Multivalent-ion chemistries such as Mg-ion are emerging as alternative battery systems to Li-ion. Current Mg-ion chemistries are limited to relatively low voltages and relatively low reversible specific capacities (1-2). Recent research on potential high voltage Mg-ion cathode materials and alternative anode materials such as transition metal oxides and metal alloys have highlighted the urgent need to understand structure activity relationships and insertion/intercalation phenomenon for development of such systems (3). Solid state NMR is a powerful tool to investigate local structure and insertion/intercalation phenomena, particularly for batteries as shown for Li-ion chemistries with 6
Li and 7
Li NMR (4, 5). However, the low natural abundance (10%) of the NMR active Mg isotope (25
Mg), highly quadrupolar nuclear spin of 25
Mg (spin 5
) and very low gyromagnetic ratio (i.e
30.6 MHz Larmor frequency relative to 1
H = 500 MHz) limits the effective use of 25
Mg NMR for solid Mg-ion battery materials (6). In this work, despite the challenges of 25
Mg NMR, our recent efforts to characterize Mg environments in cathode materials such as MgMn2
, in anode materials such as h-TiO2
and Mg-Sn alloys will be presented. Chemical magnesiation using dibutylmagnesium and preliminary electrochemical (de)mangesiation and the structral changes induced will be discussed. The results will summarize the effectiveness of the method in distinguishing side reactions or undesirable conversion reactions, including amorphous phases, from intercalation phenomenon.
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