13 research outputs found

    A microcontact impedance study on NASICON-type Li 1+x_{1+x} Al x_{x} Ti 2−x_{2−x} (PO 4 ) 3 (0 ≤ x ≤ 0.5) single crystals

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    We successfully demonstrated the applicability of microcontact impedance spectroscopy (MC IS) on Li+ conducting solid electrolytes and measured the Li+ bulk conductivity (σb) of LiTi2(PO4)3 (LTP) and Li1+xAlxTi2−x(PO4)3 (LATP) single crystals independent of microstructural effects (e.g., grain boundaries, pores, and density). The crystals had a size of about 100 μm in each direction and crystallized with NASICON-type structure (R[3 with combining macron]c). Finite element calculations were performed to validate the impedance data analysis. A strong increase in σb in the order of three magnitudes (3.16 × 10−6 to 1.73 × 10−3 S cm−1) was found after incorporating 0.1 mol Al3+ per formula unit into LTP. Moreover, since the crystal structural changes are almost linear in the LATP system up to x = 0.5, the increase of σb is most probably related to additional Li+ sites at the M3 (36f) position. The additional Li+ leads to a displacement of Li+ occupying the M1 (6b) sites towards the nearest-neighboring M3 position, and therefore opens the fast-conducting pathway within the NASICON structure. A significant change in σb was also observed as the Al3+ content further increased (x = 0.1 to 0.5). The highest σb value of 5.63 × 10−3 S cm−1 was obtained for samples with x = 0.4

    Fast Li Ion Conducting Garnet Related Li7 3xFexLa3Zr2O12 with Uncommon I43d Structure

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    [Image: see text] Fast Li-ion-conducting Li oxide garnets receive a great deal of attention as they are suitable candidates for solid-state Li electrolytes. It was recently shown that Ga-stabilized Li(7)La(3)Zr(2)O(12) crystallizes in the acentric cubic space group I4̅3d. This structure can be derived by a symmetry reduction of the garnet-type Ia3̅d structure, which is the most commonly found space group of Li oxide garnets and garnets in general. In this study, single-crystal X-ray diffraction confirms the presence of space group I4̅3d also for Li(7–3x)Fe(x)La(3)Zr(2)O(12). The crystal structure was characterized by X-ray powder diffraction, single-crystal X-ray diffraction, neutron powder diffraction, and Mößbauer spectroscopy. The crystal–chemical behavior of Fe(3+) in Li(7)La(3)Zr(2)O(12) is very similar to that of Ga(3+). The symmetry reduction seems to be initiated by the ordering of Fe(3+) onto the tetrahedral Li1 (12a) site of space group I4̅3d. Electrochemical impedance spectroscopy measurements showed a Li-ion bulk conductivity of up to 1.38 × 10(–3) S cm(–1) at room temperature, which is among the highest values reported for this group of materials
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