Unveiling the electronic properties of native solid electrolyte interphase layers on Mg metal electrodes using local electrochemistry

Magnesium-ion batteries (MIBs) are of considerable interest as environmentally more sustainable, cheaper, and safer alternatives to Li-ion systems. However, spontaneous electrolyte decomposition occurs due to the low standard reduction potential of Mg, leading to the deposition of layers known as native solid electrolyte interphases (n-SEIs). These layers may inhibit the charge transfer (electrons and ions) and, therefore, reduce the specific power and cycle life of MIBs. We propose scanning electrochemical microscopy (SECM) as a microelectrochemical tool to locally quantify the electronic properties of n-SEIs for MIBs. These interphases are spontaneously formed upon contact of Mg metal disks with organoaluminate, organoborate, or bis(trifluoromethanesulfonyl)imide (TFSI)-based electrolyte solutions. Our results unveil increased local electronic and global ionic insulating properties of the n-SEI formed when using TFSI-based electrolytes, whereas a low electronically protecting character is observed with the organoaluminate solution, and the organoborate solution being in between them. Moreover, ex situ morphological and chemical characterization was performed on the Mg samples to support the results obtained by the SECM measurements. Differences in the electronic and ionic conductivities of n-SEIs perfectly correlate with their chemical compositions. Native solid electrolyte interphases (n-SEI) of magnesium ion batteries were systematically formed using different electrolyte compositions, and the electronic and ionic properties were interrogated using scanning electrochemical microscopy (SECM) complemented by electrochemical impedance spectroscopy and ex situ analysis for chemical composition characterization.