Nuclear magnetic resonance offers a wide range of tools to analyse ionic jump processes in crystalline and amorphous solids. Both high-resolution and time-domain
1
,
2
H
,
6
,
7
Li
,
19
F
,
23
Na
NMR helps throw light on the origins of rapid self-diffusion in materials being relevant for energy storage. It is well accepted that
Li
+
ions are subjected to extremely slow exchange processes in compounds with strong site preferences. The loss of this site preference may lead to rapid cation diffusion, as is also well known for glassy materials. Further examples that benefit from this effect include, e.g. cation-mixed, high-entropy fluorides
( Ba, Ca) F
2
, Li-bearing garnets (
Li
7
La
3
Zr
2
O
12
) and thiophosphates such as
LiTi
2
(
PS
4
)
3
. In non-equilibrium phases site disorder, polyhedra distortions, strain and the various types of defects will affect both the activation energy and the corresponding attempt frequencies. Whereas in
(
Me, Ca
)
F
2
(
Me
=
Ba
,
Pb
)
cation
mixing influences F anion dynamics, in
Li
6
PS
5
X
(
X
=
Br
,
Cl
,
I
) the potential landscape can be manipulated by
anion
site disorder. On the other hand, in the mixed conductor
Li
4
+
x
Ti
5
O
12
cation-cation repulsions immediately lead to a boost in
Li
+
diffusivity at the early stages of chemical lithiation. Finally, rapid diffusion is also expected for materials that are able to guide the ions along (macroscopic) pathways with confined (or low-dimensional) dimensions, as is the case in layer-structured
RbSn
2
F
5
or
MeSnF
4
. Diffusion on fractal systems complements this type of diffusion.
This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.