NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials

Kuhn, Alexander; Kunze, Miriam; Puravankara, Sreeraj; Wiemhöfer, Hans‐Dieter; Thangadurai, Venkataraman; Wilkening, Martin; Heitjans, Paul

doi:10.1016/j.ssnmr.2012.02.001

Cited by 116 publications

(148 citation statements)

References 59 publications

Supporting

Mentioning

143

Contrasting

Unclassified

Order By: Relevance

“…A more detailed insight into the Li ion dynamics in solid electrolytes can be obtained by variable-temperature NMR relaxometry [14,[24][25][26][27][28]. Provided the jump rates follow a single Arrhenius law…”

Section: LI Nmr Relaxometrymentioning

confidence: 99%

Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Kuhn¹,

Choi

Robben

et al. 2012

Zeitschrift Für Physikalische Chemie

View full text Add to dashboard Cite

Lithium-ion dynamics in the garnet-type solid electrolyte "Li 7 La 3 Zr 2 O 12 " (LLZ) crystallizing with cubic symmetry was probed by means of variable-temperature 7 Li NMR spectroscopy and ac impedance measurements. Li jump rates of an Al-containing sample follow Arrhenius behavior being characterized by a relatively high activation energy of 0.54(3) eV and a pre-exponential factor of 2.2(5) × 10 13 s −1 . The results resemble those which were quite recently obtained for an Al-free LLZ sample crystallizing, however, with tetragonal symmetry. Hence, most likely, the significantly higher Li conductivity previously reported for a cubic LLZ sample cannot be ascribed solely to the slight structural distortions accompanying the change of the crystal symmetry. Here, even Al impurities, acting as stabilizer for the cubic polymorph at room temperature, do not lead to the high ion conductivity reported previously.

show abstract

Section: LI Nmr Relaxometrymentioning

confidence: 99%

Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Kuhn¹,

Choi

Robben

et al. 2012

Zeitschrift Für Physikalische Chemie

View full text Add to dashboard Cite

show abstract

“…In other materials where 8 Li + is known to be moving, e.g. rutile TiO2 [17,18] the relaxation rates are much faster and more strongly temperature dependent. It may be possible that the increase in relaxation with temperature is due to the onset of motion with a T1 minimum at higher temperatures above 300 K, but it is weaker than the expected activated dependence.…”

Section: Resultsmentioning

confidence: 99%

Beta Detected NMR of LaAlO₃

Karner

McFadden

Chatzichristos

et al. 2018

Proceedings of the 14th International Conference on Muon Spin Rotation, Relaxation and Resonance (ΜSR2017)

View full text Add to dashboard Cite

Using 8 Li β-NMR we studied the temperature dependence of the spin-lattice relaxation in LaAlO3 in high magnetic field. The relaxation in LAO is composed of two components: a fast-relaxing signal with a small amplitude, and a large amplitude, slow relaxing component. The data was fit using a highly-constrained model which assumes that the temperature dependence of the slow and fast component is the same at all temperatures. The 8 Li relaxation suggests a T 2 temperature dependence, indicating that the relaxation mechanism could be due to a coupling between the quadrupole moment of 8 Li and the soft-mode, low energy phonons in LAO.

show abstract

“…md and dft calculations also predict fast, anisotropic 1D diffusion of Li + along the rutile c-axis with a low hopping-barrier of ∼ 0.05 eV [21,22,24,25]. 3 These barriers are significantly lower than what is observed experimentally from macroscopic methods [26,27], though such measurements are done far from the limit of infinitely dilute lithium, where the potential energy landscape is likely altered by lattice distortions and Li + -Li + interactions [22,28]. The broad component of the resonance may be due to fast-diffusion of 8 Li + to Frenkel pairs, formed from irradiation, before they heal.…”

Section: −1mentioning

confidence: 90%

“…Macroscopic methods (e.g., impedance spectroscopy) are often used to probe ionic diffusion, but are unable to distinguish between different conductive pathways. The applicability of nmr to probe dynamics in solids is well known [3], and can be especially useful in resolving multiple diffusive pathways activated in different thermal regions [4]. Li dynamics in TiO 2 polymorphs (and related compounds) have been studied by conventional nmr [5,6,7,8,9,10], but no such investigation has been undertaken for rutile.…”

Section: Introductionmentioning

confidence: 99%

β-NMR of ⁸Li⁺ in rutile TiO₂

McFadden

Cortie

Arseneau

et al. 2014

J. Phys.: Conf. Ser.

View full text Add to dashboard Cite

Abstract. We report preliminary low-energy β-nmr measurements of 8 Li + implanted in single crystal rutile TiO2 at an applied field of 6.55 T and 300 K. We observe a broad 12 kHz wide quadrupole split resonance with unresolved features and a sharp component at the Larmor frequency. The line broadening may be caused by overlapping multi-quantum transitions or motion of 8 Li + on the scale of its lifetime (1.21 s). We also find spin-lattice relaxation that is relatively fast compared to other wide band gap insulators. The origin of this fast relaxation is also likely quadrupolar and may be due to anisotropic 8 Li + diffusion.

show abstract

NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials

Cited by 116 publications

References 59 publications

Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Beta Detected NMR of LaAlO₃

β-NMR of ⁸Li⁺ in rutile TiO₂

Contact Info

Product

Resources

About

NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials

Cited by 116 publications

References 59 publications

Li Ion Dynamics in Al-Doped Garnet-Type Li7La3Zr2O12 Crystallizing with Cubic Symmetry

Li Ion Dynamics in Al-Doped Garnet-Type Li7La3Zr2O12 Crystallizing with Cubic Symmetry

Beta Detected NMR of LaAlO3

β-NMR of 8Li+ in rutile TiO2

Contact Info

Product

Resources

About

Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Li Ion Dynamics in Al-Doped Garnet-Type Li₇La₃Zr₂O₁₂ Crystallizing with Cubic Symmetry

Beta Detected NMR of LaAlO₃

β-NMR of ⁸Li⁺ in rutile TiO₂