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Analyse de la microstructure des matériaux actifs d'électrode positive de batteries Lithium-ion

Abstract : 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.
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Pierre-Etienne Cabelguen. Analyse de la microstructure des matériaux actifs d'électrode positive de batteries Lithium-ion. Matériaux. Université Grenoble Alpes, 2016. Français. ⟨NNT : 2016GREAI069⟩. ⟨tel-01689791⟩

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