Lithium intercalation mechanism for β-SnSb in Sn-Sb thin films

Based on the first-principles plane wave pseudo-potential method, the electronic structure and electrochemical performance of LixSn4Sb4 (x=2, 4, 6, and 8) and LixSn12-xSb4 (x=9, 10, 11, and 12) phases were calculated. A Sn-Sb thin film on a Cu foil was also prepared by radio frequency magnetron sputtering. The surface morphology, composition, and lithium intercalation/extraction behavior of the fabricated film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). Lithium atoms can easily insert into and extract out of the β-SnSb cell due to the low lithium intercalation formation energy. It is found that lithium atoms first occupy the interstitial sites, and then Sn atoms at the lattice positions are replaced by excessive lithium. The dissociative Sn atoms continue to produce different Li-Sn phases, which will affect the electrode stability and lead to the undesirable effect due to their large volume expansion ratio. The calculated lithium intercalation potential is stable at about 0.7 V, which is consistent with the experimental result.     

Solid state interfacial reactions in electrodeposited Ni/Sn couples

Ni/Sn couples, prepared by sequentially electroplating Ni layers and Sn layers on metallized Si wafers, were employed to study the microstructures and growth kinetics of Ni-Sn intermediate phases, when the Ni/Sn couples were aged at room temperature or annealed at temperatures from 150 to 225℃ for various times. The results show that the NiSn phase and Ni₃Sn₄ phase are formed, respectively, in the aged couples and annealed couples. The Ni₃Sn₄ layer is continuously distributed between the Ni and Sn sides in the annealed Ni/Sn couples. The Ni₃Sn₄ growth follows parabolic growth kinetics with an apparent activation energy of 39.0 kJ/mol.     

Electrochemical Studies of Lithium Intercalation into Graphite Film Electrode for Li+-ion Batteries

To study the electrochemical kinetic properties of the Li/Graphite system, cycle voltammerty (CV), ac-impedance and chronoamperometry (CA) techniques have been used. The results showed that the diffusion of lithium ions in Li_xC₆ is the rate-determining step. The chemical diffusion coefficients of lithium (D_Li) have been estimated for different x values. As for the same material, the value of D_Li was calculated in order to compare the differences among the three techniques.     

Effect of Ag and Ni on the melting point and solderability of SnSbCu solder alloys

To improve the properties of Sn10Sb8Cu solder alloy, two new solders (SnSbCuAg and SnSbCuNi) were formed by adding small amounts of Ag or Ni into the solder alloy. The results show that the melting point of the SnSbCuAg solder alloy decreases by 14.1℃ and the spreading area increases by 16.5% compared to the matrix solder. The melting point of the SnSbCuNi solder alloy decreases by 5.4℃ and the spreading area is slightly less than that of the matrix solder. Microstructure analysis shows that adding trace Ag makes the melting point decline due to the dispersed distribution of SnAg phase with low melting point. Adding trace Ni, Cu₆Sn₅ and (Cu, Ni)₆Sn₅ with polyhedron shape on the copper substrate can be easily seen in the SnSbCuNi solder alloy, which makes the viscosity of the melting solder increase and the spreading property of the solder decline.     

Adhesion of NiCu Films DC Biased Plasma-Sputter-Deposited on MgO (001)

NiCu films about 60nm thick were deposited on MgO (001) substrates at 230℃ by DC plasma-sputtering at 2.7kV and 8mA in pure Ar gas using a Ni₉₀Cu₁₀ target. A DC bias voltage U_s of 0, 60, 110 or 140V was applied to the substrate during deposition. The adhesion of the film to the substrate was studied using a scratch test as a function of U_s. The application of U_s is very effective in increasing the adhesion of the film to the substrate. In conclusion, the adhesion increases with cleaning the substrate surface by sputtering off impurity admolecules during the film initial formation due to the energetic Ar ion particle bombardment.     

9Cr?5Si?3Al铁素体耐热钢的高温氧化行为

To improve the oxidation properties of ferritic heat-resistant steels, an Al-bearing 9Cr?5Si?3Al ferritic heat-resistant steel was designed. We then conducted cyclic oxidation tests to investigate the high-temperature oxidation behavior of 9Cr?5Si and 9Cr?5Si?3Al ferritic heat-resistant steels at 900 and 1000°C. The characteristics of the oxide layer were analyzed by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The results show that the oxidation kinetics curves of the two tested steels follow the parabolic law, with the parabolic rate constant k_p of 9Cr?5Si?3Al steel being much lower than that of 9Cr?5Si steel at both 900 and 1000°C. The oxide film on the surface of the 9Cr?5Si alloy exhibits Cr₂MnO₄ and Cr₂O₃ phases in the outer layer after oxidation at 900 and 1000°C. However, at oxidation temperatures of 900 and 1000°C, the oxide film of the 9Cr?5Si?3Al alloy consists only of Al₂O₃ and its oxide layer is thinner than that of the 9Cr?5Si alloy. These results indicate that the addition of Al to the 9Cr?5Si steel can improve its high-temperature oxidation resistance, which can be attributed to the formation of a continuous and compact Al₂O₃ film on the surface of the steel.     

Thermoelectric properties of p-type (Bi0.15Sb0.85)2Te3-PbTe graded thermoelectric materials with different barriers

The p-type (Bi_0.15Sb_0.85)₂Te₃ and PbTe are typical thermoelectric materials used for low and middle temperature range and functional graded materials (FGM) is an inevitable way to widen the working temperature range. Here two segments graded thermoelectric materials (GTM) consisting of (Bi_0.15Sb_0.85)₂Te₃, PbTe and different barriers were fabricated by the common hot pressure method. Metals Fe, Mg and Ni were used as barriers between the two segments. The diffusion of different barriers between the barriers and bases were analyzed by electron microprobe analysis (EMA). The phase and crystal structures were determined by X-ray diffraction analysis (XRD). The thermoelectric properties were measured at 303 K along the direction parallel to the pressing direction. The results show that the compositional diffusion occurs when there is no barrier at the interface of the two segments, and the diffusion of Pb is most obvious; as the barrier material, the diffusion of metals Fe, Mg and Ni between different bases is not very obvious, and the thermoelectric properties of GTM is much better than that of the original segment.     

A designed core-shell structural composite of lithium terephthalate coating on Li4Ti5O12 as anode for lithium ion batteries

A core-shell structural composite was synthesized with lithium terephthalate（Li₂C₈H₄O₄） coated on spinel Li₄Ti₅O₁₂（LTO）. The composite displays a capacity of about 200 mA h g^-1 and a good rate capability with two charge/discharge platforms at 1.55 and 0.8 V. The excellent cycling performance of the composite is attributed to the successful combination of high cycling stability of LTO and high specific capacity of Li₂C₈H₄O₄. In addition, an interesting phenomena is observed for the first time for this composite which is that lithium ions transfer between LTO and Li₂C₈H₄O₄ at a fast speed. This is investigated in details via the asymmetric charge/discharge measurement and cyclic voltammogram（CV）.The LTO/Li₂C₈H₄O₄ composite may have potential applications to be used as an anode material for the electric vehicle batteries, which is shallowly charged/discharged at ordinary times using the charge/discharge platform of LTO and fully charged/discharged at emergency to release the extra high capacity from Li₂C₈H₄O₄.     

CALCULATING MODEL OF MASS ACTION CONCENTRATIONS FOR Cd-Sb ALLOY MELT

According to the Cd-Sb alloy phase diagram, resistivity, heat capacity, partial molar entropy and viscosity,the structural units of this alloy melt have been determined as Cd and Sb atoms as well as Cd₃Sb₂, Cd₄Sb₃ and CdSb compounds.Based on these structural units and the coexistence theory of metallic melt structure involing compound formation,a calculating model of mass action concentrations has been deduced.The calculated mass action concentrations N_Cd are in good agreement with measured activities a_Cd. The Gibbs standard free energy of formatioin for above three compunds have been obtained too.     

CaCO<Subscript>3</Subscript> film synthesis from ladle furnace slag: morphological change,new material properties,and Ca extraction efficiency

A rapidly air-cooled ladle furnace slag (RA-LFS), which is a type of steelmaking slag discharged from a steel mill, was used to synthesize CaCO₃ film. The CaCO₃ film with 35 cm2 of surface area was synthesized under atmospheric conditions, and the surface morphology of the CaCO₃ films was changed by using additives (CaCl₂ and ethylene glycol). Especially, the addition of CaCl₂ changed the surface morphology of CaCO₃ film with pore and induced new material properties, such as water adsorption. The (012) face of CaCO₃ film (calcite) was rapidly decreased by the addition of CaCl₂. The major components of RA-LFS were calcium (type of CaO, 53.9wt%) and aluminum (type of Al₂O₃, 37.9wt%), and the major crystal phases of RA-LFS were C₃S, C₁₂A₇, and C₃A. The calcium extraction efficiency of RA-LFS was significantly increased after the CaCO₃ film synthesis. The material properties (hardness and elastic modulus) and the thermal characteristics of the CaCO₃ films were analyzed by nano-indentation and thermogravimetry-differential thermal analysis. The synthesized CaCO₃ films from RA-LFS and Ca(OH)₂ (reagent) showed similarities in terms of their material properties and the decomposition temperature.     

Microstructure and mechanical properties of twin-wire arc sprayed Ni-Al composite coatings on 6061-T6 aluminum alloy sheet

We have systematically studied the microstructure and mechanical properties of Ni-5wt%Al and Ni-20wt%Al composite coatings fabricated on 6061-T6 aluminum alloy sheet by twin-wire arc spraying under different experimental conditions. The abrasive wear behavior and interface diffusion behavior of the composite coatings were evaluated by dry/wet rubber wheel abrasive wear tests and heat treatment, respectively. Experimental results indicate that the composite coatings exhibit features of adhesive wear. Besides, the Vickers microhardness of NiAl and Ni₃Al intermetallic compounds is relatively larger than that of the substrate, which is beneficial for enhancing the wear resistance. With the increase of annealing temperature and time, the interface diffusion area between the Ni-Al coating and the substrate gradually expands with the formation of NiAl₃ and Ni₂Al₃ phases, and is controlled by diffusion of aluminum atoms. The grain growth exponent n of diffusion kinetics of the Ni-Al coating, calculated via a high-temperature diffusion model at 400, 480, and 550℃, is between 0.28 and 0.38. This satisfies the cubic law, which is consistent with the general theoretical relationship of high-temperature diffusion.     

Intergranular corrosion behavior of high nitrogen austenitic stainless steel

The intergranular corrosion (IGC) behavior of high nitrogen austenitic stainless steel (HNSS) sensitization treated at 650-950℃ was investigated by the double loop electrochemical potentiodynamic reactivation (DL-EPR) method. The effects of the electrolytes, scan rate, sensitizing temperature on the susceptibility to IGC of HNSS were examined. The results show that the addi-tion of NaCl is an effective way to improve the formation of the cracking of a passive film in chromium-depleted zones during the reactivation scan. Decreasing the scan rate exhibits an obvious effect on the breakdown of the passive film. A solution with 2 mol/L H₂SO₄+1 mol/L NaCl+0.01 mol/L KSCN is suitable to check the susceptibility to IGC of HNSS at a sensitizing temperature of 650-950℃ at a suitable scan rate of 1.667 mV/s. Chromium depletion of HNSS is attributed to the precipitation of Cr₂N which results in the susceptibility to IGC. The synergistic effect of Mo and N is suggested to play an important role in stabilizing the passive film to prevent the attack of IGC.     

Passivity breakdown of 13Cr stainless steel under high chloride and CO2 environment

Herein, the effect of high chloride ion (Cl-) concentration on the corrosion behavior and passive film breakdown of 13Cr martensitic stainless steel under CO₂ environment was demonstrated. The Cl- concentration was varied from 30 to 150 g/L and cyclic potentiodynamic polarization was conducted to investigate the influence of the Cl- concentration on the corrosion potential (E_corr), passive breakdown potential (E_pit), and repassivation potential (E_rep). The results of the polarization curves revealed that 13Cr stainless steel is susceptible to pitting under high Cl- concentration. The passive breakdown potential and repassivation potential decreased with the increase of Cl- concentration. The semiconducting behavior of the passive film was investigated by Mott-Schottky analysis and the point defect model (PDM). It was observed that the iron cation vacancies and oxygen vacancies were continuously generated by autocatalytic reactions and the higher Cl- concentration resulted in higher vacancies in the passive film. Once the excess vacancies condensed at the metal/film interface, the passive film became locally detached from the metal, which led to the breakdown of the passive film.     

<Emphasis Type="Italic">Ab initio</Emphasis> study of the effects of Ag/Mn doping on the electronic structure of LiFePO<Subscript>4</Subscript>

Based on density functional theory （DFT） of the first-principle for the cathode materials of lithium ion battery, the electronic structures of Li（Fe1-x）PO4 （Me = Ag/Mn, x = 0-0.40） are calculated by plane wave pseudo-potential method using Cambridge serial total energy package （CASTEP） program. The calculated results show that the Fermi level of mixed atoms Fe1-xAgx moves into its conduction bands （CBs） due to the Ag doping. The Li（Fe1-xAgx）PO4 system displays the periodic direct semiconductor characteristic with the increase of Ag-doped concentration. However, for Fe1-xMnx mixed atoms, the Fermi level is pined at the bottom of conduction bands （CBs）, which is ascribed to the interaction between Mn（3d） electrons and Fe（4s） electrons. The intensity of the partial density of states （PDOS） near the bottom of CBs becomes stronger with the increase of Mn-doped concentration. The Fermi energy of the Li（Fe1-xMnx）PO4 reaches maximum at x = 0.25, which is consistent with the experimental value of x = 0.20. The whole conduction property of Mn-doped LiFePO4 is superior to that of Ag-doped LiFePO4 cathode material, but the structural stability is reverse.     

Microstructures of spinodal phases in Cu-15Ni-8Sn alloy

The microstructures of spinodal phases in Cu-15Ni-8Sn alloy were studied by TEM. It was found that when the alloy is completely in a as-quenched state, spinodal decomposition is quick. Ordering appears after spinodal decomposition. The ordered phase with DO₂₂ structure has three variants obtained from coarsening spinodal structure. The reason of ordering appeared after spinodal decomposition is that the content of solute atoms needed by ordering is higher than the average, which can be reached by the composition fluctuation of spinodal decomposition. It was speculated that the morphology of the ordered phase is needle-like.     

Preparation of Al-Cu-Fe-(Sn,Si) quasicrystalline bulks by laser multilayer cladding

(Al₆₅Cul₂₀Fe₁₅)_100-x Sn_x (x=0, 12, 20, 30) and Al₅₇Si₁₀Cu₁₈Fe₁₅ powders were cladded on a medium carbon steel (45# steel) substrate by laser multilayer cladding, respectively. The phases and properties of the produced quasicrystalline bulks were investigated. It was found that the main phases in the Al₆₅Cul₂₀Fe₁₅ sample were crystalline λ-Al₁₃Fe₄ and icosahedral quasicrystal together with a small volume fraction of θ-Al₂Cu phase. The volume fraction of icosahedral phase decreased as the Sn content in the (Al₆₅Cul₂₀Fe₁₅)_100-x Sn_x samples increased owing to the formation of β-CuSn phase. The increase of Sn content improved the brittleness of the quasicrystal samples. The morphology of the solidification microstructure in the Al₅₇Si₁₀Cu₁₈Fe₁₅ sample changed from elongated shape to spherical shape due to the addition of Si. The nanohardness of the laser multilayer cladded quasicrystal samples was equal to that of the as-cast sample prepared by vacuum quenching. In terms of hardness, the laser cladded Al₅₇Si₁₀Cu₁₈Fe₁₅ quasicrystalline alloy has the highest value among all the investigated samples.     

Electromigration in eutectic SnAg solder reaction couples with various ambient temperatures and current densities

The electromigration behavior of eutectic SnAg solder reaction couples was studied at various temperature (25 and 120℃ when the current density was held constant at 104 A/cm2 or 5×103 A/cm2. Under the current density of 104 A/cm2, scallop type Cu₆Sn₅ spalls and migrates towards the direction of electron flow at room ambient temperature (25℃), but transforms to layer type Cu₃Sn and leaves Kirkendall voids in it at high ambient temperature (120℃). Under the current density of 5×103 A/cm2 plus room ambient temperature, no obvious directional migration of metal atoms/ions is found. Instead, the thermal stress induced by mismatch of dissimilar materials causes the formation of superficial valley at both interfaces. However, when the ambient temperature increases to 120℃, the mobility of metal atoms/ions is enhanced, and then the grains rotate due to the anisotropic property of β-Sn.     

Influence of structure and atom sites on Sn-based anode materials for lithium ion batteries: a first-principle study

To understand the influence of structure and atom sites on the electrochemical properties of Sn-based anode materials,the lithium intercalation–deintercalation mechanisms into SnNi2Cu and SnNiCu2phases were studied using the first-principle plane wave pseudo-potential method.Calculation results showed that both SnNi2Cu and SnNiCu2were unsuitable anode materials for lithium ion batteries.The Sn-based anode structure related to the number of interstitial sites,theoretical specific capacity,and volume expansion ratio.Different atom sites led to different forces at interstitial sites,resulting in variations in formation energy,density of states,and hybrid orbital types.In order to validate the calculated model,the SnNi2Cu alloy anode material was synthesized through a chemical reduction-codeposition approach.Experimental results proved that the theoretical design was reasonable.Consequently,when selecting Snbased alloy anodes,attention should be paid to maximizing the number of interstitial sites and distributing atoms reasonably to minimize forces at these sites and facilitate the intercalation and deintercalation of lithium ion.     

Ab initio study of the effects of Ag/Mn doping on the electronic structure of LiFePO_4

Based on density functional theory (DFT) of the first-principle for the cathode materials of lithium ion battery, the electronic structures of Li(Fe1-xMex)PO4 (Me = Ag/Mn, x = 0―0.40) are calculated by plane wave pseudo-potential method using Cambridge serial total energy package (CASTEP) program. The calculated results show that the Fermi level of mixed atoms Fe1-xAgx moves into its conduction bands (CBs) due to the Ag doping. The Li(Fe1-xAgx)PO4 system displays the periodic direct semiconductor characteristic with the increase of Ag-doped concentration. However, for Fe1-xMnx mixed atoms, the Fermi level is pined at the bottom of conduction bands (CBs), which is ascribed to the interaction be-tween Mn(3d) electrons and Fe(4s) electrons. The intensity of the partial density of states (PDOS) near the bottom of CBs becomes stronger with the increase of Mn-doped concentration. The Fermi energy of the Li(Fe1-xMnx)PO4 reaches maximum at x = 0.25, which is consistent with the experimental value of x = 0.20. The whole conduction property of Mn-doped LiFePO4 is superior to that of Ag-doped LiFePO4 cathode material, but the structural stability is reverse.     

Staged reaction kinetics and characteristics of iron oxide direct reduction by carbon

Staged reduction kinetics and characteristics of iron oxide direct reduction by carbon were studied in this work. The characteristics were investigated by simultaneous thermogravimetric analysis, X-ray diffraction (XRD), and quadrupole mass spectrometry. The kinetics parameters of the reduction stages were obtained by isoconversional (model-free) methods. Three stages in the reduction are Fe₂O₃→Fe₃O₄, Fe₃O₄→FeO, and FeO→Fe, which start at 912 K, 1255 K, and 1397 K, respectively. The CO content in the evolved gas is lower than the CO₂ content in the Fe₂O₃→Fe₃O₄ stage but is substantially greater than the CO₂ contents in the Fe₃O₄→FeO and FeO→Fe stages, where gasification starts at approximately 1205 K. The activation energy (E) of the three stages are 126–309 kJ/mol, 628 kJ/mol, and 648 kJ/mol, respectively. The restrictive step of the total reduction is FeO→Fe. If the rate of the total reduction is to be improved, the rate of the FeO→Fe reduction should be improved first. The activation energy of the first stage is much lower than those of the latter two stages because of carbon gasification. Carbon gasification and Fe_xO_y reduction by CO, which are the restrictive step in the last two stages, require further study.