Sodium-ion batteries (SIBs) are considered as a promising alternative to lithium-ion batteries (LIBs) for large-scale renewable energy storage units due to the abundance of sodium resource and its low cost. However, the development of anode materials for SIBs to date has been mainly limited to some traditional anodes for LIBs, such as carbonaceous materials. SnSe2 is a member of two dimensional layered transition metal dichalcogenide (TMD) family, which has been predicted to have high theoretical capacity as anode material for sodium ion batteries (756 mAh g-1), thanks to its layered crystal structure. Yet, there have been no studies on using SnSe2 as Na ion battery anode. In this thesis, we developed a simple synthesis method to prepare pure SnSe2 nanosheets, employing N2 saturated NaHSe solution as a new selenium source. The SnSe2 2D sheets achieve theoretical capacity during the first cycle, and a stable and reversible specific capacity of 515 mAh g-1 at 0.1 A g-1 after 100 cycles, with excellent rate performance. Among all of the reported transition metal selenides, our SnSe2 sample has the highest reversible capacity and the best rate performances. A combination of ex-situ high resolution transmission electron microscopy (HRTEM) and X-ray diffraction was used to study the mechanism of sodiation and desodiation process in this SnSe2, and to understand the reason for the excellent results that we have obtained. The analysis indicate that a combination of conversion and alloying reactions take place with SnSe2 anodes during battery operation, which helps to explain the high capacity of SnSe2 anodes for SIBs compared to other binary selenides. Density functional theory was used to elucidate the volume changes taking place in this important 2D material.

Sodium-ion batteries (SIBs) are rechargeable batteries analogous to lithium-ion batteries but use sodium ions (Na+) as the charge carriers. They are considered a promising alternative for lithium-ion batteries (LIBs) in renewable large-scale energy storage applications due to their similar electrochemical mechanisms and abundant sodium resources. Two-dimensional (2D) materials, with atomic or molecular thickness and large lateral lengths, have emerged as important functional materials due to their unique structures and excellent properties. These 2D nanosheets have been highly studied as sodium-ion battery anodes. They have large interlayer spacing, which can effectively buffer the big volume expansion and prevent electrode collapse during the charge-discharge process. Different strategies such as preparing composites, heterostructures, expanded structures, and chemical functionalization can greatly improve cycling stability and lead to high reversible capacity. In this dissertation, state-of-the-art SIB based on 2D material electrodes will be presented. In particular, Tin-based 2D materials and laser-scribed graphene anodes are discussed. Different strategies involving engineering both synthesis methods, intrinsic properties of materials, and device architecture are used to optimize the battery performance.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19739号 / 工博第4194号 / 新制||工||1647(附属図書館) / 32775 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 陰山 洋, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Carbonatos fosfatos isoestruturados do tipo sidorenkitas sÃo materiais com alto potencial de aplicaÃÃo em cÃtodos dos mais modernos tipos de baterias de sÃdio. Sua estrutura lamelar permite a inserÃÃo e extraÃÃo dos Ãons de sÃdio, que sÃo a principal fonte de forÃa eletromotriz da bateria. Utilizando um elemento muito mais abundante na crosta terrestre, esses dispositivos sÃo a grande promessa para substituiÃÃo da, jà bastante difundida, bateria de Ãons de lÃtio. PorÃm, o cÃtodo que contÃm as caracterÃsticas ideais para produzir o melhor desempenho, propiciando alta densidade de energia e estabilidade quÃmica, ainda està em desenvolvimento. A espectroscopia Raman continua sendo o melhor mÃtodo para caracterizar as propriedades destes compostos, pois contÃm a grande vantagem de ser altamente sensÃvel ao ambiente molecular das ligaÃÃes do oxigÃnio com os metais de transiÃÃo, o fÃsforo e o carbono. Nesta linha, realizamos um estudo de espectroscopia Raman em um conjunto de carbonatos fosfatos do tipo Na3MCO3PO4 (M = Mn, Fe, Co e Ni), obtidos por sÃntese hidrotÃrmica em microondas a 210 ÂC por 30 minutos. O sucesso na inserÃÃo de variados metais no interior de octaedros MO6, com raios iÃnicos distintos, produz uma alteraÃÃo no volume da cÃlula unitÃria do arranjo cristalino, modificando a distÃncia de equilÃbrio das ligaÃÃes atÃmicas, provocando uma alteraÃÃo substancial no nÃmero de onda dos seus modos normais de vibraÃÃo. Por isso, visto que informaÃÃes essenciais das propriedades quÃmicas e estruturais dos mais variados tipos de carbonatos fosfatos sÃo reveladas pela tÃcnica da espectroscopia Raman de forma confiÃvel, sua utilizaÃÃo se torna indispensÃvel para o desenvolvimento de mÃtodos e o planejamento de um material eficiente e comercialmente viÃvel para as inovadoras baterias de Ãons de sÃdio.

Doctor of Philosophy / Department of Chemistry / Jun Li / Electrical energy storage (EES) is crucial in todays’ society owing to the advances in electric cars, microelectronics, portable electronics and grid storage backup for renewable energy utilization. Lithium ion batteries (LIBs) have dominated the EES market owing to their wide use in portable electronics. Despite the success, low specific capacity and low power rates still need to be addressed to meet the increasing demands. Particularly, the low specific capacity of cathode materials is currently limiting the energy storage capability of LIBs. Vanadium pentoxide (V₂O₅) has been an emerging cathode material owing to its low cost, high electrode potential in lithium-extracted state (up to 4.0 V), and high specific capacities of 294 mAh g⁻¹ (for a 2 Li⁺/V₂O₅ insertion process) and 441 mAh g⁻¹ (for a 3 Li⁺/V₂O₅ insertion process). However, the low electrical conductivities and slow Li⁺ ion diffusion still limit the power rate of V₂O₅. To enhance the power-rate capability we construct two core-shell structures that can achieve stable 2 and 3 Li⁺ insertion at high rates. In the first approach, uniform coaxial V₂O₅ shells are coated onto electrospun carbon nanofiber (CNF) cores via pulsed electrodeposition. The materials analyses confirm that the V₂O₅ shell after 4 hours of thermal annealing at 300 °C is a partially hydrated amorphous structure. SEM and TEM images indicate that the uniform 30 to 50 nm thick V₂O₅ shell forms an intimate interface with the CNF core. Lithium insertion capacities up to 291 and 429 mAh g⁻¹ are achieved in the voltage ranges of 4.0 – 2.0 V and 4.0 – 1.5 V, respectively, which are in good agreement with the theoretical values for 2 and 3 Li⁺/V₂O₅ insertion. Moreover, after 100 cycles, remarkable retention rates of 97% and 70% are obtained for 2 and 3 Li⁺/V₂O₅ insertion, respectively. In the second approach, we implement a three-dimensional (3D) core-shell structure consisting of coaxial V₂O₅ shells sputter-coated on vertically aligned carbon nanofiber (VACNF) cores. The hydrated amorphous microporous structure in the “as-deposited” V₂O₅ shells and the particulated nano-crystalline V₂O₅ structure formed by thermal annealing are compared. The former provides remarkably high capacity of 360 and 547 mAh g⁻¹ in the voltage range of 4.0 – 2.0 V and 4.0 – 1.5 V, respectively, far exceeding the theoretical values for 2 and 3 Li⁺/V₂O₅ insertion, respectively. After 100 cycles of 3 Li⁺/V₂O₅ insertion/extraction at 0.20 A g⁻¹ (~ C/3), ~ 84% of the initial capacity is retained. After thermal annealing, the core-shell structure presents a capacity of 294 and 390 mAh g⁻¹, matching well with the theoretical values for 2 and 3 Li⁺/V₂O₅ insertion. The annealed sample shows further improved stability, with remarkable capacity retention of ~100% and ~88% for 2 and 3 Li⁺/V₂O₅ insertion/extraction. However, due to the high cost of Li. alternative approaches are currently being pursued for large scale production. Sodium ion batteries (SIB) have been at the forefront of this endeavor. Here we investigate the sodium insertion in the hydrate amorphous V₂O₅ using the VACNF core-shell structure. Electrochemical characterization was carried out in the potential ranges of 3.5 – 1.0, 4.0 – 1.5, and 4.0 – 1.0 (vs Na/Na⁺). An insertion capacity of 196 mAh g-1 is achieved in the potential range of 3.5 – 1.0 V (vs Na/Na⁺) at a rate of 250 mA g⁻¹. When the potential window is shifted upwards to 4.0 – 1.5 V (vs Na/Na⁺) an insertion capacity of 145 mAh g⁻¹ is achieved. Moreover, a coulombic efficiency of ~98% is attained at a rate of 1500 mA g⁻¹. To enhance the energy density of the VACNF-V₂O₅ core-shell structures, the potential window is expanded to 4.0 – 1.0 V (vs Na/Na⁺) which achieved an initial insertion capacity of 277 mAh g⁻¹. The results demonstrate that amorphous V₂O₅ could serve as a cathode material in future SIBs.

<p>The single particle model was extended to include electrode and particle volume expansion effects observed in high capacity alloying electrodes. The model was used to predict voltage profiles in sodium ion batteries with tin and tin-phosphide negative electrodes. It was seen that the profiles predicted by the modified model were significantly better than the classical model. A parametric study was done to understand the impact of properties such as particle radius, diffusivity, reaction rate etc on the performance of the electrode. The model was also modified for incorporating particles having a cylindrical morphology. For the same material properties, it was seen that cylindrical particles outperform spherical particles for large L/R values in the cylinder due to the diffusion limitations at low L/R ratios. A lattice spring-based degradation model was used to observe crack formation and creep relaxation within the particle. It was observed that the fraction of broken bonds increases with an increase in strain rate. At low strain rates, it was seen that there was a significant expansion in particle volumes due to creep deformation. This expansion helped release particle stresses subsequently reducing the amount of fracture.</p>

No description available.

This thesis concerns the use of advanced solid-state NMR methods to investigate local structural features and ion dynamics in a series of paramagnetic cathode materials for lithium and sodium ion batteries. A variety of polyanionic phosphate and fluorophosphate derivatives were explored to identify characteristics that ultimately improve battery performance. Solid-state NMR is an excellent method to probe such materials, as it offers the unique ability to track the charge-carrying alkali ion (Li or Na) over the course of the electrochemical process, adding insight not obtainable by bulk characterization techniques. Selective inversion exchange experiments were used to elucidate ion diffusion pathways in low-mobility Li ion conductors Li2MnP2O7 and Li2SnO3. Contrasting experimental results highlight significant differences observed when the method is applied to paramagnetic versus diamagnetic systems, with the former being much more complicated to study with traditional exchange spectroscopy methods. Selective inversion was similarly applied to a new lithium iron vanadate framework, LiFeV2O7, where the changing ion dynamics as a function of electrochemical state of charge were quantified, allowing for the development of a model to explain the corresponding phase changes in the material. This represents the first example of an ex situ Li-Li exchange study for a cathode material, particularly where the conductivity changes are linked directly to a change of ion exchange rates. Additionally, 23Na NMR spectroscopy was additionally used to investigate Na2FePO4F as a potential Na ion battery cathode, where ex situ NMR measurements successfully determined the local Na ion distribution in the electrode as a function of electrochemical cycling. In combination with density functional theory (DFT) calculations, the NMR results lead to the construction of a biphasic desodiation model for Na2FePO4F cathodes. Finally, possible defect formation in sodium iron fluorophosphate was investigated with a variety of methods including 23Na NMR, DFT calculations, powder X-ray diffraction and Mössbauer spectroscopy. / Thesis / Doctor of Philosophy (PhD) / Lithium ion batteries are considered to be at the forefront of current energy storage development, offering high energy density in a small and lightweight package. This thesis delineates the investigation of materials for both lithium and sodium ion batteries via nuclear magnetic resonance methods. Slow Li ion dynamics were investigated and quantified in three lithium-conducting materials: Li2MnP2O7, Li2SnO3, and LiFeV2O7 via the use of selective inversion NMR experiments. In the case of the latter, the ion dynamics were probed ex situ during the course of battery cycling, where a maximum in Li mobility is observed approximately half way through the charge-discharge cycle. Additionally, a potential Na ion cathode material, Na2FePO4F, was found by ex situ methods to reveal a biphasic mechanism for the desodiation of the electrode during charging. This mechanism and the NMR data used to discover it were further supported by ab initio calculations.

The demand for alternative secondary batteries to lithium-ion batteries (LIBs) grows. Sodium-ion batteries (SIBs) have been studied for many years and could replace LIBsfor some application. Metallic anodes for both LIBs and SIBs are interesting due totheir high energy densities. Several aspects such as reactivity, stability and depositionmorphology must be properly addressed before metallic Na could be considered apossible anode material. This study aims to evaluate deposition of Na on Alelectrodes using fundamental electrochemical theories. Na deposition was studiedusing pouch cells and sodium triflate (NaOTf) in dimethyl glycol ether (diglyme) aselectrolyte. Galvanostatic deposition using different current densities, electrolyteconcentrations and potential pulses prior to galvanostatic deposition were tested. Theelectrochemical methods used in this study were galvanostatic deposition andchronoamperometry. The morphology of deposited Na was analyzed with ex-situscanning electron microscopy (SEM). A decrease of the size of deposited Na islandswas observed for both increasing current density and decreasing electrolyteconcentration. Fluctuations and poor stability in the deposition potential wereobtained when decreasing the electrolyte concentration under 0.5 M and also whenincreasing the current density over 1 mA cm-2. The most homogeneous depositionwas obtained with a 1030 ms potential pulse amplitude (-3 V vs. Na+/Na) prior togalvanostatic deposition (1 mA cm-2, 0.5 mAh cm-2) using 0.1 M NaOTf in diglyme aselectrolyte. Reproducibility was a major issue in this study and further investigation ofseveral parameters is needed.

L'évolution des consommations énergétiques au cours des dernières décennies entraîne des modifications majeures dans la conception des systèmes électriques autonomes à fournir, que ce soit pour des applications électriques ou électroniques. La nécessité présente de réaliser des générateurs capables de délivrer l'énergie suffisante, avec une garantie de sûreté maximale, impose à la recherche l'exploration de nouvelles voies de stockage. Les voies actuelles par accumulateurs au lithium tendent à montrer leurs limites, tant stratégiques qu'environnementales. Dans ce cadre, la construction de nouveaux systèmes électrochimiques mettant en œuvre le sodium ouvre une possibilité de réalisation d'accumulateurs sans lithium. Le besoin de batteries toujours plus performantes oblige à des conceptions innovantes, abandonnant la voie liquide au profit de systèmes tout solide plus sécuritaires. De plus, la miniaturisation de l'électronique conduit à revoir le dimensionnement des batteries, vers des batteries de type micro, pour lesquelles l'intérêt d'un empilement tout solide n'est plus à démontrer. Aujourd'hui, des verres de chalcogénures au soufre permettent l'accès à des conductivités ioniques qui laissent entrevoir la possibilité d'une réalisation de batteries tout solide, à la fois sous forme de micro batteries ou de batteries massives. Un effort de recherche a été porté à la formulation de ces verres de chalcogénures afin d'obtenir des conductivités ioniques maximales et des propriétés autorisant leur utilisation comme électrolyte. La modification de ces verres met alors en lumière l'intérêt des différents éléments les composant. L'étude de la mise en forme de l'électrolyte par dépôts de type couches minces (obtenues par Radio Fréquence Magnétron Sputering, RFMS) prouve la faisabilité de ces micro batteries tout solide au sodium. Par la suite, la réalisation de batteries massives tout solide a demandé la synthèse de deux matériaux de cathode (NaCrO2 et Na[Ni0,25Fe0,5Mn0,25]O2) et de deux matériaux d'anode (Na15Sn4 et Na) permettant ainsi la mise en œuvre de quatre empilements électrochimiques, tous caractérisés comme accumulateurs. Enfin, l'amélioration des interfaces grâce à un gel-polymère a permis de perfectionner les propriétés des assemblages avec notamment une augmentation des vitesses de charge/décharge et une mobilisation accrue des matériaux actifs de cathode. / The evolution of energy consumption in recent decades has led to major changes in the design of autonomous electrical systems dedicated to either electrical or electronic applications. The present demand to build generators capable of delivering sufficient energy, with a guarantee of maximum safety, requires to explore new storage routes. The current lithium battery routes tend to show their limits, both strategic and environmental. In this context, the construction of new electrochemical systems implementing sodium opens the way of the lithium-free accumulators production. The need for ever more efficient batteries requires innovative designs, giving up the liquid path in favor of stronger solid systems. In addition, the miniaturization of electronics leads to a review of the size of the batteries, to micro-type batteries, for which the interest of a solid stack is no longer to demonstrate. Today, sulfur chalcogenide glasses allow access to ionic conductivities that suggest the possibility of a realization of all solid batteries, both in the form of micro batteries or massive batteries. A research effort has been made to formulate these chalcogenide glasses in order to obtain a maximum of ionic conductivity and properties allowing their use as electrolytes. The composition of these glasses highlights the interest of the different elements for such properties. The study of the electrolyte shaping by thin-film deposition (obtained by Radio Frequency Magnetron Sputering, RFMS) proves the feasibility of these all-solid sodium micro-batteries. Subsequently, the realization of massive all solid batteries required the synthesis of two cathode materials (NaCrO2 and Na [Ni0.25Fe0.5Mn0.25]O2) and two anode materials (Na15Sn4 and Na) thus allowing the implementation of four electrochemical stacks, all characterized as accumulators. Finally, the improvement of the interfaces thanks to a gel-polymer made it possible to improve the properties of the assemblies with notably an increase of the speeds of charge / discharge and an enhanced mobilization of the cathode active materials.