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.

Controlled Design of Functional Nano-Coatings: Reduction of Loss Mechanisms in Photoelectrochemical Water Splitting.

Efficient water splitting with photoelectrodes requires highly performing and stable photoactive materials. Since there is no material known which fulfills all these requirements because of various loss mechanisms, we present a strategy for efficiency enhancement of photoanodes via deposition of functional coatings in the nanometer range. Origins of performance losses in particle-based oxynitride photoanodes were identified and specifically designed coatings were deposited to address each loss mechanism individually. Amorphous TiO2 located at interparticle boundaries enables high electron conductivity. A thin layer of amorphous Ta2O5 can be used as protection layer for photoanodes because of its hole conductivity and thermal and chemical stability. An amorphous layer of NiOx and Co(OH)2 reduces photocorrosion or increases water oxidation kinetics because they act as a hole-capture material or water oxidation catalyst, respectively. Crystalline CoOx nanoparticles increase photocurrent and reduce the onset potential due to enhanced charge separation. The combination of all coatings deposited by a scalable, mild, and reproducible step-by-step approach leads to high-performance oxynitride-based photoanodes providing a maximum photocurrent of 2.52 mA/cm(2) at 1.23 VRHE under AM1.5G illumination.