Ce travail de thèse se base sur quatre matériaux modèles, de composition LiNi1/3Mn1/3Co1/3O2, qui différent de par leur microstructure. Le lien entre leur morphologie et les performances électrochimiques est étudié par la combinaison de la caractérisation exhaustive de leur microstructure, l’étude de leur comportement en batterie et la modélisation de leur réponse électrochimique. L’étape limitant le processus électrochimique est identifiée par voltampérométrie cyclique et nous montrons que la transition attendue d’une limitation par le transfert de charge à une limitation par la diffusion en phase solide a lieu à différents régimes selon la microstructure. Ce comportement est expliqué par l’utilisation d’outils de simulations numériques. Selon leur forme et leur agglomération, les cristallites agissent collectivement ou indépendamment les unes des autres. Ces résultats rationalisent les performances en puissance obtenues sur nos matériaux. Les résultats de simulation montrent également qu’une faible fraction de la surface développée est électroactive, ce qui remet en question la large utilisation de la surface BET dans la littérature. Nous montrons également que, si les matériaux poreux sont les plus performants en puissance gravimétrique, la tendance est inversée pour la puissance volumique. Les stratégies de nanostructuration largement employées, qui se basent sur la capacité spécifique pour caractériser les matériaux, ne doivent pas oublier faire oublier le compromis nécessaire entre surface développée et volume. / Four NMC materials are synthesized by co-precipitation. They exhibit a hierarchical architecture made of reasonably spherical agglomerates. One is constituted of flake-shaped, spatially oriented, crystallites that leave large apparent void spaces in the agglomerate, while the other results from the tight agglomeration of micron-sized cuboids. Porous material exhibits the best power performances. It is impossible to identify a geometrical parameter that predict performances, even after achieving the full characterization of the microstructures. Cyclic voltammetry reveals two behaviours depending on the shape of crystallites: processes limited by solid-state diffusion (cuboids) and the ones limited by charge transfer even at high rates (flake-shaped). This observation challenges active materials design strategies that assume diffusion as the limiting process of lithium intercalation. Focusing on enhancing kinetics could be the way to increase performances. Charge-transfer is first investigated by measuring electronic conductivities over a wide range of frequencies, allowing to discriminate relaxations arising at various length scales. We show that flake-shaped crystallites facilitate the motion of electrons at all scale levels compared to cuboids. Charge-transfer limitations originate from the electrolyte/material interface in materials exhibiting high surface areas. Numerical simulations reveal that BET measurements largely overestimate the actual electroactive surface, which is understood by HRTEM images of flake-shaped crystallites. Only a small percentage, limited to the edge plane is truly electroactive.

In the early 1970s, research carried out on rechargeable lithium batteries at the Exxon Laboratories in the US established that lithium ions can be intercalated electrochemically into certain layered transition-metal sulphides, the most promising being titanium disulphide. Stemming from this discovery for titanium disulphide, there has been increased interest on lithium-ion intercalation compounds for application in rechargeable batteries. The first rechargeable lithium cell was commercialized in late 1980s by Moli Energy Corporation in Canada. The cell comprised a spirally wound lithium foil as the anode, a separator and MoS2 as the cathode. The cell had a nominal voltage of 1.8 V and an attractive value of specific energy, which was 2 to 3 times greater than either lead-acid or nickel-cadmium cells. However, the battery was withdrawn from the market after safety problems were experienced. This paved way for the discovery of lithium-ion battery. The origin of lithium-ion battery lies in the discovery that Li+-ions can be reversibly intercalated within or deintercalated from the van der Walls gap between graphene sheets of carbon materials at a potential close to the Li/Li+ electrode. Thus, lithium metal is replaced by carbon as the anode material for rechargeable lithium-ion batteries, and the problems associated with metallic lithium mitigated. Complimentary investigations on intercalation compounds based on transition metals resulted in establishing LiCoO2 and LiNiO2 as promising cathode materials. By employing aforesaid intercalation materials, namely carbon and LiCoO2 respectively, as negative and positive electrodes in a non-aqueous lithium-salt electrolyte, a Li-ion cell with a voltage value of about 3.5 V resulted. These findings led to a novel rechargeable battery technology. Lithium-ion batteries were first introduced commercially in 1991 by the Sony Corporation in Japan. Other Japanese manufacturers soon entered the market, followed closely by American and European companies. The subsequent growth in sales of the batteries was truly phenomenal. Beginning from 1991, the lithium-ion battery market has grown from an R&D interest to sales of over 400 million units in 1999. The global market value for lithium-ion batteries at original equipment manufacturer level was estimated to be $1.86 billion in 2000. By 2006, the market is expected to grow to over 1.2 billion units with value of over $4 billion, while the average unit price is expected to fall. Initially, realizable specific energy of commercial Li-ion battery was only about 120 Wh kg-1. However, with continuing improvements in various cell components, present day Li-ion batteries can provide a specific energy density of about 200 Wh kg-1. With the ‘holy grail’ far to be realized, the current R&D efforts are focussed on furthering the specific energy of lithium-ion batteries in conjunction with safety, environmental compatibility, and cost effectiveness. In the Li-ion cell, all of its electrochemical constituents, namely anode, cathode and electrolyte are central to its performance. This thesis describes some novel studies on cathode and anode materials for lithium-ion Batteries.

From the time of the unexpected discovery of the insulating nature of NiO by Verwey half a century ago, Oxide materials have continued to occupy the centre stage of condensed matter physics. The recent discovery of high temperature superconductivity in doped cuprates has given a new impetus to the study of the strongly correlated electron systems. Besides, the occurrence of Colossal Magneto-Resistance (CMR) in doped rare earth manganite has also created renewed interest in these rather old systems. Understanding of the rich and complex phase diagram of these materials and their sensitivity to small perturbations e.g. external magnetic field of a few Tesla, temperature, change in isotope etc. are of great theoretical interest and also these materials have many potential technological applications. A common feature of all these oxide materials is that the transition metal ions have partially filled d-shells. Unlike s and p-electrons which gives rise to hybridized Bloch states, the d-electrons retain their atomic nature in a solid. This gives rise to strong Coulomb interaction among d-electrons which may be comparable or more than its kinetic energy. The strong correlation effects are evident from the experimental fact that the undoped parent compounds are insulators rather than metals as suggested by band theory, which favours a metallic state for systems with one electron per unit cell since this gives rise to partially filled bands (and hence a metallic state). These insulators termed Mott insulators, arise solely due to strong electron-electron correlations as compared to the band insulators which arise due to complete filling of one electron bands thereby giving rise to a gap (band gap)in the excitation spectra. The delicate competition between the kinetic energy and the Coulomb energy for d-electrons is broadly responsible for the wide variety of phenomena like Mott metal-insulator transition (MIT), magnetic transitions, charge ordering, orbital ordering, ferro/antiferroelectricity, and most interestingly the observation of high Tc superconductivity in doped cuprates. In this thesis we will restrict our interest to one such class of oxide materials, namely the doped rare earth manganites. In Chapter 1 we give a brief overview of the structure and basic interactions present in the doped manganites. Also, in the same Chapter we give a brief introduction to the phenomenology of manganites, particularly its phase diagram in the doping and temperature plane and various experimental features, e.g. the wide variety of phase transitions and phenomena particularly the observation of CMR, charge ordering and incipient meso-scale phase separations etc.. Then we briefly introduce a recently proposed microscopic model which is believed to be a minimal model which, for the first time, includes the three most important interactions present in the manganites namely the following -1)coupling of the orbitally degenerate eg electrons to local lattice distortions of Jahn-Teller type which gives rise to two species of electrons. The one denoted by by ℓ is associated with Jahn-Teller effects and hence is localized whereas the other denoted by b is an extended state and propagates through the lattice. 2) The strong Hund’s couplingof ℓ and b electrons to the t2g core spin and 3) the strong Coulomb correlation between the two species of electrons. Additionally, the model includes a new doping dependent ferromagnetic exchange between the t2g core spins which can arise from “virtual double exchange” mechanism which will be discussed in great detail in Chapter 1 . Finally, we give a brief account on Dynamical Mean Field Theory (DMFT) and Numerical Renormalization Group (NRG) as an impurity solver for the single impurity problem arising under single site DMFT approximation. In Chapter 2 we study the effect of inter-site ℓ - b hybridization on the ‘ℓ - b’ model. The single impurity problem arising under DMFT approximation has close connection with the Vigman-Finkelshtein (VF)model. Then we briefly introduce the VF model and bring out its close connection with the impurity problem. We consider both the particle-hole symmetric as well as the U → ∞ particle-hole asymmetric cases. We derive various spectral functions at T = 0K and discuss the nature of fixed points under various circumstances. We explicitly show that for the particle-hole symmetric case the Hamiltonian flows from X-ray edge singularity fixed point to Free Electron fixed point under Renormalization Group transformation. This is evident from the spectral properties of the model. We write down the effective Hamiltonian at the free electron fixed point. For the particle-hole asymmetric case the model flows from X-ray edge singularity fixed point to Free Electron/Strong Coupling fixed point with additional potential scattering terms. We write down the effective Hamiltonian at this fixed point and derive various leading order deviations. We found all of them to be irrelevant in nature also most interestingly the quasi-particles describing the under lying Fermi liquid state are found to be asymptotically non-interacting. We also calculate the Fermi liquid parameter, z, by analyzing the energy level structure of a non-interacting Hamiltonian with effective renormalized parameter. Also, we consider the case of ‘self consistent bath hybridization’ without ℓ - b hybridization for Bethe lattice with infinite coordination. Low energy qualitative features are found to be same but some of the high energy features get qualitatively modified. In Chapter 3 we discuss the transport properties of doped manganites in the insulating phases and also the Hall effect in the metallic phase. In the first part of this chapter we calculate the resistivity based on the ‘ℓ - b’model and try to fit it to the semiconducting form: ρ(T )= ρ0(T /T0)−nexp[Δ(T )/kBT ] and extract the “transport gap”, Δ(T ). This gap can be characterized in terms of the “spectral gap” which can be defined for the ℓ - b model. It is found that the transport gap in the paramagnetic phase can be characterized in terms of the near constant “spectral gap” in this phase whereas the same in the ferromagnetic phase can be characterized in terms of the zero temperature spectral gap. In the last part of this chapter we calculate the Hall resistivity (ρxy) of these materials in the metallic phase. Ρxy is found to be negative and linear in applied field -quite consistent with the experimental findings but this fails to explain the positive linear Hall resistivity at low temperatures and its crossover as a function of field and temperature. We then present a reasonable explanation for this discrepancy and support it by calculating the Hall density of states for a two band “toy model” involving inter species hybridization. In Chapter 4 we calculate the optical conductivity, σ(ω), in ℓ - b model. σ(ω) arises from two independent processes. One of the processes involves ‘b’ electrons only and termed as ‘b - b channel’ and this gives rise to a Drude peak in the low frequency region. another process termed as the ‘ℓ - b channel’ involves hopping of an ℓ-electron to a neighbouring empty site and transforms into a ‘b’like state. This process gives rise to a broad mid-infrared peak. The total conductivity is the sum of contributions from these two incoherent channels. Calculated σ(ω) for metallic systems shows lot of similarities with experimental observations particularly the temperature evolution of the mid-infrared peak and the spectral weight transfer between the two peaks. But for the insulating systems the calculated optical conductivity showed trends similar to more recent experimental observations on some insulating systems (x =0.125) but contradicts with earlier experimental observations on some other insulating system (x =0.1). Finally, in the concluding chapter, we summarize results from all the chapters and also sketch some possible future directions of investigations.