Research progress of alkaline earth metal iron-based oxides as anodes for lithium-ion batteries

Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.

Review of Iron-Based Catalysts for Carbon Dioxide Fischer-Tropsch Synthesis

Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.

A critical review towards the causes of the iron-based catalysts deactivation mechanisms in the selective oxidation of hydrogen sulfide to elemental sulfur from biogas

Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.

Thermodynamics of Modifying Effect of Rare Earth Oxide on Inclusions in Hardfacing Metal of Medium-High Carbon Steel

The modifying effect of rare earth (RE) oxide on inclusions in hardfacing metals of medium-high carbon steel was investigated by means of thermodynamics. The thermodynamic analysis for inclusion formation shows that RE oxide can be reduced to RE element by carbon, then the RE element can react with oxygen and sulfur to form the RE oxide, RE sulfide and RE oxide-sulfide in hardfacing molten pool. The deoxidization and the desulphurization can be carried out and the liquid metal can be purified. In addition, RE oxide can also react with sulfur to form RE oxide-sulfide directly. Therefore, the harmful effect of sulfur can be decreased.

Formation of carbonitride precipitates in hardfacing alloy with niobium addition

Niobium, as the most effective second-phase forming element, was added in the Fe-Crl3-C-N hard- facing alloy to get carbonitride precipitates. Morphology and composition of carbonitride in the hardfacing alloy were studied by optical microscopy, scanning electron microscopy, and electron probe microanalyzer. The ther- modynamics and the effect on the matrix of the formation of carbonitride were also discussed. It was found that niobium carbonitrides are complex Nb（C, N） precipitate distributed on grain boundary and matrix of the hardfacing alloy. Under as-welded condition, primary carbonitride particles were readily precipitated from the hardfacing alloy with large size and morphology as they were formed already during solidification. Under heat treatment condi- tion, a large number of secondary carbonitrides can pre- cipitate out with very fine size and make a great secondary hardening effect on the matrix. As a result, addition of niobium in the hardfacing alloy can prevent the formation of chromium-rich phase on grain boundaries and inter- granular chromium depletion.

Microstructure of Fe-Based Alloy Hardfacing Coating Reinforced by TiC-VC Particles

Mierostrueture of the Fe-based alloy hardfaeing coating reinforced by TiC-VC particles was investigated by means of SEM, TEM, XRD and EPMA. The thermodynamics and effect of elements on the carbides were discussed. The result shows that TiC-VC carbides can be formed during arc welding. Carbides with particle size of 2 ～4μm are uniformly dispersed in the matrix. Evidently the covering components and their amount affect the microstrueture and hardness of the coatings. An excellent microstructure and hardness of hardfacing coating were obtained, while the amount of graphite, FeTi and FeV was controlled within the range of 8%- 10%, 15%- 18% and 8%- 12%, respectively.

Mechanism of Cracking Resistance of Hardfacing Specimens of Steel 5CrNiMo Improved by Rare Earth Oxide

The cracking morphology of the hardfacing specimens taken from steel 5CrNiMo was observed. Meanwhile, the residual stress fields were measured and simulated. Based on experiment mentioned above, the improved structure and modified inclusion in hardfacing metal with rare earth （RE） oxide were analyzed. The results show that, the hardfacing crack is initiated from the coarse dendritic crystal grain boundary, inclusions and coarse austenite grain boundary in the HAZ and propagated by the residual stress existing in the center of the hardfacing metal and HAZ. The primary columnar grain structure can be refined by adding RE oxide in the coating of the electrode. The inclusion in the hardfacing metal can be modified as well. Meanwhile, if the martensite transformation temperature is decreased, the largest value of the residual tensile stress in the dangerous region can be reduced.

Effect of heat treatment on the microstructure and hardness of C-Cr-W-Mo-V-RE Fe-based hardfacing layer

After different heat treatment processes, the metal compound, the microstructure and the hardness of the C-Cr-W- Mo-V-RE Fe-based hardfacing layers are investigated by means of metallographic microscope, X-ray diffraction （ XRD ）, energy dispersive spectrum（ EDS ）, transmission electron microscope（TEM） and hardness tester. The results show that the hardfacing layers have higher tempering stability and secondary hardening property. After quenching at 820 ℃ ,the hardness value（ HRC37 ） and the microstructure of the layers are similar to that normalized at 820 - 1 000 ℃. The tempering stability and the hardness increases with increasing quench temperature, which is attributed to the amount of the alloy element in the matrix. These results are very helpful for improving the mechanical properties of the hardfacing layers.

Effect of molybdenum on the microstructure and wear resistance of hypoeutectic Fe-Cr-B-C hardfacing alloys

Hypoeutectic Fe-Cr-B-C hardfacing alloys with different molybdenum( Mo) contents( The design content was 0,2,3. 3 and 4. 5 wt. %,respectively) were deposited using the flux-cored wire by means of metal active gas arc welding. The effects of Mo on the refinement of microstructures,eutectic microstructure changes and improvement of wear resistance were investigated. The main results were shown as follows: the added Mo could increase the volume fraction of eutectic microstructure and reduce the size of coarse primary austenite as well as the volume fraction. The carboboride of M3( B,C) could be observed in hypoeutectic Fe-Cr-B-C hardfacing alloys at the Mo design content of ≤2. 0 wt. %,while that of M23( B,C)6was formed when 3. 3 wt. % Mo was added.Additionally,the wear resistance of alloys was increased with the increase in Mo content. Specifically,the highest wear resistance of alloys was achieved at 4. 5 wt. % Mo design content,which was 113. 7% higher than that in alloys without Mo.

Microstructure and wear property of hardfacing alloy with nitrogen strengthening

The nitrogen-alloying hardfacing alloy of the martensitic stainless steel was deposited on a low carbon steel substrate using hardfacing flux-cored wire. Microstructure and surface hardness of hardfacing alloy were investigated and measured by optical microscope and microhardness tester. Carbonitrides of the hardfacing alloy were observed by electron probe. The wear behaviour of the hardfacing alloy was studied using the belt abrasion test apparatus and the worn surface was analyzed by scanning electron microscopy. The results showed that carbonitride particles in the hardfacing alloy are complex MX （ M： alloy elements ; X： C, N） precipitate with fine size. These carbonitride particles distributed homogeneously in the hardfacing alloy and had a good strengthening effect on the wear property. The wear property of the hardfacing alloy with nitrogen was better than the one without nitrogen.

Reliability evaluation of hardness test methods of hardfacing coatings with hypoeutectic and hypereutectic microstructures

Hardfacing coatings involve hard carbide/boride phases dispersed in a relatively soft steel matrix.For the hardness measurements of hardfacing coatings,depending on the microstructure,both the hardness test method and the applied load affect the hardness results;therefore,they affect the wear performance predictions of the coating.For this reason,the proper hardness test method should be determined according to the microstructure of the coating,and the reliability of the obtained hardness data should be established.This study aimed to determine the most suitable hardness test method for hypoeutectic and hypereutectic microstructures of hardfacing coatings by analyzing the reliability of Rockwell-C and Vickers hardness test results.Reliability analyses showed that Rockwell-C is not a suitable hardness test method for hypereutectic hardfacing coatings.Based on the relationship between wear resistance and hardness,Vickers hardness method was found more suitable for the considered materials.

Effect of Titanium Content on Microstructure and Wear Resistance of Hardfacing Alloy

The hardfacing alloys with different concentrations of titanium were deposited on carbon steel substrates by shielded metal arc welding, and the effect of titanium content on the microstructure characteristics of the hardfacing alloys was investigated. The wear resistance test of the hardfacing alloys was carried out by using a slurry rubber wheel abrasion test machine, and the wear behaviour was also studied. The results indicate that the addition of titanium can effectively promote the precipitation of the complex carbides of Nb and Ti due to the prior precipitation of titanium carbide which acts as nucleation sites for complex carbides. With the increase of titanium content, the wear resistance of the hardfacing alloys is increased gradually resulting from the refinement of microstructure and dispersive distribution of fine carbide precipitates. And the wear mechanism is mainly minimum plastic deformation with interrupted grooves due to the strengthening and protecting effects of carbide precipitates.

Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

A systematic study was undertaken to investigate the effects of the manganese incorporation manner on the textural properties, bulk and surface phase compositions, reduction/carburization behaviors, and surface basicity of an iron-based Fischer-Tropsch synthesis （FTS） catalyst. The catalyst samples were characterized by N2 physisorption, X-ray photoelectron spectroscopy （XPS）, H2 （or CO） temperature-programmed reduction （TPR）, CO2 temperature-programmed desorption （TPD）, and M5ssbauer spectroscopy. The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor （CSTR）. The characterization results indicated that the manganese promoter incorporated by using the coprecipitation method could improve the dispersion of iron oxide, and decrease the size of the iron oxide crystallite. The manganese incorporated with the impregnation method is enriched on the catalyst＇s surface. The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H2, CO, and syngas because of the excessive enrichment of manganese on the catalyst surface. The catalyst added manganese using the coprecipitation method has the highest CO conversion （51.9%） and the lowest selectivity for heavy hydrocarbons （C12＋）.

Tempering Stability of Fe-Base Hardfacing Layer Containing RE and Multiple Alloying

After tempering treatment at different conditions, the tempering stability of Fe-base hardfacing layer containing RE and multiple alloying was investigated. The results show that after heat preservation at 560 ℃ and tempering for 4 h the hardness value of Fe-base hardfacing layer containing RE and multiple alloying can reach HRC57; By repeatedly heating circle 700 ℃17 ℃ for 150 times, the hardness value of Fe-base hardfacing layer can reach HRC43, tempering stability is higher and causes the secondary hardening phenomenon. Reasons for higher tempering stability of Fe-base hardfacing layer were analyzed by means of metallographic, XRD, TEM and EDS.

New Iron-based SiC Spherical Composite Magnetic Abrasive for Magnetic Abrasive Finishing

SiC magnetic abrasive is used to polish surfaces of precise, complex parts which are hard, brittle and highly corrosion-resistant in magnetic abrasive finishing（MAF）. Various techniques are employed to produce this magnetic abrasive, but few can meet production demands because they are usually time-consuming, complex with high cost, and the magnetic abrasives made by these techniques have irregular shape and low bonding strength that result in low processing efficiency and shorter service life. Therefore, an attempt is made by combining gas atomization and rapid solidification to fabricate a new iron-based SiC spherical composite magnetic abrasive. The experimental system to prepare this new magnetic abrasive is constructed according to the characteristics of gas atomization and rapid solidification process and the performance requirements of magnetic abrasive. The new iron-based SiC spherical composite magnetic abrasive is prepared successfully when the machining parameters and the composition proportion of the raw materials are controlled properly. Its morphology, microstructure, phase composition are characterized by scanning electron microscope（SEM） and X-ray diffraction（XRD） analysis. The MAF tests on plate of mold steel S136 are carried out without grinding lubricant to assess the finishing performance and service life of this new SiC magnetic abrasive. The surface roughness（Ra） of the plate worked is rapidly reduced to 0.051 μm from an initial value of 0.372 μm within 5 min. The MAF test is carried on to find that the service life of this new SiC magnetic abrasive reaches to 155 min. The results indicate that this process presented is feasible to prepare the new SiC magnetic abrasive; and compared with previous magnetic abrasives, the new SiC spherical composite magnetic abrasive has excellent finishing performance, high processing efficiency and longer service life. The presented method to fabricate magnetic abrasive through gas atomization and rapid solidification presented can significantly improve the finishing performance and service life of magnetic abrasive, and provide a more practical approach for large-scale industrial production of magnetic abrasive.

Microstructures and properties of non-preheated hardfacing welding

A new type of non-preheated hardfacing electrode was developed using H08A as the core and the coat contents including ferrotitaninm, ferrovanadium, graphite, rutile etc. The microstrnctures and properties of hardfacing metal were systematically researched. The results show the hardness of hardfacing metal increases with increasing of ferrotitanium, ferrovanadium, graphite in the coat, but the crack resistance and processing weldability become worse. The carbides formed by arc metallurgic reaction are uniformly dispersed in the matrix structure. The phases of hardfacing metal consist of α-Fe, γ-Fe, VC, TiC and Fe3 C.The carbides are compression aggregation of TiC and VC, and their appearances present irregular block. The matrix microstrncture of hardfacing metal is lath martensite. The hardfacing layers with better crack resistance and wearability are achieved and no visible cracks occur when using non-preheated electrode in continuous welding process. Hardness of hardfacing metal is more than 60HRC, and its relative wearability is five times of wearability of D667 electrode in abrasive wear test.

Measurement of Residual Stress Field of Hardfacing Metal with RE Oxide and Its Numerical Simulation

The temperature and residual stress fields of a medium-high carbon steel, welded by a cracking resistance electrode with rare earth (RE) oxide, were measured by thermo-vision analyzer and X-ray stress analyzer respectively. Meanwhile, the martensitic transformation temperatures of matrix, hard-face welding (hardfacing) metal welded by conventional hardfacing electrode and that welded by cracking resistance electrode with RE oxide were determined. According to the experimental data and the thermo-physical, mechanical parameters of materials, finite element method (FEM) of temperature and stress fields was established. In this FEM, the effect of martensitic transformation on residual stress of hardfacing metal of medium-high carbon steel was taken into account. The results show that, by adding RE oxide in the coat of hardfacing electrode, the martensitic transformation temperature can be decreased, so that the residual tensile stress on the dangerous position can be decreased. Therefore, the cracking resistance of hardfacing metal can be improved.

Signal Detection of Carbon in Iron-Based Alloy by Double-Pulse Laser-Induced Breakdown Spectroscopy

Although single-pulse lasers are often used in traditional laser-induced breakdown spectroscopy （LIBS） measurements, their measurement outcomes are generally undesirable because of the low sensitivity of carbon in iron-based alloys. In this article, a double-pulse laser was applied to improve the signal intensity of carbon. Both the inter-pulse delay and the combination of laser wavelengths in double-pulse laser-induced breakdown spectroscopy （DP-LIBS） were optimized in our experiment. At the optimized inter-pulse delay, the combination of a first laser of 532 nm and a second laser of 1,064 nm achieved the highest signal enhancement. The properties of the target also played a role in determining the mass ablation enhancement in DP-LIBS configuration.

Effect of Al_2O_3 Binder on the Precipitated Iron-Based Catalysts for Fischer-Tropsch Synthesis

A series of iron-based Fischer-Tropsch synthesis （FTS） catalysts incorporated with Al2O3 binder were prepared by the combination of co-precipitation and spray drying technology. The catalyst samples were characterized by using N2 physical adsorption, temperature-programmed reduction/desorption （TPR/TPD） and MSssbauer effect spectroscopy （MES） methods. The characterization results indicated that the BET surface area increases with increasing Al2O3 content and passes through a maximum at the Al2O3/Fe ratio of 10/100 （weight basis）. After the point, it decreases with further increase in Al2O3 content. The incorporation of Al2O3 binder was found to weaken the surface basicity and suppress the reduction and carburization of iron-based catalysts probably due to the strong K-Al2O3 and Fe-Al2O3 interactions. Furthermore, the H2 adsorption ability of the catalysts is enhanced with increasing Al2O3 content. The FTS performances of the catalysts were tested in a slurry-phase continuously stirred tank reactor （CSTR） under the reaction conditions of 260 ℃, 1.5 MPa, 1000 h^-1 and molar ratio of H2/CO 0.67 for 200 h. The results showed that the addition of small amounts of Al2O3 affects the activity of iron-based catalysts to a little extent. However, with further increase of Al2O3 content, the FTS activity and water gas shift reaction （WGS） activity are decreased severely. The addition of appropriate Al2O3 do not affect the product selectivity, but the catalysts incorporated with large amounts of Al2O3 have higher selectivity for light hydrocarbons and lower selectivity for heavy hydrocarbons.

Crystal chemistry and structural design of iron-based superconductors

The second class of high-temperature superconductors （HTSCs）, iron-based pnictides and chalcogenides, necessarily contain Fe2X2 （＂X＂ refers to a pnictogen or a chalcogen element） layers, just like the first class of HTSCs which possess the essential CuO2 sheets. So far, dozens of iron-based HTSCs, classified into nine groups, have been discovered. In this article, the crystal-chemistry aspects of the known iron-based superconductors are reviewed and summarized by employing ＂hard and soft acids and bases （HSAB）＂ concept. Based on these understandings, we propose an alternative route to exploring new iron-based superconductors via rational structural design.