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

• Published in: Scientific reports Vol. 8; no. 1; pp. 11970 - 8
• Main Authors: Lunghammer, S., Prutsch, D., Breuer, S., Rettenwander, D., Hanzu, I., Ma, Q., Tietz, F., Wilkening, H. M. R.
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 10-08-2018; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 639/301/299/891; 639/638/298/924; Ambient temperature; Conductivity; Conductors; Diffusion coefficient; Energy storage; Flammability; Humanities and Social Sciences; Ion exchange; Ion transport; Ions; multidisciplinary; NMR; Nuclear magnetic resonance; Science; Science (multidisciplinary); Spectroscopy
• ISSN: 2045-2322; 2045-2322
• DOI: 10.1038/s41598-018-30478-7

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. Na
3
Zr
2
(SiO
4
)
2
PO
4
-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 Na
3.4
Sc
0.4
Zr
1.6
(SiO
4
)
2
PO
4
that is characterized by an unprecedentedly high self-diffusion coefficient of 9 × 10
−12
m
2
s
−1
at −10 °C. Thus, well below ambient temperature the Na ions have access to elementary diffusion processes with a mean residence time
τ
NMR
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.