Coupled anion and cation dynamics of silver orthophosphate in the picosecond range

Meyer, Hinrich‐Wilhelm; Jurányi, Fanni; Wilmer, D.

doi:10.1016/j.ssi.2006.07.038

Cited by 5 publications

(2 citation statements)

References 23 publications

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“…To the best of our knowledge, this is the first time that an ion diffusion and reorientational motion occurring at the same frequency scale are found in BH 4 -based systems. However, similar observations were reported for a number of orthophosphate-based ionic conductors, − such as Na 3 PO 4 . For these compounds, there is a strong evidence of dynamic coupling between the anion rotation and cation diffusion, as discussed in terms of the “paddle-wheel” mechanism .…”

Section: Resultssupporting

confidence: 81%

Nuclear Magnetic Resonance Studies of BH₄ Reorientations and Li Diffusion in LiLa(BH₄)₃Cl

et al. 2013

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To study the reorientational motion of BH 4 groups and the translational diffusion of Li + ions in the novel bimetallic borohydride chloride LiLa(BH 4 ) 3 Cl, we have measured the 1 H, 11 B, and 7 Li NMR spectra and spin−lattice relaxation rates in this compound over the temperature range of 23−418 K. At low temperatures (T < 110 K), the proton spin− lattice relaxation rates are governed by fast reorientations of BH 4 groups. This reorientational process can be satisfactorily described in terms of a two-peak distribution of the activation energies with the peak E a values of 41 and 50 meV. Above 200 K, the NMR data are governed by a combined effect of two types of motion occurring at the same frequency scale: Li ion diffusion and another (slower) reorientational motion of BH 4 groups. These results suggest that the Li ion jumps and the slower reorientational jumps of BH 4 groups in LiLa(BH 4 ) 3 Cl may be correlated. The estimate of the tracer Li ion diffusion coefficient at room temperature (5.2 × 10 −8 cm 2 /s) following from our experimental data indicates that LiLa(BH 4 ) 3 Cl can be considered as a promising solid-state ionic conductor.

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Section: Resultssupporting

confidence: 81%

Nuclear Magnetic Resonance Studies of BH₄ Reorientations and Li Diffusion in LiLa(BH₄)₃Cl

et al. 2013

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“…Rotational dynamics of polyhedral and molecular species may further be exploited as an additional avenue to enhance ionic conductivity in solid-state ion conductors via the “paddle wheel” mechanism, in which rotations of these species couple to hopping of mobile ions to promote long-range diffusion. Coupled dynamics between the polyhedral framework and mobile ions have been demonstrated to enhance ionic conductivity in several materials systems, including Li 2 SO 4 , Na 3 PO 4 , Ag 3 PO 4 , and the closo -borates Na 2 (B 12 H 12 ) 0.5 (B 10 H 10 ) 0.5 . The impacts of rotational dynamics upon ionic conductivity may be further enhanced by incorporating dynamic molecular species into pre-existing solid-state electrolyte materials.…”

Section: Introductionmentioning

confidence: 99%

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li₆PS₅CN

Maughan

Pekarek

et al. 2021

Chem. Mater.

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Rapid advancements in safe and high-energy-density energy storage are predicated on identifying new solid-state ion conductors with low activation energies and high ionic conductivities for all-solid-state battery technologies. Halide argyrodites are among some of the top candidates for solid-state electrolytes, as they can achieve ionic conductivities that approach liquid electrolytes. Incorporating dynamic pseudohalide species in argyrodite solid electrolytes presents an exciting opportunity to exploit lattice dynamics as a design principle to modulate the ion conduction properties of solid-state ion conductors. In the present study, we have prepared the new argyrodite Li 6 PS 5 CN containing orientationally disordered cyanide ions. The new cyanide argyrodite Li 6 PS 5 CN exhibits an activation barrier to Li-ion transport of 471 ± 25 meV and a room-temperature ionic conductivity of 6(2) × 10 −5 S cm −1 in comparison to the activation barrier of 502 ± 16 meV and an ionic conductivity of 2.3(1) × 10 −4 S cm −1 measured for the bromide analogue Li 6 PS 5 Br. Structural studies of both compounds by high-resolution X-ray diffraction indicate that Li 6 PS 5 CN and Li 6 PS 5 Br adopt nearly identical crystal structures with similar lattice parameters, which indicates that lower activation barriers in Li 6 PS 5 CN arise due to the cyanide ion itself rather than due to changes in the geometry of conduction pathways in the local lithium environment. The orientational disorder of the quadrupolar cyanide ion in Li 6 PS 5 CN points to a complex interplay of lattice polarizability and molecular dynamics that lower the activation barrier for lithium-ion conductivity in the cyanide argyrodite.

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Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

Soloninin

Skoryunov

Babanova

et al. 2019

Journal of Alloys and Compounds

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Coupled anion and cation dynamics of silver orthophosphate in the picosecond range

Cited by 5 publications

References 23 publications

Nuclear Magnetic Resonance Studies of BH₄ Reorientations and Li Diffusion in LiLa(BH₄)₃Cl

Nuclear Magnetic Resonance Studies of BH₄ Reorientations and Li Diffusion in LiLa(BH₄)₃Cl

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li₆PS₅CN

Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

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Coupled anion and cation dynamics of silver orthophosphate in the picosecond range

Cited by 5 publications

References 23 publications

Nuclear Magnetic Resonance Studies of BH4 Reorientations and Li Diffusion in LiLa(BH4)3Cl

Nuclear Magnetic Resonance Studies of BH4 Reorientations and Li Diffusion in LiLa(BH4)3Cl

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li6PS5CN

Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

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Nuclear Magnetic Resonance Studies of BH₄ Reorientations and Li Diffusion in LiLa(BH₄)₃Cl

Nuclear Magnetic Resonance Studies of BH₄ Reorientations and Li Diffusion in LiLa(BH₄)₃Cl

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li₆PS₅CN