An efficient molten-salt electro-deoxidation strategy enabling fast-kinetics and long-life aluminum-selenium batteries

Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the shuttle effect of soluble intermediate product and sluggish reaction kinetics in the solid-solid conversion process during cycling.Herein,we propose an unprecedented design concept for fabricating uniform Se/C hollow microspheres with controllable morphologies through low-temperature electro-deoxidation in neutral NaCl-AlCl_(3) molten salt system.Such Se/C hollow microspheres are demonstrated to hold a favorable hollow structure for hosting Se,which can not only suppress the dissolution of soluble intermediate products into the electrolyte,thereby maintaining the structural integrity and maximizing Se utilization of the active material,but also promote the electrical/ionic conductivity,thus facilitating the rapid reaction kinetics during cycling.Accordingly,the as-prepared Se/C hollow microspheres exhibit a high reversible capacity of 720.1 mAh g^(−1)at 500 mA g^(−1).Even at the high current density of 1000 mA g^(−1),Se/C delivers a high discharge capacity of 564.0 mAh g^(−1),long-term stability over 1100 cycles and high Coulombic efficiency of 98.6%.This present work provides valuable insights into short-process recovery of advanced Se-containingmaterials and value-added utilization for energy storage.

Reaction mechanism of preparation of titanium by electro-deoxidation in molten salt

The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were carried out for solving the puzzle of reduction mechanism.The results showed that the reduction process proceeded step by step.TiO2 was first reduced to Ti3O5 or Ti2O3,and then further reduced to Ti3O,Ti2O,TiO and Ti.In addition,direct electrochemical reduction of titanium dioxide was the primary cathodic reaction;meanwhile,some calciothermic reduction reactions also happened at the cathode.Cyclic voltammograms of solid titanium dioxide and molybdenum wire in molten salts with different compositions were also studied.

Preparation of ZrMn_2 hydrogen storage alloy by electro-deoxidation in molten calcium chloride

ZrMn2 alloy was electro-synthesized directly from cathode pellets compacted with powdered mixture of MnO2 and ZrO2 in molten calcium chloride. Sintering temperature, cell voltage and electrolysis time were the dominant factors that affected the characteristics of the final product. The results confirmed the formation of pure ZrMn2 alloy through the electro-deoxidation of the mixed oxide pellets at 3.1 V for 12 h in 900 °C CaCl2 melt. The X-ray diffraction（XRD） and cyclic voltammetry analysis suggested that the electro-deoxidation proceeded from the reduction of manganese oxides to Mn, followed by ZrO2 or CaZrO3 reduction on the pre-formed Mn to ZrMn2 alloy. The cyclic voltammetry measurements using powder microelectrode showed that the prepared ZrMn2 alloy has a good electrochemical hydrogen storage property.

Electro-deoxidation of V_2O_3 in molten CaCl_2-NaCl-CaO

The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.

Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

Pr^（3＋）-activated barium tungsto-molybdate solid solution phosphor Ba（Mo_（1-z）W_z）O_4：Pr^（3＋）is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr^（3＋）-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO_4] for [MoO_4] can significantly enhance its luminescence, which may be due to the fact that Ba（Mo_（1-z）W_z）O_4：Pr^（3＋）owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity,well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white lightemitting diodes（LEDs）.

Formation mechanism and preparation of YAl_(2) intermetallics by electro-deoxidation with different sintering conditions

A study was carried out on the preparation of YAl_(2) intermetallics from mixed oxide precursors using the method of electro-deoxidation.Y2O_(3) and Al_(2)O_(3) mixed in molar proportions of 1:2 were sintered at temperatures ranging from 800 to 12000C for different hours.The sintered pellet was then electrolyzed in a molten CaCl_(2) at850℃using a graphite anode at a potential of 3.1 V.In this work,effects of sintering on the composition and the oxygen content in cathodic products were studied by X-ray diffraction(XRD)and oxygen-nitrogen analyzer.Sintering mainly affects the porosity of the pellets,and it is found that porosity decreases gradually with the increase in sintering temperature and the extension of sintering time.When sintered at 9000C for 4 h,the oxygen content in the cathodic product decreases to 1.85 wt%,and the efficiency of electro-deoxidation is 94.48%.At the same time,the mechanism of electrolysis was speculated.The results suggest that the formation of YAl_(2) is a multi-step process.During the reduction process from mixed oxides Y2O_(3)/Al_(2)O_(3) to YAl_(2) included many intermediate materials,such as YAlO_(3),Y3Al5O12 and YAl3,YAl_(2) intermediate alloy was prepared finally.

Binary molten salt in situ synthesis of sandwich-structure hybrids of hollowβ-Mo2C nanotubes and N-doped carbon nanosheets for hydrogen evolution reaction

Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.

不同燃料组合在液态氟盐冷却高温堆中的物理性能研究

液态氟盐冷却高温堆是第四代反应堆中的一种具有极大优势的堆型,对其燃料的研究工作具有重要的意义。本工作采用SCALE5.1程序包,对六种不同燃料组合在高温球床堆中的物理性能进行了研究,分别比较了剩余反应性、等效满功率运行天数、燃耗和中子能谱等重要参数。结果显示,采用233U或235U启堆时,使用232Th的实际转换成裂变材料的量不如使用238U转换的多,并会消耗更多的核燃料;采用239Pu启堆时,使用232Th可使反应堆维持较长的时间,而使用238U却导致反应堆很快不能自持。研究表明,从节约核燃料和延长堆芯寿期的角度看,在不进行在线换料后处理的情况下,232Th在热堆中的表现不如238U,但在超热堆中238U的表现不如232Th。

Direct electrochemical preparation of CeCo_5 alloy from mixed oxides

CeCo5 alloy was prepared from the mixture of cobalt oxide （Co3O4） and cerium oxide （CeO2） powders by electro-deoxidation in molten calcium chloride. The effects of the cell voltage and sintering temperature on the electrolysis process were reported. The electro-deoxidation mechanism was investigated by potentiodynamic polarization using a molybdenum cavity electrode in conjunction with characterization of the products from constant voltage electrolysis under different conditions by XRD and SEM. The electrochemical property of CeCo5 alloy was investigated by cyclic voltammetry measurements. The results show that the electro-deoxidation rate increases with increasing the cell voltage and decreasing the sintering temperature. The pure CeCo5 can be prepared by direct electro-deoxidation of mixed CeO2/Co3O4 pellets sintered at 850 °C when the cell voltage of 3.1 V is applied. The electro-deoxidation proceeds by the simultaneous reduction of Co3O4 to Co and reduction of CeO2 to CeOCl, followed by CeOCl reduction on the pre-formed Co to form CeCo5 alloy which shows a good cycling stability.

Direct synthesis of La-Mg-Ni-Co type hydrogen storage alloys from oxide mixtures

(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capacities of the synthesized alloys were measured. Non-hygroscopic LaNiO;phase formed during sintering（at 1200 °C for 2 h） as a result of the reaction of hygroscopic La;O;with NiO. Another sinter product was Mg;Ni;O phase. Both mixed oxide sinter products facilitated the La-Ni and Mg-Ni phase formations. X-ray diffraction peaks indicated that the first stable phase appeared in the alloy structure was LaNi;which formed upon reduction of La;NiO;phase. Increase in Mg content caused formation of La;Mg;Ni;phase in the alloy structure and the presence of this phase improved the hydrogen storage performance of the electrodes. It was observed that(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys have promising discharge capacities change between 319 m Ah/g and 379 m Ah/g depending on the alloy Mg content.

Electrochemical process for recovery of metallic Mn from waste LiMn_(2)O_(4)-based Li-ion batteries in NaCl−CaCl_(2)melts

new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_(4) reduction process by the electrochemical method on the coated electrode surface occurs in three steps:Mn(IV)→Mn(III)→Mn(II)→Mn.The products of this electro-deoxidation are CaMn2O4,MnO,(MnO)x(CaO)1−x,and Mn.Metal Mn appears when the electrolytic voltage increases to 2.6 V,which indicates that increasing the voltage may promote the deoxidation reaction process.With the advancement of the three-phase interline(3PI),electric deoxygenation gradually proceeds from the outer area of the crucible to the core.At high voltage,the kinetic process of the reduction reaction is accelerated,which generates double 3PIs at different stages.

Enhanced photocatalytic hydrogen production activity of highly crystalline carbon nitride synthesized by hydrochloric acid treatment

Crystalline carbon nitride(CCN)prepared by a molten-salt method is attracting increased attention because of its promising properties and excellent photocatalytic activity.In this work,we further improve the crystallinity of CCN through synthesis by the molten-salt method under the action of aqueous hydrochloric acid(HCl)solution.Our results showed that the crystallinity of the as-prepared samples increased with increasing HCl concentration and reached the maximum value at 0.1 mol L^-1.This can be attributed to the removal of some potassium ions(K+)from the terminal amino groups of CCN by the aqueous HCl solution,which results in a release of the polymerization sites.As a result,the crystallinity of the as-prepared samples further increased.Moreover,the obtained 0.1 highly crystalline carbon nitride(0.1HCCN;treated with 0.1 mol L^-1 aqueous HCl solution)exhibited an excellent photocatalytic hydrogen evolution of 683.54μmol h^-1 g^-1 and a quantum efficiency of 6.6%at 420 nm with triethanolamine as the sacrificial agent.This photocatalytic hydrogen evolution was 2 and 10 times higher than those of CCN and bulk carbon nitride,respectively.The enhanced photocatalytic activity was attributed to the improved crystallinity and intercalation of K+into the xHCCN interlayer.The improved crystallinity can decrease the number of surface defects and hydrogen bonds in the as-prepared sample,thereby increasing the mobility of the photoinduced carriers and reducing the recombination sites of the electron-hole pairs.The K+intercalated into the xHCCN interlayer also promoted the transfer of the photoinduced electrons because these ions can increase the electronic delocalization and extend theπ-conjugated systems.This study may provide new insights into the further development of the molten-salt method.

Rare earth recovery from fluoride molten-salt electrolytic slag by sodium carbonate roasting-hydrochloric acid leaching

Fluorinated rare earth molten-salt electrolytic slag contains a considerable amount of rare earth elements,as well as a variety of heavy metals and fluorides that cause environmental pollution.Therefore,it is of great importance to fully utilise this resource.In this study,the transformation mechanism of fluorinated rare earth molten-salt electrolytic slag roasted with sodium carbonate,and the regulation mechanism of rare earth leaching under different roasting conditions were investigated with the help of thermodynamic calculation of the reactions and kinetic analysis.The thermodynamic and differential thermal thermogravimetric(DTA-TG)analysis shows that the transformation of rare earth fluoride to rare earth oxide is promoted at elevated temperature.Furthermore,the leaching experimental results show that increasing the temperature,time,hydrochloric acid concentration,and liquid-solid ratio can effectively promote the recovery of rare earths.The optimum experimental conditions are a roasting temperature of 700℃,roasting time of 2 h,and sodium carbonate to molten salt electrolytic slag mass ratio of 0.6,followed by leaching at 80℃with a liquid-solid ratio of 10:1 by adding 3 moI/L hydrochlo ric acid with stirring for 2 h.Under these conditions,the rare earths in the molten salt electrolytic slag are biologically transformed at a lower temperature and the leaching efficiency of rare earths exceeds 98%.

Electrochemical derusting in molten Na_(2)CO_(3)–K_(2)CO_(3)

The formation of a rust layer on iron and steels surfaces accelerates their degradation and eventually causes material failure.In addition to fabricating a protective layer or using a sacrificial anode, repairing or removing the rust layer is another way to reduce the corrosion rate and extend the lifespans of iron and steels.Herein, an electrochemical healing approach was employed to repair the rust layer in molten Na_(2)CO_(3)-K_(2)CO_(3).The rusty layers on iron rods and screws were electrochemically converted to iron in only several minutes and a metallic luster appeared.Scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS) analyses showed that the structures of the rust layer after healing were slightly porous and the oxygen content reached a very low level.Thus, high-temperature molten-salt electrolysis may be an effective way to metalize iron rust of various shapes and structures in a short time, and could be used in the repair of cultural relics and even preparing a three-dimensional porous structures for other applications.

Recovery of rare earth elements from rare earth molten salt electrolytic slag via fluorine fixation by MgCl_(2)roasting

Rare earth fluoride molten-salt electrolytic slag(REFES)is a precious rare earth element(REE)secondary resource,and conside rable amounts of REEs exist in REFES as REF_(3);they are difficult to dissolve in acid or water and impede efficient REE extraction.In REFES recovery,the REF_(3)species in REFES are usually transformed into acid-soluble rare earth compounds by NaOH roasting or sulfating roasting and then extracted by acid leaching,Moreover,the fluorides in REFES are released as HF gas in the roasting process or enter the liquid phase during the water washing process;both of these processes cause fluorine pollution.Fixing the fluorine into the solid slag provides a way to avoid fluorine pollution.In this study,a novel method was proposed to extract REEs from REFES via MgCl_(2)roasting followed by HCl leaching.Thermodynamics calculations and the rmogravimetry-differential thermal analyses(TG-DTA)were conducted to investigate the reactions occurring in the roasting process,First,MgCl_(2)reacts with the REF_3and RE_(2)O_(3)to form RECl_(3)and REOCl,respectively.Second,the RECI_(3)absorbs water and forms RE(OH)_(3).Third,MgCl_(2)·6H_(2)O is gradually dehydrated to MgCl_(2)·2H_(2)O and reacts with REF_(3)and RE(OH)_(3),and REOCl,MgF_(2)and MgO are formed.Through HCl leaching,the REOCl in the roasting products is leached by HCl acid,while fluoride re mains in the solid slag as MgF_2.The optimum experimental conditions are as follows:mass ratio of MgCl_(2)to REFES of 30%,roasting temperature of 700℃,roasting time of 2 h,hydrochloride acid concentration of 4 mol/L,leaching time of 2 h,leaching temperature of 90℃and leaching L/S ratio of 20:1.The efficiencies for total leaching of the REEs,La,Ce,Pr,and Nd are 99.13%,99.20%,98.42%,99.38%,and 99.08%,respectively.Moreover,the concentration of fluoride in the leaching solution is 2.191×10^(-6)mol/L.This method has a short process flow with low reagent costs,and the problem of fluoride pollution from REFES recovery is solved;thus,our study has great industrial application potential.

Preparation of High-Entropy Alloy-Ceramic Coating Compos-ites on Steel Surfaces by Combined Process and Their Mechanical Properties

A combined process of molten salt electro-deoxidation and vacuum hot-pressing sintering was proposed to prepare AlCrFeNiTi_(x) high-entropy alloy(HEA)-TiN ceramic coating composites on low-carbon steel surfaces,where nitrides were introduced from BN isolater between graphite mold and HEA powders.The effect of Ti content on the microstructure,ultimate tensile strength,hardness,and wear resistance of the composites was investigated,and the bonding mechanism was elucidated.Results demonstrate that the composites have excellent hardness and wear resistance.The hardness of composites is significantly increased with the increase in Ti content.The extremely high wear resistance is attributed to the extremely high melting point and high thermal hardness of TiN,which can effectively prevent oxidation deformation of the worn surface.

Molten-salt Synthesis and Properties of ZnS with Hexagonal Prism Morphology

ZnS with hexagonal prism morphology has been synthesized successfully by molten-salt method with ZnS nanoparticles as precursors, and the ZnS nanoparticles were prepared by one-step solid-state reaction of Zn（CH3COO）2·2H2O with Na2S·9H2O at ambient temperature. Crystal structure and morphology of the product were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and HRTEM. Ultraviolet-visible optical absorption spectrum of the ZnS hexagonal prism shows a distinct red shift from that of bulk ZnS crystals and photoluminescence spectrum exhibits strong emissions at 380 and 500 nm, respectively. Further experiments were designed and the formation mechanism of the ZnS hexagonal prism has been also discussed in brief.

Synthesis,formation mechanism,and intrinsic physical properties of several As/P-containing MAX phases

321 phases are an atypical series of MAX phases,in which A=As/P,with superior elastic properties,fea-turing in the MA-triangular-prism bilayers in the crystal structure.Until now,besides Nb 3 As 2 C,the pure phases of the other 321 compounds have not been realized,hampering the study of their intrinsic prop-erties.Here,molten-salt sintering(MSS)and solid-state synthesis(SSS)were applied to synthesize As/P-containing 321 phases and 211 phases.Analyzing the phase composition of the end-product via multiple-phase Rietveld refinement,we found that MSS can effectively improve the purity of P-containing MAX phases,with the phase content up to 99%in Nb_(3)P_(2)C and 75.4(5)%in Nb 2 PC.In contrast,MSS performed poorly on As-containing MAX phases,only 8.9(4)%for Nb 3 As 2 C and 64(2)%for Nb 2 AsC,as opposed to the pure phases obtained by SSS.The experimental analyses combined with first-principles calculations reveal that the dominant formation route of Nb_(3)P_(2)C is through NbP+Nb+C→Nb_(3)P_(2)C.Moreover,we found that the benefits of MSS on P-containing MAX phases are on the facilitation of three consid-ered chemical reaction routes,especially on Nb 2 PC+NbP→Nb_(3)P_(2)C.Furthermore,the intrinsic physical properties and Fermi surface topology of two 321 phases consisting of electron,hole,and open orbits are revealed theoretically and experimentally,in which the electron carriers are dominant in electrical trans-port.The feasible synthesis methods and the formation mechanism are instructive to obtain high-purity As/P-containing MAX phases and explore new MAX phases.Meanwhile,the intrinsic physical properties will give great support for future applications on 321 phases.

Molten-LiCl induced thermochemical prelithiation of SiOx:Regulating the active Si/O ratio for high initial Coulombic efficiency

The low initial Coulombic efficiency(ICE)of SiOx anode caused by the irreversible generation of LiySiOz and Li20 during lithiation process limits its application for high energy-density lithium-ion batteries.Herein,we report a molten-salt-induced thermochemical.prelithiation strategy for regulating the electrochemically active Si/O ratio of SiOx and thus enhancing ICE through thermal treatment of pre-synthesized LiNH2-coated SiOx in molten LiCl at 700℃.Bulk SiOx micro-particle was transformed into pomegranatelike prelithiated micro-cluster composite(M-Li-SiOx)with SiOx core and outer nano-sized agglomerates consisting of Li2Si20s,SiO2,and Si.Through the analysis of the reaction intermediates,molten-UC!could initiate reactions and promote mass transfer by the continuous extraction of oxygen component from SiOx particle inner in the form of inert Li2Si20s and SiO2 nanotubes to realize the.prelithiation.The degree of prelithiation can be regulated by adjusting the coating amount of LiNH2 layer,and the resulted M-Li-SiOx displays a prominent improvement of ICE from 58.73%to 88.2%.The graphite/M-Li-SiOx(8:2)composite electrode delivers a.discharge capacity of 497.29 mAh·g^(-1) with an ICE of 91.79%.By pairing graphite/M-Li-SiOx anode and LiFeP04 cathode in a full-cell an enhancement of energy density of 37.25%is realized compared with the full-cell containing graphite/SiOx anode.Furthermore,,ex-situ X-ray photoelectron spectroscopy(XPS)/Raman/X-ray diffraction(XRD)and related electrochemical measurements reveal the SiOx core and Si of M-Li-SiOx participate in the lithiation,and pre-generated Li2Si20s with u+diffusivity and pomegranate-like.structure reduces the reaction resistance and interface impedance of the solid electrolyte interphase(SEI)film.

Synthesis of crystalline carbon nitride with enhanced photocatalytic NO removal performance:An experimental and DFT theoretical study

The pristine carbon nitride derived from the thermally-induced polymerization of nitrogen-containing precursors(e.g.cyanamide,dicyanamide,melamine and urea)displays low crystallinity because of the predominantly kinetic hindrance.Herein,we reported a modified molten-salts method to fabricate the crystalline carbon nitride under ambient pressure,which is expected to the large-scale production of crystalline carbon nitride.The obtained crystalline carbon nitride displayed about 3.0 times higher photocatalytic NO removal performance than that of pristine carbon nitride under visible light irradiation(λ<400 nm).Detailed experimental characterization and theoretical calculation revealed the crucial roles of crystallinity in crystalline carbon nitride for the enhanced photocatalytic NO removal performance.This research provided deep insights into the crystallinity of carbon nitride for the enhanced photocatalytic performance.