$\rm\bf {^{23}Na}$ NMR spin-lattice relaxation reveals ultrafast $\rm\bf Na{^{+}}$ ion dynamics in the solid electrolyte $\rm\bf Na{_{3.4}}Sc{_{0.4}}Zr{_{1.6}}(SiO{_{4}}){_{2}}PO{_{4}}$

Autor: Lunghammer, S., Prutsch, D., Breuer, S., Rettenwander, D., Hanzu, I., Ma, Q., Tietz, F., Wilkening, M.
Rok vydání: 2017
Předmět:
Druh dokumentu: Working Paper
Popis: 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. $\rm Na{_{3}}Zr{_{2}}(SiO{_{4}}){_{2}}PO{_{4}}$-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 broad-band conductivity spectroscopy and nuclear magnetic resonance (NMR) relaxation to study Na ion dynamics from the {\mu}m to the angstrom length scale. Spin-lattice relaxation NMR revealed a very fast Na ion exchange process in $\rm Na{_{3.4}}Sc{_{0.4}}Zr{_{1.6}}(SiO{_{4}}){_{2}}PO{_{4}}$ that is characterized by an unprecedentedly high self-diffusion coefficient of $\rm 9 \times 10{^{-12}} m{^{2}}s{^{-1}}$ at $\rm -10{\deg}C$. Thus, well below ambient temperature the Na ions have access to elementary diffusion processes with a mean residence time $\rm {\tau}_{NMR}$ of only $\rm 2\; ns$. 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 $\rm Na{^{+}}$ jumps, involving especially the transition sites in Sc-NZSP, trigger long-range ion transport and push ionic conductivity up to $\rm 2\; mS\; cm{^{-1}}$ at room temperature.
Databáze: arXiv