No / Occupational health nurses will be familiar by now with the process of NMC revalidation, but concerns remain about how to plan ahead and meet the requirements in practice.

This thesis details electrical and physical measurements of pulsed laser deposition-applied thin film coatings of Alumina, Ceria, and Yttria-stabilized Zirconia (YSZ) on a LiNi0.5Mn0.3Co0.2O2 (NMC) cathode in a Lithium ion battery. Typical NMC cathodes exhibit problems such as decreased rate performance and an opportunity for increased capacity exists by raising operation voltage beyond the electrolyte stability window. Very thin (~10 nm) coatings of stable oxides provide a pathway to solve both problems. As well, the electrochemical impedance spectra of the uncoated and coated cells were measured after different numbers of cycles to reveal the property variation in the cathode. Further understanding of the mechanism of rate performance enhancement and chemical protection by thin oxide coatings will continue to improve battery capability and open up new applications. Ceria-coated Li-NMC cells show the best capacity and rate performance in battery testing. Through electrochemical impedance spectroscopy (EIS), the surface film resistance was found to remain stable or even drop slightly after repeated cycling at high voltage. CeO2 is proposed as a coating for Lithium ion battery cathodes owing to its high chemical stability and the demonstrated but not yet well understood electrical conductivity. Alumina-coated cathode shows comparable performance as that of the uncoated cell in the early stage of the test, but through the course of testing the rate capability and recoverable capacity is improved. This is possibly due to Al2O3?s well-known abilities as HF scavenger and chemically inert nature. YSZ-coated cathode performs worse than the uncoated ones in terms of capacity, rate capability, and EIS-related figures of merit. The reason for the poor performance is not yet known, and repeatability tests are under way to verify performance. High voltage cycling reveals no obvious difference in irreversible loss between the coated or uncoated cells. The reason for the lack of distinction could be the relatively small percentage of surface coating compared to the thick doctor-blade processed cathode layer.

"A ¡°mixed cathodes¡± LIB recycling process was first proposed and developed in the CR3 center at Worcester Polytechnic Institute. This process can efficiently and economically recover all the valuable metal elements in LIB waste. In the end of the recovery process, lithium, nickel, manganese, and cobalt ions will be recovered in the leaching solution. The objective of this work is to utilize the leaching solution to synthesis NixMnyCoz(OH)2 precursors and their corresponding LiNixMnyCozO2 cathode materials. The synthesized cathode materials can be used to build new LIBs, allowing the overall process to be a ¡°closed loop¡±. "

Rechargeable lithium ion batteries are common materials in everyday applications. The most frequently used cathode material, LiCoO2, provides high energy density and stable charge/discharge performance. However, LiCoO2 is toxic and relatively expensive, therefore, other alternatives are being sought after in the development of battery materials, such as LiMn0.33Ni0.33Co0.33O2 (identified commonly as 333 compound). The 333 compound is now popular due to its comparable performance with LiCoO2, lower price, enhanced stability, and more environmentally friendly characteristics. In addition, Li1.2Mn0.54Ni0.13Co0.13O2 (HENMC) is still on the stage of testing and it attracts wide attention due to its higher rechargeable capacity and thermal stability. However, there are still challenges confronted: cycle stability and low rate capability. In order to verify all the roles played by different elements shown in NMC materials and explore the corresponding performance with different formula units, compositional analysis is needed. ICP-MS (inductively coupled plasma mass spectrometry) can provide bulk compositional information and has been used in recent work, giving a general idea of the composition of NMC materials. However, compositional inhomogeneity analysis has usually been neglected in these studies. Therefore, the objective of this work was to explore this variation in composition locally with higher spatial resolution, at the NMC particle level. This work was carried out through the use of scanning electron microscopy – energy dispersive spectroscopy (SEM-EDS) and Auger electron spectroscopy (AES). Furthermore, nano-scale quantitative analysis was done with transmission electron microscopy – energy dispersive spectroscopy (TEM-EDS). Moreover, an optimal approach and procedure of compositional analysis by using EDS and AES was explored with proper standards and operation conditions to provide consistent and stable results. The optimal quantification method was applied to investigate the compositions of 333 compound before and after ball milling and HENMC specimen before and after cycling. The results support the structural changes and in turn the electrochemical performance of the battery material. In the 333 compound, the electrochemical performance of the battery was deteriorated due to ball milling, during which Zr was introduced and particles were more compact. In HENMC, during cycling, the Mn distribution was homogeneous at the beginning, then inhomogeneous and homogeneous again, supporting the hypothesis of the transformation of phases: formation of spinel phase and potential SEI layer. In-depth structural analysis of different NMC materials has been reported previously by other groups. However, the structural effects due to cycling, within particles still needs investigation. Therefore, X-ray diffraction (XRD) was used to investigate the bulk material crystalline structure. Local nano-scale level structural variations amongst different isolated primary particles were investigated by the electron diffraction pattern based on TEM. The 333 compound and HENMC cycling was examined before and after cycling. After cycling, in the 333 compound, the O1 phase domains with P-3m1 space group appear inside the O3 phase with R-3m lattice. With more cycling, more domains appear. For HENMC, the original pristine samples exhibit the rhombohedral and monoclinic phases. After cycling, more and more spinel phase appear. Finally, after 100 cycles, we observe evidence of the potential solid electrolyte interphase (SEI) formation. In all, all the results above support the phase changes of 333 compound and HENMC. More investigations are needed to understand the degradation process of both compounds. / Thesis / Master of Materials Science and Engineering (MMatSE)

Le but de cette thèse était d'étudier et de mieux comprendre les mécanismes d'interaction entre protéines laitières (caséines micellaires natives NMC et protéines de lactosérum natives WPI) sous forme de poudres dispersées (5% p/v) dans des milieux fortement ionisés par des sels (NaCl, CaCl2). D'une manière générale notre étude a été organisée en trois parties. Premièrement, nous avons étudié l'influence des milieux ioniques (eau distillé, solution de NaCl, solution de CaCl2) sur la réhydratation de protéines laitières. Dans une seconde partie nous avons caractérisé les dispersions en milieux ionisés par les études respectives de la structure secondaire des protéines, de la taille et de la morphologie des particules en cours de dispersion et de l'hydrophobicité des protéines. Dans la troisième et dernière partie nous nous sommes intéressés aux propriétés fonctionnelles des protéines du lactosérum par l'effet combiné de la température (30 - 90°C) et de la concentration en NaCl (0,75 - 3%). La réhydratation des protéines du lait a montré deux comportements distincts en fonction du type de sel d'une part (NaCl, CaCl2) et de la concentration d'autre part (0 - 12%). Dans les dispersions de NMC, avec l'ajout et l'augmentation de la concentration de NaCl on observe (DLS, TEM), une désintégration des micelles de taille 150 nm en petites micelles de 20-30 nm qui sont plus ou moins agrégées. En définitive, les propriétés fonctionnelles des protéines du WPI dépendent en même temps de la concentration en sel et de la température appliquée / The overall objective of this work was to investigate the mechanisms of protein-salt interactions and linkage between milk proteins powders and milk proteins dispersions (5% w/v) mainly NMC and WPI under various ranges of ionic environments (distilled water, NaCl solution and CaCl2 solution. In the first phase, we investigated the influence of the ionic environments on milk proteins powders rehydration profiles. The second phase of this study includes the characterization of milk proteins dispersions in an aqueous ionic environment regarding changes in the protein: secondary structure (ß-sheet, alpha-helix, ß-turns and unordered structures), size, morphological features and surface hydrophobicity by using FTIR, TEM, and DLS with other complimentary techniques. In the last part, the functionality of whey proteins was studied by the combined effect of heat and different ratios of salts. For this purpose, the study was exclusively focalized in an aqueous ionic medium composed of NaCl (0.75-3%) at different temperatures (30-90°C). The results obtained from the first part showed two distinct rehydration behaviors depending on the salts type and concentration. For the NMC dispersions under salt increase, spherical micelles with an average size around 150 nm disintegrated in sub-micelles around 20-30 nm and more or less aggregated were observed by DLS and TEM. WPI dispersions in water were composed of well separated proteins by a spherical shape with two populations around 6 and 70 nm. Salt increase resulted in an aggregation of the proteins and the formation of denser aggregates. Moreover, a combined salt/heat resulted showed a stabilizing effect on the secondary structural elements of both Amide I and III bands and higher denaturation temperatures observed by FTIR and µDSC respectively. A size and morphological investigation showed a transition from spherical/compact protein aggregates to linear ones. Finally, this work demonstrated that whey protein functional properties depend on both salt and how heat treatment is applied

La plupart des batteries Li-ion aujourd’hui utilisent des électrolytes à base de LiPF6 un sel de lithium connu pour son instabilité chimique au-delà de 60°C car il se dégrade en libérant PF5 et LiF. En présence de traces d’eau il génère en plus des composés oxyfluorophosphorés et du HF qui peut être dommageable à la fois pour les performances et pour le vieillissement de l’accumulateur. Plusieurs sels sont candidats au remplacement de LiPF6, notamment ceux basés sur les anions fluorosulfonylamidures et les anions de Hückel. Ce travail concerne l’étude des propriétés physico-chimiques et de transport des électrolytes à base de 4,5-dicyano-2- (trifluoromethyl)imidazolide de lithium (LiTDI) et bis(fluorosulfonyl)amidure de lithium (LiFSI) pour une utilisation au sein d’accumulateurs de type Li-ion. Dans ce travail il a d’abord été montré que LiTDI n’est que faiblement dissocié dans les mélanges de carbonates d’alkyles utilisés dans les batteries Li-ion tels que le binaire (EC/DMC) ce qui limite sa conductivité. Pour pouvoir remédier à cet inconvénient, une étude des phénomènes de solvatation et d’associations ioniques a été menée et a conduit à proposer un mélange ternaire de solvants (EC/GBL/MP) dans lequel LiTDI est plus dissocié. Le mélange ternaire proposé améliore à la fois les propriétés de transport et les caractéristiques thermiques de l’électrolyte sans compromettre le domaine de stabilité chimique et électrochimique. Enfin, le nouvel électrolyte EC/GBL/MP contenant LiTDI, a été testé en accumulateurs dans les conditions opératoires usuelles (régime C/10 et température ambiante) et sévères (régime 10C et des températures allant de -20 °C à 60 °C). Le problème de corrosion de l’aluminium de LiFSI a aussi été pris en compte. Un électrolyte prometteur à base d’un mélange LiTDI/LiFSI montrant de meilleures performances que chaque sel utilisé séparément dans EC/DMC a été présenté. Les conclusions de cette thèse prouvent que LiTDI ou LiFSI peuvent être utilisés comme sels de lithium dans les électrolytes pour accumulateurs Li-ion. / Most of the Li-ion batteries used in electrical devices contain a solution of LiPF6 in alkylcarbonate solvents with the risk of releasing PF5 at elevated temperatures and HF in the presence of water. Several salts are candidates for the replacement of LiPF6, including those based on fluorosulfonylamides and Hückel anions. This work concerns the study of physicochemical and transport properties of lithium 4,5-dicyano-2- (trifluoromethyl)imidazolide (LiTDI) and lithium bis(fluorosulfonyl)amide (LiFSI) based electrolytes and their use in Li-ion battery. First it was revealed that LiTDI is only weakly dissociated in alkylcarbonate mixtures used in Li-ion batteries such as EC/DMC limiting its conductivity. To overcome this disadvantage, a study of the solvation phenomena and of ionic association within the electrolytes was conducted. This study led to a ternary mixture of solvents (EC/GBL/MP) in which LiTDI is more dissociated. This new solvent mixture improves both the transport properties and the thermal stability of the LiTDI based electrolyte without compromising its chemical and electrochemical stability. Finally, the new LiTDI in EC/GBL/MP electrolyte was tested in NMC/graphite batteries under normal (C/10 rate and room temperature) and severe (10C rate and temperatures varying from - 20 ° C to 60 °C) operating conditions. The aluminium corrosion problem encountered by LiFSI based electrolytes was taken into account and a LiTDI/LiFSI salt mixture based electrolyte showing promising results was presented. The findings of this thesis show that LiTDI or LiFSI can be used as lithium salts in electrolytes for Li-ion batteries.

En raison de leur faible pression de vapeur et de leur stabilité électrochimique (5~6 V) et thermique, les dinitriles N≡C-(CH2)n-C≡N sont proposés comme solvants d’électrolytes alternatifs aux carbonates d’alkyles habituellement utilisés dans les batteries Li-ion. L’objectif de cette thèse est d’étudier le comportement physico-chimique de ces électrolytes alternatifs (viscosité, conductivité ionique, comportement thermique, propriétés volumétriques, etc.) et leur compatibilité avec une application dans les batteries Li-ion. Deux systèmes de batteries sont étudiés en utilisant une électrode positive d’oxyde lamellaire (LiNi1/3Mn1/3Co1/3O2) associée à une électrode négative à bas potentiel (graphite) ou à plus haut potentiel (Li4Ti5O12). La cyclabilité des électrodes en demi-pile et en pile complète est étudiée en fonction de la composition de l’électrolyte et de la nature du dinitrile utilisé. Les techniques de caractérisations suivantes : spectroscopie d’impédance électrochimique, microscopie électronique et spectroscopie de photoélectrons aux rayons X, sont utilisées pour suivre le processus de passivation des électrodes par formation d’une interface solide (SEI). L’effet de la présence d’additifs favorisant la formation de la couche de passivation a été étudié et leur efficacité est ainsi clairement mise en évidence. / Due to their low vapor pressure as well as their electrochemical (5~6 V) and thermal stability, dinitriles N≡C-(CH2)n-C≡N are proposed as alternative electrolyte solvents to alkyl carbonates commonly used in Li- ion batteries. The objective of this thesis is to study the physico-chemical behavior of these alternative electrolytes (viscosity, ionic conductivity, thermal behavior, volumetric properties, etc.) and their use in Li-ion batteries. Two battery systems are studied using a lamellar oxide (LiNi1/3Mn1/3Co1/3O2) as positive electrode associated with graphite or Li4Ti5O12 as negative electrodes. The cyclability of electrodes in half-cell and full-cell is studied according to the electrolyte composition and the nature of the dinitrile used. Characterization techniques like: electrochemical impedance spectroscopy, electron microscopy and X-Ray photoelectrons spectroscopy, are used to study the passivation of the negative electrode and the stability of the positive electrode. The effect of adding specific solid electrolyte interphase (SEI) builders is investigated and their efficiency is hence clearly demonstrated.

The objective of this report was to implement battery cycling and an intermittent current interruption (ICI) method for determining battery resistance into a simple lithium-ion battery model in the finite element methods (FEM) program COMSOL Multiphysics, andevaluate how accurately the model reflects the behaviour of voltage and internal resistance with respect to experimental results. The ICI technique consists of repeating the steps of first having a longer charging period and then having a short current interruption, where the internal resistance is calculated from the voltage drop that occurs when the current is turned off. The model was evaluated against measurements, made with the same technique (ICI), on assembled NMC-graphite batteries. Codes written in the statistical programming language “R” were used to process the data from both COMSOL and the experiments. Both the batteries and the model were constructed with a reference electrode, to enable measurement of each electrode by itself. The results as documented in this report show that it is possible to simulate the measurement technique in COMSOL, but that both the resistance and voltage profiles differed quite a lot from the behaviour of the tested batteries. The resistance of the positive electrode did however give good results and it was possible to improve the model by changing some parameters. The magnitude of the resistance, which was already quite close, could be improved by changing the porosity and particle size, and the voltage profiles were improved when using voltage-data achieved from the real measurements.

This thesis deals with description of preparation and use of monomers and copolymers for gel polymer electrolytes usable in electrochemical power sources. This thesis is divided in theoretical and experimental part. The theoretical part describes electrolytes focused on gel polymer electrolytes, measuring methods and materials used for experiments. The experimental part deals with calculation of composition of polymer electrolytes, method of preparation and evaluation of measured results. The method of applying GPE to a negative LTO electrode and a positive NMC electrode is described too. Linear Sweep Voltammetry (LSV) and Potentiostatic Electrochemical Impedance Spectroscopy (PEIS), Cyclic Voltammetry (CV) and Galvanostatic Cycling with Potential Limitation (GCPL) were chosen for measurement of properties.

Indiana University-Purdue University Indianapolis (IUPUI) / The geometric and electrochemical characteristics of different lithium ion batteries (LIBs) are investigated in this study. The core work is to study the impact of the calendering process on NMC cathode electrodes performance. X-ray CT image processing by Python, MATLAB, ImageJ and Avizo is utilized in this study. NMC electrodes with different calendering conditions were fabricated to calculate electrochemical properties of the cells. Charge/discharge of the electrodes under 0.1C, 0.2C, 0.4C, 1C, 2C, 4C and 0.1C (retention test) rates were cycled for three times respectively between 4.2 V and 3.0 V. Electrochemical impedance spectroscopy testing was used to further explain the effects of NMC density on rate capability. Geometric properties of NMC electrodes with different calendering conditions were calculated from the computed tomography data of the electrodes. A synchrotron transmission X-ray microscopy tomography system at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain the tomography data. X-ray CT image processing before the data analysis was introduced. Python based Tomopy and ASTRA toolbox were used to filter the original HDF5 data and reconstruction. ImageJ was used to help remove noise, adjust contrast and cropping. Iso2mesh and image processing tool box were used in MATLAB to generate meshed 3D structure of CT data. Geometric properties of NMC electrodes including porosity, pore size distribution, particle size distribution, specific surface area and tortuosity were calculated from the computed tomography data of the electrodes. The geometric and electrochemical analysis show that calendering can increase the electrochemically active area, which lead to improving of the rate capability. However, more calendering will result in crushing of NMC particles, which can reduce the electrode capacity at relatively high C rates. This study shows that the optimum electrochemical performance of NMC electrode at 94:3:3 weight ratio of NMC:binder:carbon black can be achieved by calendering to 3.0 g/cm3 NMC density. LTAP solid electrolyte and NMC cathode material mix electrode-electrolyte X-ray CT data was studied in last chapter. By using 8 kev X-ray energy, we could distinguish NMC active material, LTAP solid electrolyte and the others three phase. On the basis of NMC electrode image processing method, dilation and multiply threshold method is applied to get three-phase 3D geometry. A comparing of connection area between NMC and LTAP of 700psi and 1300psi electrode was analyzed. Geometric properties like tortuosity, di_usion length and e_ective di_usivity were generated from the CT data.