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Abstract

Molybdenum atomic-doping on bio-waste derived nitrogen-doped conductive carbon electrocatalyst was synthesized and investigated for the dinitrogen reduction to ammonia in alkaline media. The assessment of the catalytic activity was found to be non-trivial as nearly any external source can be the cause of ammonia contamination. In a closed-cell set-up using isotopically labelled 15N2 as feed gas for 48h chronoamperometry at -0.1 V vs RHE that the current density was correlated to the availability of the gas. Non-precious metals were incorporated in an oxidized carbon black conductive matrix and investigated for their activity towards oxygen evolution reaction in 0.1 M H2SO4, 0.5 M H2SO4 and 0.1 M HClO4. The stability of the deposited catalyst was insufficient and their deterioration was attributed to the oxidation of the carbon support as well as the dissolution of the metal ions upon high anodic potentials. The same metal-incorporated oxidized conductive carbon black agents were investigated for the enhancement of the performance of Si/C anodes in lithium-ion batteries. It was found that cobalt incorporation in the oxidized matrix displayed a significant influence in the electrochemical kinetics and consequent rate performances. With 0.8% cobalt ions by mass incorporated in oxidized KetJen Black the average capacity of the Si/C anode was increased by 180% at 1.5 A.g-1. This metal incorporation approach was extended to other ionic species (copper, iron and nickel) and other carbon conductive agents (SuperP). The electrolyte affinity, the desolvation process and the improved electronic conductivity synergistically improved the rate performance without compromising the gravimetric capacity of the electrode. The deposition of ultra-thin aluminium oxide by atomic layered deposition on the surface of LiNi0.5Co0.2Mn0.3O2 cathode material in lithium-ion batteries for the improvement of cyclic performances at high voltages (4.3-4.6 V) was investigated. One source of the failure mechanisms of the battery comes from unwanted side reactions between surface species and the electrolyte. The aluminium oxide layers of 1.42 nm and 2,36 nm were found to be beneficial at current densities exceeding 1.0 C (1 C = 170 mAh.g-1), and especially at 5.0 C with an increase of about 20 mAh.g-1 and 35 mAh.g-1 compared to uncoated NCM523, respectively. The capacity retention was found to be improved for all coated samples compared to pristine upon 140 cycles at 1.0 C. Mitigating side reactions and increasing the specific capacity at higher C-rates by atomically controlled layered deposition of inexpensive metal oxides is desirable for the implementation next-generation of safer and stable fast-charging high-voltage lithium-ion batteries.

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