Hydrogen is widely regarded as a prime energy carrier for bridging the gap between renewable energy supply and demand. As the energy-generating component of the hydrogen cycle, affordable and reliable fuel cells are of key importance to the growth of the hydrogen economy. However, the use of scarce and costly Pt as an electrocatalyst for the oxygen reduction reaction (ORR) remains an issue to be addressed, and in this regard, metal–organic frameworks (MOFs) are viewed as promising non-noble alternatives because of their self-assembly capability and tunable properties. Herein, recent (2018–2020) works on MOF-based electrocatalysts containing N-doped C, Mn, Fe, Co, multiple metals, and multiple sites are reviewed and summarized with a focus on ORR activity, and the principal physicochemical properties and electrochemical performance of these catalysts realized using rotating electrodes are compared.

In this study, a carbon-coated LiFePO₄ (LFP/C) powder was chemically grafted with trifluoromethylphenyl groups in order to increase its hydrophobicity and to protect it from moisture. The modification was carried out by the spontaneous reduction of in situ generated 4-trifluoromethylphenyl ions produced by the diazotization of 4-trifluoromethylaniline. X-ray photoelectron spectroscopy was used to analyze the surface organic species of the modified powder. The hydrophobic properties of the modified powder were investigated by carrying out its water contact angle measurements. The presence of the trifluoromethylphenyl groups on the carbon-coated LiFePO₄ powder increased its stability in deionized water and reduced its iron dissolution in the electrolyte used for assembling the battery. The thermogravimetric and inductively coupled plasma atomic emission spectroscopy analyses revealed that 0.2–0.3 wt.% Li was deinserted during grafting and that the loading of the grafted molecules varied from 0.5 to 0.8 wt.% depending on the reaction conditions. Interestingly, the electrochemical performance of the modified LFP/C was not adversely affected by the presence of the trifluoromethylphenyl groups on the carbon surface. The chemical relithiation of the grafted samples was carried out using LiI as the reducing agent and the lithium source in order to obtain fully lithiated grafted powders.

We propose a innovative concept to boost the electrochemical performance of cathode composite electrodes using surface-modified carbons with hydrophilic moieties to increase their dispersion in a Lithium Nickel Manganese Cobalt Oxide (NMC) cathode and in-situ generate Li-rich carbon surfaces. Using a rapid aqueous process, the hydrophilic carbon is effectively dispersed in NMC particles followed by the conversion of its acid surface groups (e.g. –COOH), which interact with the NMC particles due to their basicity, into grafted Li salt (–COO⁻Li⁺). The solid-state batteries prepared using the cathode composites with surface-modified carbon exhibit better electrochemical performance. Such modified carbons led to a better electronic conduction path as well as facilitating Li⁺ ions transfer at the carbon/NMC interface due to the presence of lithiated carboxylate groups on their surface.

The deposition of a thin Li_xSn_y alloy layer by plasma vapor deposition (PVD) on the surface of a Li foil is reported. The formation of a Li-rich alloy is confirmed by the volume expansion (up to 380%) of the layer and by the disappearance of metallic Sn peaks in the X-ray diffractogram. The layer has a much higher hardness than bare Li and can withstand aggressive cycling at 1C. Post-mortem scanning electron microscope observations revealed that the alloy layer remains intact even after fast cycling for hundreds of cycles. A concept of double modification by adding a thin ceramic/polymer layer deposited by a doctor blade on top of the Li_xSn_y layer was also reported to be efficient to reach long-term stability for 500 cycles at C/3. Finally, a post-treatment after Sn deposition consisting of a plasma cleaning of the Li_xSn_y alloy layer led to a strong improvement in the cycling performance at 1C. The surface is smoother and less oxidized after this treatment. The combination of a Li-rich alloy interlayer, the increase in hardness at the electrolyte/Li interface, and the absence of dissolution of the layer during cycling at high C-rates are reasons for such an improvement in electrochemical performance.