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For the development of safe and long-lasting lithium-ion batteries we need electrolytes with excellent ionic transport properties. Argyrodite-type Li6PS5X (X: Cl, Br, I) belongs to a family of such a class of materials offering ionic conductivities, at least if Li6PS5Br and Li6PS5Cl are considered, in the mS cm-1 range at room temperature. Although already tested as ceramic electrolytes in battery cells, a comprehensive picture about the ion dynamics is still missing. While Li6PS5Br and Li6PS5Cl show an exceptionally high Li ion conductivity, that of Li6PS5I with its polarizable I anions is by some orders of magnitude lower. This astonishing effect has not been satisfactorily understood so far. Studying the ion dynamics over a broad time and length scale is expected to help shed light on this aspect. Here, we used broadband impedance spectroscopy and 7Li NMR relaxation measurements and show that very fast local Li ion exchange processes are taking place in all three compounds. Most importantly, the diffusion-induced NMR spin-lattice relaxation in Li6PS5I is almost identical to that of its relatives. Considering the substitutional disorder effects in Li6PS5X (X = Br, Cl), we conclude that in structurally ordered Li6PS5I the important inter-cage jump processes are switched off, hindering the ions from taking part in long-range ion transport.
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Chemical reactions induced by mechanical treatment may give access to new compounds whose properties are governed by chemical metastability, defects introduced and the size effects present. Their interplay may lead to nanocrystalline ceramics with enhanced transport properties being useful to act as solid electrolytes. Here, the introduction of large amounts of La into the cubic structure of BaF2 served as such an example. The ion transport properties in terms of dc-conductivity values of the F(-) anion conductor Ba1-xLaxF2+x (here with x = 0.4) considerably exceed those of pure, nanocrystalline BaF2. So far, there is only little knowledge about activation energies and jump rates of the elementary hopping processes. Here, we took advantage of both impedance spectroscopy and (19)F NMR relaxometry to get to the bottom of ion jump diffusion proceeding on short-range and long-range length scales in Ba0.6La0.4F2.4. While macroscopic transport is governed by an activation energy of 0.55 to 0.59 eV, the elementary steps of hopping seen by NMR are characterised by much smaller activation energies. Fortunately, we were able to deduce an F(-) self-diffusion coefficient by the application of spin-locking NMR relaxometry.
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INTRODUCTION: Correct ligamentous balancing is an important determinant of the clinical outcome in total knee arthroplasty (TKA). Many surgeons prefer a tight rather than a lax knee during implantation of a TKA. The hypothesis in this study was that patients with a slightly laxer knee joint might perform better than patients with a tight knee joint after implantation of a TKA. PATIENTS AND METHODS: Twenty-two patients with bilateral knee arthroplasties were clinically and radiologically evaluated at a mean follow-up of 4.5 years, ranging from 2 to 7 years. There were 12 women and 10 men with an average age of 68.9 years (range 32-82 years) at the time of surgery. A modified HSS score (excluding laxity), varus and valgus stress X-rays in 30 degrees of knee flexion, and the subjective outcome of both knees were compared. A knee was considered tight when it opened less than 4 degrees and lax if it opened 4 degrees or more on stress X-ray. RESULTS: There was a trend towards improved range of motion and HSS score for the laxer knee joints. However, the difference did not achieve statistical significance. Eleven of the 22 patients considered one side subjectively better than the other side. In 10 out of these 11 TKA, the slacker knee joint was the preferred side ( p<0.05). CONCLUSIONS: As the present study compared bilateral knee joints after TKA, the same patient could act as a control group, and subtle subjective differences were revealed which are not quantifiable. The results showed that patients with a preferred side felt significantly more comfortable on the laxer side, indicating that during intraoperative ligamentous tensioning, some varus and valgus laxity at 20-30 degrees of flexion might be preferable to an over-tight knee joint. Further biomechanical and prospective investigations will be necessary to establish the correct soft-tissue tensioning.
