Jump relaxation in solid electrolytes

Structural characterization of noncrystalline solids and glasses using solid state NMR

Solid-State Li NMR with Applications to the Translational Dynamics in Ion Conductors

7Li nuclear magnetic resonance (NMR) linewidths and spin–lattice relaxation times for poly(propylene‐glycol) complexed with a range of concentrations of LiCF3SO3 are reported over the temperature region from 205 to 405 K. Calculations suggest that the spin–lattice relaxation mechanism is caused by the interaction between the 7Li (I=3/2) quadrupole moment and fluctuations in the surrounding electric field gradients, whereas the line shapes are influenced by both the dipolar and quadrupolar interactions. The motional parameters reported indicate that ion–polymer or ion–ion interactions are important in determining the Li+ cation mobilities. This is reflected in the lengthening of the correlation time with increase in Li+ ion concentration which suggests a decreased mobility for the cations resulting from a transient coordination of the cation to the polymer matrix or ion aggregation. Also, the activation energies in this study (∼0.24 eV) are in agreement with values obtained from recent pulsed field gradient studies suggesting that the NMR techniques employed in this study are approriate methods for probing the dynamics of ion transport on a macroscopic scale in these materials.

A 7Li nuclear magnetic resonance study of LiCF3SO3 complexed in poly(propylene‐glycol)

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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Substitutional disorder: structure and ion dynamics of the argyrodites Li6PS5Cl, Li6PS5Br and Li6PS5I.

7 Li NMR spin-lattice relaxation rates at 16 MHz and 117 MHz have been measured at various temperatures for glasses in the non-oxide chalcogenide system B 2 S 3 -Li 2 S-LiX with X=Cl, Br, I. As compared with the corresponding oxide glasses these materials are distinguished by a higher ionic conductivity, and the relaxation maxima are better accessible. The relaxation rates display anomalous temperature and frequency dependences. Attempts to interpret the non-BPP-type relaxation in terms of appropriate diffusion models are discussed

M. Wulff

Papers

7Li NMR spin-lattice relaxation and ionic diffusion in lithium thioborate glasses