After three decades of commercialization, graphite remains the preferred active material for intercalation-type Li-ion battery anodes. Still, the characterization of staging continues to be elusive at the sub-micro- and nano-scales, the typical dimensions of graphite crystallites. Here, the intercalation of Al-based anions in graphitic materials was studied using X-ray powder diffraction (XRD) and Raman spectroscopy. While, in the first case, the analysis was done ex-situ and in mm3-samples, a more localized view was provided by the laser probe which could, furthermore, interrogate the electrochemical process in real-time (in-situ). To do this, an electrochemical cell for Raman studies was custom-made for Al batteries working with non-aqueous electrolytes. Two C materials were used: natural graphite (NG) and processed expandable graphite (EG). Owing to the smaller flake size, higher graphitization degree and larger crystallites of the NG, the Al/NG cells exhibited better performance than the Al/EG ones. Interestingly, discrepancies were observed in the stage numbers estimated from XRD and Raman. These were thought to arise from the, respectively, long- and short-range atomic order scales that are analyzed by those two techniques. To confirm this, in-situ Raman multi-point studies were performed. The results show the presence of domains with mixed stage graphite intercalation when the cells were fully charged, explaining the staging discrepancies.

Natural graphite from cheap and abundant natural sources is an attractive anode material for lithium ion batteries. We report on modifications of such a common natural graphite, whose electrochemical performance is very poor, with solutions of (NH4)2S2O8, concentrated nitric acid, and green chemical solutions such of e.g. hydrogen peroxide and ceric sulfate. These treatments resulted in markedly im-proved electrochemical performance (reversible capacity, coulombic efficiency in the first cycle and cycling behavior). This is attributed to the effective removal of active defects, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. These changes inhibit the decomposition of electrolyte solution, pre-vent the movement of graphene planes along a-axis direction, and provide more passage and storage sites for lithium. The methods are mild, and the uniformity of the product can be well controlled. Pilot experiments show promising results for their application in industry.

Orientador: Prof. Dr. André Gustavo Scagliusi Landulfo / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Física, 2017.

La récupération de chaleur fatale est un véritable challenge pour l’amélioration de l’efficacité énergétique. Le stockage par chaleur latente est une solution qui répond à cet enjeu. Nous nous intéressons aux procédés industriels avec un rapport puissance sur énergie élevé. L’un des procédés identifiés est la stérilisation de produits agroalimentaires. Cependant, les matériaux à changement de phase, peu conducteurs, ne permettent pas d’obtenir des puissances thermiques suffisantes pour ces applications. L’amélioration de la surface d’échange ou l’augmentation de la conductivité thermique du matériau sont alors nécessaires. Un premier dispositif expérimental de stockage thermique comparant différentes techniques d’intensification des transferts a été réalisé. Le concept à base de paraffine et de Graphite Naturel Expansé (GNE) s’est montré le plus performant par rapport à des solutions de type ailettes ou poudre de graphite. La caractérisation thermique du matériau composite GNE/paraffine sélectionné a été réalisée par plusieurs méthodes. Des valeurs de conductivité thermique effective de l’ordre 20 W.m-1.K-1 ont été obtenues. Dans un second temps, un démonstrateur de 100kW/6kW.h est dimensionné et réalisé. Ce dispositif testé sur un procédé de stérilisation existant permet une économie d’énergie de 15%, conforme aux prévisions. L’identification de la conductivité thermique plane du matériau et l’influence de la résistance thermique de contact sont réalisées à l’aide d’un dispositif expérimental, couplé à un modèle numérique. Enfin, le développement d’un dispositif de vieillissement permet l’étude de la stabilité thermique de ce matériau. / Waste heat recovery is a challenge for the improvement of energy efficiency. Latent heat storage is a solution that addresses this issue. We focus on industrial processes with high energy on power ratios. One of the identified processes is the sterilization of food products. However, phase change materials, which have low thermal conductivities, do not provide sufficient thermal powers for these applications. The improvement of the heat exchange surface or the increase in thermal conductivity of the material are then necessary. A first experimental thermal storage comparing various heat transfer intensification techniques was achieved. The concept based on paraffin and Expanded Natural Graphite (ENG) has proven to be the most efficient compared to solutions using fins or graphite powder. The thermal characterization of the selected composite material ENG/paraffin was performed by several methods. Effective thermal conductivities values of about 20 W.m-1.K-1 were obtained. In a second step, a 100kW/6kW.h demonstrator is designed and realized. This device tested on an existing sterilization process provides an energy saving of 15%, as expected. The identification of the planar thermal conductivity of the composite material and the influence of the thermal contact resistance are carried out using an experimental device, coupled to a numerical model. Finally, an aging device is used to study the thermal stability of this material

Natural graphite from cheap and abundant natural sources is an attractive anode material for lithium ion batteries. We report on modifications of such a common natural graphite, whose electrochemical performance is very poor, with solutions of (NH4)2S2O8, concentrated nitric acid, and green chemical solutions such of e.g. hydrogen peroxide and ceric sulfate. These treatments resulted in markedly im-proved electrochemical performance (reversible capacity, coulombic efficiency in the first cycle and cycling behavior). This is attributed to the effective removal of active defects, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. These changes inhibit the decomposition of electrolyte solution, pre-vent the movement of graphene planes along a-axis direction, and provide more passage and storage sites for lithium. The methods are mild, and the uniformity of the product can be well controlled. Pilot experiments show promising results for their application in industry.

This diploma thesis deals with an issue of lithium-ion batteries, primarily with negative (anode) electrode materials. Natural graphite in two forms, namely flake and expanded graphite, is used in the thesis as active electrode material. It is concerned with study of their capacity and output characteristics depending on the pressing pressure and discharging current. The first part of thesis consists of theory and describes basic principles and the composition of lithium-ion batteries. Materials, their characteristics used in production and theoretical description of measurement techniques are presented then. The second part of the thesis is focused on production, assembling and measurement of the characteristics of the produced electrodes. The aim of the thesis is finding the effects of changes of pressing pressure on the capacity, stability during cycling and stability at higher loads.

This diploma thesis deals with the issue of lithium-ion accumulators. The thesis focuses on the negative electrode of lithium-ion accumulators made of natural graphite. The first part of this thesis points to the issue of electrochemical cells. In the theoretical part the thesis deals with the SEI layer, advantages, disadvantages, characteristics, operating principle and the use of lithium-ion accumulators. The practical part focuses on the electrochemical properties of negative electrode, especially the determination of the diffusion coefficient. Thesis also deals with electrochemical impedance spectroscopy (EIS) and its use in determining the equivalent replacement circuit and calculating the diffusion coefficient.

第22回名古屋大学年代測定総合研究センターシンポジウム平成21(2009)年度報告