower formation energy in NaFePO4 than Na2FePO4F. The higher probability of tunnel occupation with a relatively immobile Fe2+ cation - along with a greater volume change on redox cycling - contributes to the poor electrochemical performance of NaFePO4. Secondly, work on the Na2FePO4F system is extended to include investigation of the surface structures and energetics. The equilibrium morphology is found to be essentially octagonal, compressed slightly along the [010] direction, and is dominated by the (010), (021), (122) and (110) surfaces. The calculated growth morphology is a more ``rod-like'' nanoparticle, with the (021), (023), (110) and (112) planes predominant. The (010) surface lies parallel to the Na layers in the ac plane and is unlikely to facilitate Na+ intercalation. As such, its prominence in the equilibrium morphology, and absence from the growth morphology, suggests nanoparticles synthesised in a kinetically limited regime should provide higher rate performance than those synthesised in close to equilibrium conditions. Surface redox potentials for Na2FePO4F derived using DFT vary between 2.76 - 3.37 V, in comparison to a calculated bulk cell voltage of 2.91 V. Most significantly, the lowest energy potentials are found for the (130) and (001) planes suggesting that upon charging Na+ will first be extracted from these surfaces, and inserted lastly upon discharging. Thirdly, the mixed phosphates Na4M3(PO4)2P2O7 (M=Fe, Mn, Co, Ni) are explored as a fascinating new class of materials reported to be attractive Na-ion cathodes, displaying low volume changes upon cycling indicative of long lifetime operation. Key issues surrounding intrinsic defects, Na-ion migration mechanisms and voltage trends have been investigated through a combination of atomistic energy minimisation, molecular dynamics and DFT simulations. The MD results suggest Na+ diffusion extends across a 3D network of migration pathways with an activation barrier of 0.20-0.24 eV, and diffusion coefficients (DNa) of 10-10-10-11 cm2s-1 at 325 K, suggesting high rate capability. The cell voltage trends, explored using DFT methods, indicate that doping the Fe-based cathode with Ni can significantly increase the voltage, and hence energy density. Finally, DFT simulations of K+-stabilised α-MnO2 have been combined with aberration corrected-STEM techniques to study the surface energetics, particle morphologies and growth mechanism. α-K0.25MnO2 grown through a hydrothermal synthesis method is found to produce primary nanowires with preferential growth along the [001] direction. Primary nanowires attach through a shared (110) interface to form larger secondary nanowires. This is in agreement with DFT simulations with the {100}, {110} and {211} surfaces displaying the lowest surface energies. The ranking of surface energies is driven by Mn coordination environments and surface relaxation. The calculated equilibrium morphology of α-K0.25MnO2 is consistent with the observed primary nanowires from high resolution electron microscopy images.

Lithium-ion (Li-ion) batteries are critically important for portable electronics, electric vehicles, and grid-level energy storage. The development of next-generation Li-ion batteries requires high-capacity electrodes with a long cycle life. However, the high capacity of Li storage is usually accompanied by large volume changes, dramatic morphological evolution, and mechanical failures in the electrodes during charge and discharge cycling. To understand the degradation of electrodes and resulting loss of capacity, this thesis aims to develop mechanistic-based models for predicting the chemo-mechanical processes of lithiation and delithiation in high-capacity electrode materials. To this end, we develop both continuum and atomistic models that simulate mass transport, interface reaction, phase and microstructural evolution, stress generation and damage accumulation through crack or void formation in the electrodes. The modeling studies are tightly coupled with in-situ transmission electron microscopy (TEM) experiments to gain unprecedented mechanistic insights into electrochemically-driven structural evolution and damage processes in high-capacity electrodes. Our models are successfully applied to the study of the two-phase lithiation and associated stress generation in both crystalline and amorphous silicon anodes, which have the highest known theoretical charge capacity, as well as the lithiation/sodiation-induced structural changes and mechanical failures in silicon-based multilayer electrodes. The modeling studies have uncovered unexpected electrochemical reaction mechanisms and revealed novel failure modes in silicon-based nanostructured anodes. Our modeling research provides insights into how to mitigate electrode degradation and enhance capacity retention in Li-ion batteries. More broadly, our work has implications for the design of nanostructured electrodes in next-generation energy storage systems.

[EN] The outstanding physico-chemical properties of graphene have gained considerable interest of the scientific community in last years due to the wide variety of applications in which this material could be used. In this doctoral thesis new nanomaterials based on graphene has been developed and their uses in fields such as Li-ion batteries, photocatalytic generation of hydrogen and photovoltaics have been studied. It has been shown that grapene oxide can be combined with other layered materials such as hydrotalcites and, after chemical reduction by pyrolysis, it is possible to obtain hybrid materials (metal oxides-reduced graphene oxide) that can be employed as anodes in Li-ion batteries, since they exhibit interesting properties derived from the combination of their components (chapter 3). A new way to prepare iron oxide nanoparticles embedded in a graphenic matrix has been presented, showing that this composite exhibits a high capacity of energy storage and durability when it is used as an anode in Li-ion batteries (chapter 4). It has been demonstrated that, although graphene oxide acts as an active photocatalysts under UV irradiation, this can be sensitized with dyes and, in particular, with ruthenium tris-2,2'-bipiridine, which can provide photoactivity under visible light for the generation of hydrogen from water (chapter 5). A new method to prepare phosphorous doped graphene has been described. This nanomaterial acts as a photocatalyst and, under certain conditions, is able to generate considerable amount of hydrogen from water using a UV-Vis lamp as an irradiation source. The values of hydrogen generation rate obtained are comparable to those of the most active organic heterogeneous photocatalysts described in the state of the art (chapter 6). A new method to prepare a p-n heterojunction has been presented, which is based on the combination of boron doped graphene and nitrogen doped graphene. This heterojunction is able to generate higher photocurrent and photovoltage than the separated semiconductor components (chapter 7). / [ES] Las extraordinarias propiedades físico-químicas del grafeno han despertado el interés de la comunidad científica en los últimos años debido a las múltiples aplicaciones en las que se podría usar este material. En esta tesis doctoral se han desarrollado nuevos nanomateriales basados en grafeno y se ha estudiado su uso en campos como las baterías de ion-Li, la producción fotocatalítica de hidrógeno y la fotovoltaica. Se ha demostrado que el óxido de grafeno se puede combinar con otros materiales laminares como las hidrotalcitas y que, tras su reducción química por pirólisis, es posible obtener materiales híbridos (óxidos metálicos/óxido de grafeno reducido) que pueden ser empleados como ánodos en baterías de ion-Li, ya que poseen interesantes propiedades derivadas de la combinación de sus componentes (capítulo 3). Se ha presentado una forma novedosa de preparar nanopartículas de óxido de hierro embebidas en una matriz grafénica, estableciendo que este composite posee una elevada capacidad de almacenamiento de carga y durabilidad cuando es empleado como ánodo en baterías de ion-Li (capítulo 4). Se ha comprobado que, aunque el óxido de grafeno es un fotocatalizador activo con luz ultravioleta, éste se puede sensibilizar con colorantes y, en particular, con rutenio tris-2,2'-bipiridilo, el cual le proporciona fotoactividad frente a la luz visible para la generación de hidrógeno a partir de agua (capítulo 5). Se ha descrito un método novedoso de preparar grafeno dopado con fósforo. Este nanomaterial se comporta como fotocatalizador y bajo ciertas condiciones, es capaz de generar cantidades importantes de hidrógeno a partir de agua utilizando lámpara de UV-Vis, midiéndose valores de velocidad de generación de hidrógeno que son comparables con los de los fotocatalizadores orgánicos heterogéneos más activos descritos en el estado del arte (capítulo 6). Se ha presentado una forma novedosa de preparar una heterounión p-n basada en la combinación de grafeno dopado con boro y grafeno dopado con nitrógeno. Esta heterounión es capaz de generar mayor fotocorriente y fotovoltaje que los componentes semiconductores por separado (capítulo 7). / [CA] Les extraordinàries propietats fisico-químiques del grafè han despertat l'interès de la comunitat científica en els últims anys a causa de les múltiples aplicacions en les que es podria fer servir aquest material. En aquesta Tesi doctoral s'han desenvolupat nous nanomaterials basats en grafè i s'ha estudiat el seu ús en camps com les bateries d'ió-Li, la producció fotocatalítica d'hidrogen i la fotovoltaica. S'ha demostrat que l'òxid de grafè es pot combinar amb altres materials laminars com les hidrotalcites i que, després de la seva reducció química per piròlisi, és possible obtenir materials híbrids (òxids metàl¿lics / òxid de grafè reduït) que poden ser utilitzats com ànodes en bateries d'ió-Li, ja que posseeixen interessants propietats derivades de la combinació dels seus components (capítol 3). S'ha presentat una forma nova de preparar nanopartícules d'òxid de ferro embegudes en una matriu grafénica, establint que aquest composite té una elevada capacitat d'emmagatzematge de càrrega i durabilitat quan és utilitzat com a ànode en bateries d'ió-Li (capítol 4). S'ha comprovat que, tot i l'òxid de grafè és un fotocatalitzador actiu amb llum ultraviolada, aquest es pot sensibilitzar amb colorants i, en particular, amb ruteni tris-2,2'-bipiridil, el qual li proporciona fotoactivitat enfront de la llum visible per a la generació d'hidrogen a partir d'aigua (capítol 5). S'ha descrit un mètode nou de preparar grafè dopat amb fòsfor. Aquest nanomaterial es comporta com fotocatalitzador i sota certes condicions, és capaç de generar quantitats importants d'hidrogen a partir d'aigua utilitzant llum d'UV-Vis, mesurant valors de velocitat de generació d'hidrogen que són comparables amb els dels fotocatalitzadors orgànics heterogenis més actius descrits en l'estat de l'art (capítol 6). S'ha presentat una forma nova de preparar una heterounió p-n basada en la combinació de grafè dopat amb bor i grafè dopat amb nitrogen. Aquesta heterounió és capaç de generar major fotocorrent i fotovoltatge que els components semiconductors per separat (capítol 7). / Latorre Sánchez, M. (2015). Nanomateriales basados en grafeno y su aplicación en nuevos sistemas de energía [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/54135

The aim of this thesis is to investigate pyroborates, M2B2O5, and orthoborates, M3(BO3)2, where M = Mg, Mn, Co, Ni, as high capacity and high voltage Li- and Mg-ion cathode materials. We explore the layered orthoborates (M3(BO3)2 which, to our knowledge, have not been previously considered as Li- or Mg-ion cathodes, perhaps due to the lack of Li analogues. Structural analysis shows that mixed metal orthoborates form a solid solution, with cation order driven by the presence of directional d orbitals. Electrochemical studies show that Mg can be removed from the structure and replaced with Li in a 1:1 ion ratio. In the compound Mg2Mn(BO3)2 removal of 1 Mg is achieved giving a capacity of 209.9 mAh g 1. The pyroborates (M2B2O5) are an unexplored family of borate polyanions, which offer higher theoretical capacities and voltages than LiMBO3 due to their more condensed frameworks. There are no known Li containing pyroborates, we use electrochemical ion exchange, with the aim of replacing each Mg with 2 Li to form LixMB2O¬5. The stoichiometry can be varied to alter the redox couple utilised and the Mg available for removal. MgxM2-xB2O5 has been synthesised for M = Mn, Co, Fe and Ni and all forms have been shown to form a solid solution with cation ordering over the two M sites. In MgMnB2O5 we have shown that Mg can be fully removed while retaining the pyroborate structure. Subsequently up to 1.1 Li can be inserted giving discharge capacities of 240 mAhg-1 above 1.5 V. After 100’s of cycles 2 Li can be reversibly cycled. The insertion of Li has been confirmed by 7Li NMR and the oxidation state changes in Mn have been investigated by SQUID magnetometry and XANES spectroscopy. Electrochemical studies in materials where M = Fe, Co, and Ni show high voltage plateaus ( > 3.5 V) but limited capacity at room temperature. Increased temperatures improves cycling, with Co and Fe based compounds reaching full theoretical capacities ( > 200 mAhg-1). As Mg can be removed from the structure, the pyroborates could be of interest in Mg-ion batteries, which offer benefits in energy density, cost, and safety. Mg-ion battery research is still in its infancy, therefore here we develop methods to reliably test Mg-ion cathodes and electrolytes. We demonstrate that despite significant side reactions, Mg can be reversibly cycled in the MgMnB2O5 system in a full Mg-ion cell, showing that pyroborates are a promising family of materials for high capacity, high voltage Mg-ion cathodes. This study shows that the pyroborates and orthoborates are a promising family of materials for Li- and Mg-ion cathodes, with the light weight structure leading to high specific capacities. The ability to replace Mg for Li in polyanion materials without disrupting the crystal structure opens a new way to search for novel, high energy density, Li-ion cathodes.

Dans les années à venir, les secteurs du transport et du résidentiel-tertiaire vont faire l'objet de contraintes de plus en plus sévères, que ce soit au niveau de leur consommation d'énergie ou de leur émission de polluants. Dans le domaine du transport, la hausse régulière du trafic et l'augmentation du poids et de la puissance des véhicules thermiques ont été plus significatives que la baisse de consommation unitaire des moteurs, contribuant à accroître un peu plus l'empreinte énergétique et environnementale des véhicules. Dans l'habitat, la consommation d'énergie et les émissions liées se sont accru fortement du fait de la croissance des besoins en électricité spécifique, le confort et la technologie exigeant là encore davantage d'énergie que par le passé, et ce malgré une baisse des usages liés à la cuisson et au chauffage. Avec cette thèse sur le stockage de l'électricité, une pierre se voit ajoutée à l'édifice naissant des alternatives durables à un modèle énergétique en disgrâce. Plus précisément, sont étudiés dans ce mémoire les différents usages de batteries lithium-ion utilisées comme fonction de stockage d'énergie à la convergence des besoins de l'habitat solaire et du transport électrique. Derrière le terme "habitat solaire", on entend une maison particulière équipée en toiture d'une installation de panneaux photovoltaïques. Derrière le terme "transport électrique", on entend à la fois la mobilité électrique de véhicules électriques et le transport d'électricité sur le réseau. Après une présentation du cadre contextuel et des champs d'étude de la thèse, un balayage du sujet permet de dégager certains axes de recherche directement exploitables et valorisables. Concrètement, l'hypothèse de départ d'un travail centré sur le véhicule électrique est validée. L'inventaire systématique des interactions de convergence entre les pôles de l'habitat solaire et ceux du transport électrique permet ensuite d'isoler des cas concrets d'usages convergents du stockage de l'électricité qui, à moyen terme, feront référence dans le domaine énergétique. Typiquement, le cœur de thèse se focalise sur l'amélioration de l'autoconsommation de la production photovoltaïque pour les besoins des charges domestiques et du véhicule électrique. Tout au long de cette démarche, des applications concrètes au cas de la Corse sont présentées.

This diploma thesis deals with problematics of electrochemical power sources with focus on lithium accumulators, their construction and functioning priciple. It also discusses the safety of li-ion batteries with respect to their flammability. In addition, the flame retarders, which help to lower the flammability, are listed. The thesis describes Cyclic Voltammetry and Galvanostatic Cycling with Potencial which are lithium-ion cell measuring methods. In the last part, the influence of various flame retarders on negative electrode is compared based on the conducted tests.