Nuclear Magnetic Resonance Spin-lattice Relaxation Research Articles

Motional freedom of dimethylammonium ions in a cyanoelpasolite, [(CH3)2NH2]2KCo(CN)6, which exhibits phase transition associated with a distinct change in dielectric property.

The temperature dependence of the 1H nuclear magnetic resonance spin-lattice relaxation time T1 of [(CH3)2NH2]2KCo(CN)6 and the partially deuterated analogue [(CD3)2NH2]2KCo(CN)6 has been reported. A change in the molecular motion of organic cations through the first-order phase transition at Tc = 246 K has been discussed. Although this first-order transition has been reported as an isosymmetric transition, in which the space group of the crystal does not change, the number of the 14N nuclear quadrupole resonance line changed from three in the high-temperature phase to twelve in the low-temperature phase indicating the lowering of crystal symmetry.

Self-diffusion and ionic exchange in mechanosynthesized, nanocrystalline solid solutions of PbF2 and CaF2[sbnd]19F 2D NMR visualizes the flourine hopping preferences

Ionic conductors based on PbF2, being one of the archetypes to study ion dynamics, serve as excellent model substances to study the elementary steps of translational anion dynamics in the solid state. Here, high-energy ball milling was employed to prepare a structurally disordered, metastable solid solution by mixing PbF2 with CaF2. The cation-mixed lattice in cubic Ca0.4Pb0.6F2 provides a range of magnetically distinct fluorine sites. We used 2D 19F magic angle spinning nuclear magnetic resonance (NMR) exchange spectroscopy to reveal the site preference of the F anions when hopping through the lattice. It turned out that the F anions located in sites coordinated by Pb cations are more mobile than those residing near or in Ca-rich environments. Conductivity measurements and variable-temperature 19F NMR spin-lattice relaxation experiments provide activation energies (0.24 eV, 0.40 eV) from which we deduce that in cation-mixed Ca0.4Pb0.6F2 anion diffusivity, on the angstrom length-scale, is mainly determined by vacant F− sites. Macroscopic ion transport has to be characterized by an activation energy of 0.55 eV suggesting that the F anions also use interstitial sites for long-range ionic transport.

Concomitant Polymorphism in an Organic Solid: Molecular and Crystal Structure and Intra- and Intermolecular Potential Contributions to tert-Butyl and Methyl Group Rotation.

We investigate the relationship between structure (crystal and molecular) and tert-butyl and methyl group dynamics in 2-(tert-butyl)-9-(4-(tert-butyl)phenyl)anthracene. Powder and single-crystal X-ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X-ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert-butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state 1 H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments support the powder and single-crystal X-ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert-butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert-butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations.

Ion dynamics in Al-Stabilized Li7La3Zr2O12 single crystals – Macroscopic transport and the elementary steps of ion hopping

Li7La3Zr2O12 (LLZO) garnet-type ceramics are considered as very promising candidates for solid electrolytes and have been extensively studied in the past few years. Several studies report on an increase in ionic conductivity by doping with ions, such as Al3+ and Ga3+, to stabilize the cubic modification of LLZO. Unfortunately, so far ion dynamics have mainly been studied using powdered samples. Such studies may suffer from chemical heterogeneities concerning Al distribution. Here, we took advantage of Al-stabilized LLZO single crystals to throw light on the elementary steps of ion hopping. We used 7Li nuclear magnetic resonance (NMR) spin-lattice relaxation measurements and conductivity spectroscopy to probe dynamic parameters from both a microscopic and macroscopic point of view. At 293 K the total conductivity turned out to be 0.082 mS cm−1, which is remarkably good for LLZO exhibiting an Al-content of only 0.37 wt%. Most importantly, 7Li NMR spin-lock transients revealed two overlapping diffusion-induced processes. Overall, activation energies from spin-lock NMR excellently agree with that from conductivity measurements; both techniques yield values around 0.36 eV. The corresponding diffusion coefficients deduced from NMR and conductivity measurements almost coincide. The magnetic spin fluctuations sensed by NMR provide an in-depth look at the elementary jump processes, which can barely be revealed by macroscopic impedance spectroscopy providing average values. In particular, we were able to precisely measure the local hopping barrier (0.20 eV) characterizing forward-backward jumps between the sites 24d and 96h.

The spin-1/2 coupled tetramer system Ba(TiO) Cu4(PO4)4 probed by magnetization, specific heat, and 31P NMR

We present the synthesis and a detailed investigation of structural and magnetic properties of polycrystalline Ba(TiO) Cu4(PO4)4 (BTCPO) via X-ray diffraction, magnetic susceptibility, heat capacity, and 31P Nuclear Magnetic Resonance (NMR) measurements. BTCPO has a 2D layered structure with interlinked Cu4O12 tetramer units. A broad maximum is observed around 16.5 K in our magnetization data accompanied by a sharp anomaly around T = 9.5 K in the heat capacity. An anomaly at about T = 10 K is also found in the temperature dependence of the 31P NMR spin-lattice relaxation rate 1/T1. A power law behavior for the heat capacity as well as for the 31P 1/T1 below the ordering temperature could be obtained. The 31P NMR lineshape is asymmetric and the NMR shift tracks the bulk spin-susceptibility. We estimated the isotropic and axial components of the hyperfine coupling tensor to be as the Ahfiso⋍6794Oe/μB and Ahfax⋍818Oe/μB, respectively.

Investigating the Internal Processes of Thermo-Electrochemical Cells Using in-Situ Magnetic Resonance Imaging

Thermo-electrochemical cells are emerging as a promising and efficient method to convert waste heat to electricity. In addition to developing novel redox electrolyte materials to increase the energy densities, it is crucial for future developments to understand the internal chemical and thermodynamical processes happening inside the thermo-electrochemical cell while it is under operating conditions. Although the temperature and concentration distributions between the electrodes and the variations of the convection currents with cell orientation have been modelled mathematically, it has been a challenge to study these internal processes using experimental techniques. Magnetic resonance imaging (MRI) is a non-invasive and well-established diagnosis technique in medical research to investigate physiology, but it also has the capability to study spatial properties of materials, chemical and thermodynamic processes in energy storage devices using different image contrast options including spin density, relaxation time and velocity [1]. The goals of this study are to develop an MRI method to study the internal chemical and thermodynamic processes within a functioning thermo-electrochemical cell, and understanding how these are affected by the electrolyte, the cell geometry and the orientation of the thermal gradient. A cobalt redox couple based electrolyte, which has been shown to be a promising candidate for thermo-electrochemical cells [2], was used for the in-situ experiments inside specialised cells custom built for MRI experiments, and temperature and concentration dependent 1H nuclear magnetic resonance spin-lattice relaxation time (T1) measurements were used to interpret the 1H T1 weighted MRI images of the working cells.

Numerical study of the temperature dependence of the NMR relaxation rate across the superfluid–Bose glass transition in one dimension

We study the nuclear magnetic resonance (NMR) spin-lattice relaxation rate $1/T_1$ in random one-dimensional spin chains as function of the temperature and disorder strength. In the zero temperature limit, the system displays a disorder-induced quantum phase transition between a critical Tomonaga-Luttinger liquid (TLL) phase and a localized Bose glass phase. The $1/T_1$ is investigated across this transition using large-scale simulations based on matrix product state techniques. We find that this quantity can detect the transition and probe the value of the dimensionless TLL parameter $K$. We also compute the NMR relaxation rate distributions for each temperature and disorder strength considered. In particular we discuss the applicability of the stretched exponential fit to the return-to-equilibrium function in order to extract the $1/T_1$ experimentally. The results presented here should provide valuable insights in regards of future NMR experiments in realistic disordered spin compounds.

Structural and magnetic properties of a new cubic spinel LiRhMnO4

We report the structural and magnetic properties of a new system LiRhMnO$_{4}$ (LRMO) through x-ray diffraction, bulk magnetization, heat capacity and $^{7}$Li nuclear magnetic resonance (NMR) measurements. LRMO crystallizes in the cubic space group $\mathit{Fd}$$\bar{3}$$\mathit{m}$. From the DC susceptibility data, we obtained the Curie-Weiss temperature $\mathrm{\theta}_{\mathrm{CW}}$ = -26 K and Curie constant $\mathit{C}$ = 1.79 Kcm$^{3}$/mol suggesting antiferromagnetic correlations among the magnetic Mn$^{4+}$ ions with an effective spin $\mathit{S}$ = $\frac{3}{2}$. At $\mathit{H}$ = 50 Oe, the field cooled and zero-field cooled magnetizations bifurcate at a freezing temperature, $T_{f}$ = 4.45 K, which yields the frustration parameter $\mathit{f=\frac{\mid\theta_{CW}\mid}{T_{f}}}>$5. AC susceptibility, shows a cusp-like peak at around $T_{f}$, with the peak position shifting as a function of the driving frequency, confirming a spin-glass-like transition in LRMO. LRMO also shows typical spin-glass characteristics such as memory effect, aging effect and relaxation. In the heat capacity, there is no sharp anomaly down to 2 K indicative of long-range ordering. The field sweep $^{7}$Li NMR spectra show broadening with decreasing temperature without any spectral line shift. The $^{7}$Li NMR spin-lattice and spin-spin relaxation rates also show anomalies due to spin freezing near $T_{f}$.

Singlet ground state in the alternating spin- 12 chain compound NaVOAsO4

We present the synthesis and a detailed investigation of structural and magnetic properties of polycrystalline NaVOAsO$_4$ by means of x-ray diffraction, magnetization, electron spin resonance (ESR), and $^{75}$As nuclear magnetic resonance (NMR) measurements as well as density-functional band structure calculations. Temperature-dependent magnetic susceptibility, ESR intensity, and NMR line shift could be described well using an alternating spin-$1/2$ chain model with the exchange coupling $J/k_{\rm B}\simeq 52$ K and an alternation parameter $\alpha \simeq 0.65$. From the high-field magnetic isotherm measured at $T=1.5 $ K, the critical field of the gap closing is found to be $ H_{\rm c}\simeq 16$ T, which corresponds to the zero-field spin gap of $\Delta_0/k_{\rm B}\simeq 21.4$ K. Both NMR shift and spin-lattice relaxation rate show an activated behavior at low temperatures, further confirming the singlet ground state. The spin chains do not coincide with the structural chains, whereas the couplings between the spin chains are frustrated. Because of a relatively small spin gap, NaVOAsO$_4$ is a promising compound for further experimental studies under high magnetic fields.

1H and 13C NMR Studies on New Ionic Plastic Crystals Constructed by Ellipsoidal Cations with [BEt3Me] Anion

Abstract Two new ionic plastic crystals of [NEtMe2Pr][BEt3Me] and [NEt2MePr][BEt3Me] were found. In contrast, the highest-temperature solid-phase of [NEtMe2Bu][BEt3Me] and [NEt2MeBu][BEt3Me] were assigned to rotator phases. Solid-state 1H and 13C nuclear magnetic resonance (NMR) measurements revealed that both the cations and anions perform isotropic reorientations in the plastic phase. Conversely, the cations of [NEtMe2Bu] and [NEt2MeBu] undergo rotation about an axis. Based on these results, it is revealed that ellipsoidal cations of [NEtMe2Pr]+ and [NEt2MePr]+ can form plastic crystalline phases with [BEt3Me]−. In the lower temperature solid-phase of the plastic phase, a rotator phase was also found in [NEtMe2Pr][BEt3Me] and [NEt2MePr][BEt3Me] salts. This is rarely reported in alkylammonium compounds with [BEt3Me]. 1H NMR spin-lattice relaxation time (T1) measurements showed that activation energies of isotropic reorientation were slightly large when compared to those reported in other ionic plastic crystals constructed with globular cations. This difference can be explained by assuming the aspect ratio. On differential scanning calorimetry (DSC) charts, small entropy changes were recorded at melting points of four compounds. These results support the observation that cations and anions have large degrees of freedom of motion in the highest-temperature solid-phases (plastic and rotator phases).

Lithium ion dynamics in LiZr2(PO4)3 and Li1.4Ca0.2Zr1.8(PO4)3.

High ionic conductivity, electrochemical stability and small interfacial resistances against Li metal anodes are the main requirements to be fulfilled in powerful, next-generation all-solid-state batteries. Understanding ion transport in materials with sufficiently high chemical and electrochemical stability, such as rhombohedral LiZr2(PO4)3, is important to further improve their properties with respect to translational Li ion dynamics. Here, we used broadband impedance spectroscopy to analyze the electrical responses of LiZr2(PO4)3 and Ca-stabilized Li1.4Ca0.2Zr1.8(PO4)3 that were prepared following a solid-state synthesis route. We investigated the influence of the starting materials, either ZrO2 and Zr(CH3COO)4, on the final properties of the products and studied Li ion dynamics in the crystalline grains and across grain boundary (g.b.) regions. The Ca2+ content has only little effect on bulk properties (4.2 × 10-5 S cm-1 at 298 K, 0.41 eV), but, fortunately, the g.b. resistance decreased by 2 orders of magnitude. Whereas, 7Li spin-alignment echo nuclear magnetic resonance (NMR) confirmed long-range ion transport as seen by conductivity spectroscopy, 7Li NMR spin-lattice relaxation revealed much smaller activation energies (0.18 eV) and points to rapid localized Li jump processes. The diffusion-induced rate peak, appearing at T = 282 K, shows Li+ exchange processes with rates of ca. 109 s-1 corresponding, formally, to ionic conductivities in the order of 10-3 S cm-1 to 10-2 S cm-1.

Heterogeneous F anion transport, local dynamics and electrochemical stability of nanocrystalline La1−xBaxF3−x

Solid state ion conductors exhibiting fast ion dynamics are of utmost importance for the development of modern energy storage systems or sensors. For the realization of fluoride ion batteries (FIBs), that is, batteries relying on F− ions as charge carriers, materials with fast fluorine anion dynamics are needed. Here we used high-energy ball milling to incorporate BaF2 into the tysonite structure of LaF3 and studied ion dynamics by both broadband impedance and 19F nuclear magnetic resonance (NMR) spectroscopy. The nanocrystalline solid solution formed revealed increased ion conductivity compared to pure LaF3. Apart from the formation of F vacancies through aliovalent substitution, the increase in conductivity is also stimulated by the introduction of lattice strain and the high degree of local disorder produced. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19F NMR spin-lattice relaxation is sensitive. In this work, we tried to correlate short-range ion diffusion with long-range transport properties measured by conductivity spectroscopy. Additionally, we used electrochemical polarization and cyclic voltammetry to judge whether the ternary fluoride shows a sufficiently high electrochemical stability to work in FIBs.

Fast Na ion transport triggered by rapid ion exchange on local length scales

The realization of green and economically friendly energy storage systems needs materials with outstanding properties. Future batteries based on Na as an abundant element take advantage of non-flammable ceramic electrolytes with very high conductivities. Na3Zr2(SiO4)2PO4-type superionic conductors are expected to pave the way for inherently safe and sustainable all-solid-state batteries. So far, only little information has been extracted from spectroscopic measurements to clarify the origins of fast ionic hopping on the atomic length scale. Here we combined broadband conductivity spectroscopy and nuclear magnetic resonance (NMR) relaxation to study Na ion dynamics from the µm to the angstrom length scale. Spin-lattice relaxation NMR revealed a very fast Na ion exchange process in Na3.4Sc0.4Zr1.6(SiO4)2PO4 that is characterized by an unprecedentedly high self-diffusion coefficient of 9 × 10−12 m2s−1 at −10 °C. Thus, well below ambient temperature the Na ions have access to elementary diffusion processes with a mean residence time τNMR of only 2 ns. The underlying asymmetric diffusion-induced NMR rate peak and the corresponding conductivity isotherms measured in the MHz range reveal correlated ionic motion. Obviously, local but extremely rapid Na+ jumps, involving especially the transition sites in Sc-NZSP, trigger long-range ion transport and push ionic conductivity up to 2 mS/cm at room temperature.

Ion Dynamics in Al-Doped Cubic Li7La3Zr2O12 Garnet-Type Single Crystals

Li7La3Zr2O12 (LLZO) garnet-type materials are regarded as promising candidates for solid electrolytes and have been extensively investigated in the past few years.[1,2] Several studies report on an increase in conductivity by doping with ions to stabilize the cubic structure.[3,4] In the present study we focus on the ionic transport processes in Al-doped LLZO single crystals. To investigate ionic motions we used 7Li nuclear magnetic resonance (NMR) spectroscopy and impedance spectroscopy. With the help of rotating-frame spin-lock NMR spin-lattice relaxation (SLR) we looked at localized and medium-ranged ionic motions, respectively. Impedance spectroscopy was used to shed light on the long range ion dynamics. At room temperature the total conductivity turned out to be 0.082 mS cm- 1 at, which is remarkably good for LLZO with an Al-content of only 0.34 wt%.[5] Most importantly, 7Li NMR spin-lock NMR of revealed two overlapping diffusion-induced processes that share almost the same activation energy. A similar behavior has recently been seen for Mo-bearing LLZO.[6] Overall, activation energies gathered from spin-lock NMR and impedance measurements are in good agreement with each other; both techniques yield values around 0.36 eV. The solid-state coefficient (D) and the self-diffusion coefficient (Dsd), calculated from impedance spectroscopy and NMR spin-lock SLR, respectively, almost coincide. This excellent agreement points out that the two methods are sensitive to very similar motional correlations functions probing magnetic spin fluctuations and electrical relaxation processes, respectively.

Imaging of nuclear magnetic resonance spin-lattice relaxation activation energy in cartilage.

Samples of human and bovine cartilage have been examined using magnetic resonance imaging to determine the proton nuclear magnetic resonance spin–lattice relaxation time, T1, as a function of depth within through the cartilage tissue. T1 was measured at five to seven temperatures between 8 and 38°C. From this, it is shown that the T1 relaxation time is well described by Arrhenius-type behaviour and the activation energy of the relaxation process is quantified. The activation energy within the cartilage is approximately 11 ± 2 kJ mol−1 with this notably being less than that for both pure water (16.6 ± 0.4 kJ mol−1) and the phosphate-buffered solution in which the cartilage was immersed (14.7 ± 1.0 kJ mol−1). It is shown that this activation energy increases as a function of depth in the cartilage. It is known that cartilage composition varies with depth, and hence, these results have been interpreted in terms of the structure within the cartilage tissue and the association of the water with the macromolecular constituents of the cartilage.

NMR Characterization of the Na+ Ion Transport in Mixed Ionic Liquids Electrolytes

In the market of medium- and large- scale energy supplies, sodium (Na+) ion batteries are considered a possible alternative to current technologies. This is because sodium is naturally more abundant and cheaper than the ubiquitous lithium. Room temperature Na+ batteries typically employ organic solvents such as propylene carbonate. However, room temperature ionic liquids – while more viscous – are safer, and because of this attention is being paid towards their partial or complete replacement of organic solvents. Towards this endeavor, we investigated ions dynamics in mixtures of varying concentrations of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) or sodium bis(fluorosulfonyl)imide (NaFSI) salts, combined with the 1-butyl-1-methylpyrrolidinium (PYR1,4) FSI and PYR1,4 TFSI ionic liquids. We used variable-temperature 1H and 23Na Nuclear Magnetic Resonance (NMR) spin-lattice relaxation times (T1) and self-diffusion coefficients (D) measurements to investigate the short- and long- range ions dynamics and a preview of or results are shown in Figure 1. Both T1 (1H and 23Na) and 1H D data show greater short- and long- range dynamics for mixtures containing the FSI salt or ionic liquid. A more comprehensive discussion will be presented. Figure 1. Variable-temperature Na+ spin-lattice relaxation times (left) and 1H self-diffusion coefficients (right) for mixtures of various mol% of NaFSI or NaTFSI salt with PYR1,4 based ILs. Figure 1

Ion dynamics in a new class of materials: nanoglassy lithium alumosilicates

In many cases nanocrystalline materials, prepared through high-energy ball milling, reveal enhanced ion dynamics when compared to the situation in the coarse-grained analogues. This effect, which has particularly been seen for lithium alumosilicates, has been ascribed to structural disorder, i.e., the introduction of defect sites during mechanical treatment. Much less is, however, known about ion transport in nanostructured amorphous materials, e.g., nanoglassy compounds, which are regarded as a new class of functional materials. Following earlier studies on nanoglassy lithium alumosilicates and borates, here we studied ion dynamics in nanoglassy petalite LiAlSi4O10. While conductivity spectroscopy unequivocally reveals that long-range ion dynamics in nanoglassy LiAlSi4O10 decreases upon milling, local dynamics, sensed by 7Li nuclear magnetic resonance (NMR) spin-lattice relaxation, points to enhanced Li ion mobility compared to the non-treated glass. Most likely, as for nanocrystalline ceramics also for nanoglassy samples a heterogeneous structure, consisting of bulk and interfacial regions, is formed. For LiAlSi4O10 these interfacial regions, characterized by a higher degree of free volume, might act as hosts for spins experiencing fast longitudinal NMR relaxation. Obviously, these regions do not form a through-going network, which would allow the ions to move over long distances as quickly as in the unmilled glass.

Magnetic Resonance and Conductivity Study of Lead–Cadmium Fluorosilicate Glasses and Glass-Ceramics

The fluorine motional dynamics in fluorosilicate glasses and glass-ceramics of the SiO2–PbF2–CdF2 system was investigated by complex impedance spectroscopy and 19F nuclear magnetic resonance (NMR) spectroscopy, and the coordination environment of a Cu2+ paramagnetic probe was examined by electron paramagnetic resonance (EPR) spectroscopy. Glass-ceramics were obtained by heat treatment of glass at a temperature between the glass-transition (Tg) and the onset of crystallization (Tx). Ionic conductivity of about 1.6 × 10–4 S/cm was obtained at 500 K for glass. The conductivity of the glass-ceramics was found to be lower than that obtained for the glass. The temperature dependence of the 19F NMR spin–lattice relaxation times was investigated between 300 and 770 K. The 19F NMR results of glass exhibit the qualitative features associated with fluorine mobility, namely, the presence of a relaxation rate maximum below Tg. The NMR relaxation data of the glass-ceramics were analyzed assuming two fluorine dynamics. ...

Mismatch in cation size causes rapid anion dynamics in solid electrolytes: the role of the Arrhenius pre-factor.

Crystalline ion conductors exhibiting fast ion dynamics are of utmost importance for the development of, e.g., sensors or rechargeable batteries. In some layer-structured or nanostructured compounds fluorine ions participate in remarkably fast self-diffusion processes. As has been shown earlier, F ion dynamics in nanocrystalline, defect-rich BaF2 is much higher than that in the coarse-grained counterpart BaF2. The thermally metastable fluoride (Ba,Ca)F2, which can be prepared by joint high-energy ball milling of the binary fluorides, exhibits even better ion transport properties. While long-range ion dynamics has been studied recently, less information is known about local ion hopping processes to which 19F nuclear magnetic resonance (NMR) spin-lattice relaxation is sensitive. The present paper aims at understanding ion dynamics in metastable, nanocrystalline (Ba,Ca)F2 by correlating short-range ion hopping with long-range transport properties. Variable-temperature NMR line shapes clearly indicate fast and slow F spin reservoirs. Surprisingly, from an atomic-scale point of view increased ion dynamics at intermediate values of composition is reflected by increased absolute spin-lattice relaxation rates rather than by a distinct minimum in activation energy. Hence, the pre-factor of the underlying Arrhenius relation, which is determined by the number of mobile spins, the attempt frequency and entropy effects, is identified as the parameter that directly enhances short-range ion dynamics in metastable (Ba,Ca)F2. Concerted ion migration could also play an important role to explain the anomalies seen in NMR spin-lattice relaxation.

Fast Na Ion Transport Triggered By Rapid Ion Exchange on Local Length Scales

The realization of green and economically friendly energy storage systems needs materials with outstanding properties. Future batteries based on Na as an abundant element take advantage of nonflammable ceramic electrolytes with very high conductivities. Na3Zr2(SiO4)2PO4-type superionic conductors are expected to pave the way for inherently safe and sustainable all-solid-state batteries. So far, only little information has been extracted from spectroscopic measurements to clarify the origins of fast ionic hopping on the atomic length scale. Here we combined broadband conductivity spectroscopy and nuclear magnetic resonance (NMR) relaxation to study Na ion dynamics from the μm to the angstrom length scale. Spin-lattice relaxation NMR revealed a very fast Na ion exchange process in Na3.4Sc0.4Zr1.6(SiO4)2PO4 that is characterized by an unprecedentedly high self-diffusion coefficient of 9 ' 10−12 m2s−1 at –10 °C. Thus, well below ambient temperature the Na ions have access to elementary diffusion processes with a mean residence time τNMR of only 2 ns. The underlying asymmetric diffusion- induced NMR rate peak and the corresponding conductivity isotherms measured in the MHz range reveal correlated ionic motion. Obviously, local but extremely fast Na jumps, involving especially the transition sites in Sc-NZSP, trigger long-range ion transport and push ionic conductivity up to 2 mS/cm at room temperature.