Shangshu Li

Solid Oxide Membrane (SOM) Process for Facile Electrosynthesis of Metal Carbides and Composites

Abstract Metal carbides (MCs) and composites including TiC, SiC, TaC, ZrC, NbC, Ti5Si3/TiC, and Nb/Nb5Si3 have been directly electrosynthesized from their stoichiometric metal oxides/carbon (MOs/C) mixture precursors by an innovative solid oxide membrane (SOM)-assisted electrochemical process. MOs/C mixture powders including TiO2/C, SiO2/C, Ta2O5/C, ZrO2/C, Nb2O5/C, TiO2/SiO2/C, Nb2O5/SiO2 were pressed to form porous pellets and then served as cathode precursors. A SOM-based anode, made from yttria-stabilized zirconia (YSZ)-based membrane, was used to control the electroreduction process. The SOM electrochemical process was performed at 1273 K (1000 °C) and 3.5 to 4.0 V in molten CaCl2. The oxygen component contained in the MOs/C precursors was gradually removed during electroreduction process, and thus, MOs/C can be directly converted into MCs and composites at the cathode. The reaction mechanism of the electroreduction process and the characteristics of the obtained MCs and composites products were systematically investigated. The results show that the electrosynthesis process typically involves compounding, electroreduction, dissolution-electrodeposition, and in situ carbonization processes. The products can be predesigned and controlled to form micro/nanostructured MCs and composites. Multicomponent multilayer composites (MMCs) have also been tried to electrosynthesize in this work. It is suggested that the SOM-assisted electroreduction process has great potential to be used for the facile and green synthesis of various MCs and composites.

Electrochemical Preparation of Ti 5 Si 3 /TiC Composite from Titanium-Rich Slag in Molten CaCl 2

Ti5Si3/TiC composite has been successfully prepared from the titanium-rich slag/SiO2/C mixtures precursors by an electrochemical process. The electrochemical production process was carried out in molten CaCl2 salt at 1000 °C and 3.8 V. A pressed cylindrical pellet of titanium-rich slag/SiO2/C mixtures served as a cathode, and a solid oxide oxygen-ion-conducting membrane (SOM) tube filled with carbon-saturated liquid tin acted as an anode. The phase transformation of the cathode pellets during electrolysis process was investigated, the microstructure of the obtained products was characterized. It is found that the reaction pathways can be divided into three main stages during the electro-reduction process. The first stage is the generation of calcium compound, the second stage is the electrochemical reduction of the compound, and the third stage is the formation of Ti5Si3/TiC composite. The prepared Ti5Si3/TiC composite exhibits homogenous and nodular particle morphology.

Controlled Synthesis of TiC Nanoparticles Using Solid Oxide Membrane Technology in Molten CaCl2

Metal carbides (MCs), especially transition metal carbides have attracted a lot of attentions due to their unique properties, such as high strength and hardness, good chemical and thermal stability. In this paper, a new route was proposed for preparing TiC nanoparticles directly from TiO2/C precursor by using solid oxide membrane (SOM) technology in molten CaCl2. The TiO2/C pellet pressed under 8 MPa was used as the cathode, and a yttria-stabilized zirconia (YSZ) tube filled with carbon-saturated liquid tin was served as the anode. This process employs an inert SOM to separate the anodic reaction area from the molten electrolyte to control the electrolysis process. The electrochemical process was carried out in molten CaCl2 at 1000 °C and 4.0 V from 0.5 to 4 h. The characteristics of the phase composition and morphology of the electrolysis products were investigated. The product electrolyzed was examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive spectrometer (EDS). The results show that TiC nanoparticles can be obtained directly from TiO2/C mixture at 1000 °C, 4.0 V and for 4 h in molten CaCl2 and the current efficiency is calculated to be 74.1%. In conclusion, we suggest that the SOM process is a promising environmentally friendly and low energy costs electrochemical method for the facile and controllable electrodeoxidation of MOx/C precursors to micro/nanostructured MCs.