Preparation of RE-containing magnesium alloys via molten-salt-mediated magnesiothermic reduction

RE-containing magnesium alloys were prepared via molten-salt-mediated magnesiothermic reduction by using RE_(2)O_(3)(RE=Y,Nd and Gd)and Mg metal as raw materials.The thermomechanical analysis of the magnesiothermic reduction reactions in molten salt was investigated.Then the molten-salt-mediated magnesiothermic reduction process was studied from three different perspectives.After that,the RE-containing magnesium alloy was characterized by using chemical analysis,XRD analysis and SEM analysis.The magnesiothermic reduction was a liquid-liquid reaction with relatively weak driving force.During the melting process and the magnesiothermic reduction process,magnesium metal and the obtained alloy went up and down as a whole in molten salt,which improved the process safety without introducing chloride inclusions.Meanwhile,the hydrolysis of the RECl_(3^(-))containing molten salt occurred at elevated temperature,which severely impeded the magnesiothermic reduction process.After the magnesiothermic reduction at 750°C for 2.0 h,the content of RE and the common impurity elements in the obtained RE-containing alloy met the both requirements of the commercial WE43A and WE43B.

Effect of Pore Structures on the Electrochemical Performance of Porous Silicon Synthesized from Magnesiothermic Reduction of Biosilica

Two kinds of porous silicon（PS） were synthesized by magnesiothermic reduction of rice husk silica（RHS） derived from the oxidization of rice husks（RHs）. One was obtained from oxidization/reduction at 500 ℃ of the unleached RHs, the other was synthesized from oxidization/reduction at 650 ℃ of the acidleached RHs. The structural difference of the above PS was compared： the former had a high pore volume（PV, 0.31 cm3/g） and a large specific surface area（SSA, 45.2 m^2/g）, 138 % and 17 % higher than the latter, respectively. As anode materials for lithium ion batteries, the former had reversible capacity of 1 400.7 m Ah/g, 987 m Ah/g lower than the latter; however, after 50 cycles, the former had 64.5 % capacity retention（907 m Ah/g）, which was 41.2 % higher than the latter（555.7 m Ah/g）. These results showed that the electrochemical performance of PS was significantly affected by its pore structures, and low reduction temperature played the key role in increasing its porosity, and therefore improving its cycling performance.

Synthesis of vanadium powder by magnesiothermic reduction of V_(2)O_(3)in a reactive molten salt

As an important strategic metal,vanadium is generally used to prepare special steels,titanium alloys,and hydrogen storage materials.A new method of producing vanadium(metal)powder from V_(2)O_(3)using block Mg is presented herein.Using an auxiliary molten salt,V_(2)O_(3)was successfully transformed into V by Mg reduction.The by-product,MgO,was transformed into MgCl_(2)by adding ZrCl_(4),which prevented the generation of MgV_(2)O_(4)and allowed the reaction to proceed smoothly.The rod-like alloy phases,Zr_(0.03)V_(1.97),which formed in the presence of excess Mg,may hinder the diffusion of oxygen from the product.The recovery rate of vanadium after separation and purification was approximately 45%–50%,where the main loss occurred during ball milling.Under the optimal conditions(Mg content of 48.3%,reduction time of 1.5 h,and temperature of 850℃),the purity of vanadium exceeded 99 wt.%,and the O content decreased to 0.34 wt.%.

Graphene-encapsulated blackberry-like porous silicon nanospheres prepared by modest magnesiothermic reduction for high-performance lithium-ion battery anode

Porous silicon(Si)nanostructures have aroused much interest as lithium-ion battery anodes because of the large space to accommodate the volume change in lithiation and delithiation and shorter ion transfer distance.However,fabrication of porous structures tends to be difficult to control and complex,so,the final electrochemical performance can be compromised.Herein,a modest magnesiothermic reduction(MMR)reaction is demonstrated to produce blackberry-like porous Si nanospheres(PSSs)controllably using magnesium silicide(Mg_(2)Si)as Mg source and SiO_(2)nanospheres as the reactant.This improved MR method provides good control of the kinetics and heat release compared to the traditional MR(TMR)method using Mg powder as the reactant.The PSSs obtained by MMR reaction has higher structural integrity than that fabricated by TMR.After encapsulation with reduced graphene oxide,the Si/C composite exhibits superior cycling stability and rates such as a high reversible capacity of 1034 mAh·g^(-1)at0.5 C(4200 mAh·g^(-1)at 1.0 C)after 1000 cycles,capacity retention of 79.5%,and high rate capacity of 497 mAh·g^(-1)at 2.0 C.This strategy offers a new route to fabricate highperformance porous Si anodes and can be extended to other materials such as germanium.

Intermetallic ferric nickel silicide alloy derived from magadiite by magnesiothermic reaction as bifunctional electrocatalyst for overall water splitting

As the cleanest energy source,hydrogen energy is regarded as the most promising fuel.Water electrolysis,as the primary means of hydrogen production,has constantly been the focus of attention in the energy conversion field.Developing eco-friendly,cheap,safe and efficient catalysts for electrochemical water splitting(EWS)is the key challenge.Herein,the intermetallic silicide alloy is first synthesized via a facile magnesiothermic reduction and employed as bifunctional electrocatalysts for EWS.Ferric-nickel silicide(denoted as FeNiSi)alloy is designed and shows a good electrocatalytic performance for EWS.The lattice distortions of FeNiSi enhance the electrocatalytic activity.Besides,the porous structure affords more active sites and improves the reaction kinetics.As a consequence,FeNiSi delivers an excellent performance with overpotential of 308 mV for oxygen evolution reaction(OER)and 386 mV for hydrogen evolution reaction(HER)at 10 mA·cm−2 in 1 M KOH.The stability structure of intermetallic silicide achieves an outstanding durability with an unchanged potential of 1.66 V for overall water splitting at 10 mA·cm−2 for 15 h.This work not only provides a facile method for the synthesis of intermetallic silicide with considerable porous structures,but also develops the potential of intermetallic silicide alloy as bifunctional electrocatalysts for EWS,which opens up a new avenue for the design and application of intermetallic silicide alloy.

Low-temperature Magnesiothermic Synthesis of Mesoporous Silicon Carbide from an MCM-48/Polyacrylamide Nanocomposite Precursor

Mesoporous silicon carbide with high specific surface area was successfully synthesized from an MCM-48/ polyacrylamide nanocomposite precursor in the temperature range of 550-600 ℃ （below the melting point of Mg） by means of a magnesiothermic reduction process. The MCM-48/polyacrylamide precursor nanocomposite was prepared by in-situ polymerization of acrylamide monomer in the presence of mesoporous MCM-48 synthesized by sol-gel method. The physicochemical properties and microstructures of the nanocomposite precursor and the low-temperature SiC product were characterized by X-ray diffraction （XRD）, differential scanning calorimetry-thermo gravimetric analysis （DSC-TGA）, transmission electron microscopy （TEM） and N2 adsorption-desorption. TEM micrographs and Brunauer-Emmett-Teller （BET） gas adsorption studies showed that the SiC powder was nanocrystalline and had a specific surface area of 330 m2/g and a mesoporosity in the range of 2-10 nm. The presence of an exothermic peak in the DSC trace corresponds to the self-combustion process of the SiC magnesiothermic synthesis. The results also show that the carbon in excess to that required to produce SiC plays a role in the reduction of the SiO2. The mechanism of magnesiothermic synthesis of mesoporous SiC is discussed.

Pomegranate-type Si/C anode with SiC taped,well-dispersed tiny Si particles for lithium-ion batteries

Severe volume expansion and inherently poor lithium ion transmission are two major problems of silicon anodes.To address these issues,we proposed a pomegranate-type Si/C composite anode with highly dispersed tiny silicon particles as the core assisted by small amount of SiC.Skillfully exploiting the high heat from magnesiothermic reduction,SiC can assist the good dispersion of silicon and provide good interface compatibility and chemical stability.The silicon anchored to the carbon shell provides multipoint contact mode,that together with the carbon shell frame,significantly promoting the transfer of dual charge.Besides,the pomegranate-type microcluster structure also improves the tap density of the electrode,reduces the direct contact area between active material and electrolyte,and enhances the electrochemical performance.

A combination of hierarchical pore and buffering layer construction for ultrastable nanocluster Si/SiO_(x)anode

Porous Si can be synthesized from diverse silica(SiO_(2))via magnesiothermic reduction technology and widely employed as potential anode material in lithium ion batteries.However,concerns regarding the influence of residual silicon oxide(SiO_(x))component on resulted Si anode after reduction are still lacked.In this work,we intentionally fabricate a cauliflower-like silicon/silicon oxide(CF-Si/SiO_(x))particles from highly porous SiO_(2)spheres through insufficient magnesiothermic reduction,where residual SiO_(x)component and internal space play an important role in preventing the structural deformation of secondary bulk and restraining the expansion of Si phase.Moreover,the hierarchically structured CF-Si/SiO_(x)exhibits uniformly-dispersed channels,which can improve ion transport and accommodate large volume expansion,simultaneously.As a result,the CF-Si/SiO_(x)-700 anode shows excellent electrochemical performance with a specific capacity of^1,400 mA·h·g^(−1)and a capacity retention of 98%after 100 cycles at the current of 0.2 A·g^(−1).

Meso-porous silicon-coated carbon nanotube as an anode for lithium-ion battery

Meso-porous Si-coated carbon nanotube （CNT） composite powders were prepared by combining a sol-gel method and the magnesiothermic reduction process. Meso-porous Si-coated CNT electrodes exhibit excellent cycle and rate performances as anodes in Li-ion batteries （LIBs）, which can be attributed to the efficient accommodation of volume change from meso-porous Si structure and the enhanced electrical conductivity from CNT core. This simple synthesis and subsequent reduction process provide a scalable route for the large-scale production of Si-C composite nanostructures, which can be utilized in a variety of applications, such as in photocatalysis, photoelectrochemical cells （PECs）, and LIBs.