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In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries
Published on: November 10, 2014
Li ion diffusion in the anode material Li12Si7: ultrafast quasi-1D diffusion and two distinct fast 3D jump processes
Alexander Kuhn1, Puravankara Sreeraj, Rainer Pöttgen
1Institute of Physical Chemistry and Electrochemistry, and ZFM-Center for Solid State Chemistry and New Materials, Leibniz University Hannover, Callinstr. 3-3a, 30167 Hannover, Germany. kuhn@pci.uni-hannover.de
Abstract:
The intermetallic compounds Li(x)Si(y) have attracted considerable interest because of their potential use as anode materials in Li ion batteries. In addition, the crystalline phases in the Li-Si phase diagram turn out to be outstanding model systems for the measurement of fast Li ion diffusion in solids with complex structures. In the present work, the Li self-diffusivity in crystalline Li(12)Si(7) was thoroughly probed by (7)Li NMR spin-lattice relaxation (SLR) measurements. Variable-temperature and -frequency NMR measurements performed in both the laboratory and rotating frames of reference revealed three distinct diffusion processes in Li(12)Si(7). The diffusion process characterized by the highest Li diffusivity seems to be confined to one dimension. It is one of the fastest motions of Li ions in a solid at low temperatures reported to date. The Li jump rates of this hopping process followed Arrhenius behavior; the jump rate was ~10(5) s(-1) at 150 K and reached 10(9) s(-1) at 425 K, indicating an activation energy as low as 0.18 eV.
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