Influence of substituting Ni with Co on hydriding and dehydriding kinetics of melt spun nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1−x Co _x (x=0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg₂Ni but results in the formation of secondary phase MgCo₂. No amorphous phase is detected in the as-spun Co-free alloy, but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However, it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4, the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy, and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).     

Gaseous and electrochemical hydrogen storage kinetics of as-quenched nanocrystalline and amorphous Mg2Ni-type alloys

The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1?x Co _x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo₂ and Mg instead of altering the major phase Mg₂Ni. No amorphous phase is detected in the as-quenched Cofree alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient (D) along with the limiting current density (I _L ) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.     

Effect of melt spinning on gaseous hydrogen storage characteristics of nanocrystalline and amorphous Nd-added Mg_2Ni-type alloys

Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous hydrogen storage characteristics were investigated. The XRD, TEM and SEM linked with EDS detections reveal that the as-spun Nd-free alloy holds an entire nanocrystalline structure but a nanocrystalline and amorphous structure for the as-spun Nd-added alloy, implying that the addition of Nd facilitates the glass forming in the Mg_2Ni-type alloy. Furthermore, the degree of amorphization of the as-spun Nd-added alloy and thermal stability of the amorphous structure clearly increase with the spinning rate rising. The melt spinning ameliorates the hydriding and dehydriding kinetics of the alloys dramatically. Specially, the rising of the spinning rate from 0(the as-cast was defined as the spinning rate of 0 m/s) to 40 m/s brings on the hydrogen absorption saturation ratio(R_5~a)(a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increasing from 36.9% to 91.5% and the hydrogen desorption ratio(R_(1 0)~d)(a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) rising from 16.4% to 47.7% for the(x=10) alloy, respectively.     

Corrosion Behavior of Mg65Cu25-xZnxGd10 （x=0, 5）Metallic Glass

The effect of substitutional element Zn on corrosion behavior of Mg65Cu25Gd10 glass was investigated. The amorphous structure of Mg65Cu25-xZnxGd10 （x=0,5） alloys were examined by X-ray diffractometry and differential scanning calorimetry （DSC）. The dissolution rates of Mg65Cu25-xZnxGd10 （x=0, 5） metallic glasses in a 5 wt% NaCl solution with pH value of 7 were determined by a hydrogen evolution testing method. The corrosion behavior of these alloys was characterized using dipping tests with 5 wt% NaCl, in combination with electrochemical measurements and scanning electron microscopy （SEM）. Results show that the anti-corrosion ability of Mg65Cu25Gd10 alloy is significantly improved due to the addition of Zn. Possible mechanism responsible for the improvement is discussed.     

Structures and Electrochemical Performances of As-spun RE-Mg-Ni-Mn-based Alloys Applied to Ni-MH Battery

The La-Mg-Ni-Mn-based AB₂-type La_1-xCe_xMgNi_3.5Mn_0.5 (x = 0, 0.1, 0.2, 0.3, and 0.4) alloys were fabricated by melt spinning technology. The effects of Ce content on the structures and electrochemical hydrogen storage performances of the alloys were studied systematically. The XRD and SEM analyses proved that the experimental alloys consist of a major phase LaMgNi₄ and a secondary phase LaNi₅. The variation of Ce content causes an obvious change in the phase abundance of the alloys without changing the phase composition. Namely, with the increase of Ce content, the LaMgNi₄ phase augments and the LaNi₅ phase declines. The lattice constants and cell volumes of the alloys clearly shrink with increasing Ce content. Moreover, the Ce substitution for La results in the grains of the alloys clearly refined. The electrochemical tests showed that the substitution of Ce for La obviously improves the cycle stability of the as-spun alloys. The analyses on the capacity degradation mechanism demonstrate that the improvement can be attributed to the ameliorated anti-corrosion and anti-oxidation ability originating from substituting partial La with Ce. The as-spun alloys exhibit excellent activation capability, reaching the maximum discharge capacities just at the first cycling without any activation treatment. The substitution of Ce for La evidently improves the discharge potential characteristics of the as-spun alloys. The discharge capacity of the alloys first increases and then decreases with growing Ce content. Furthermore, a similar trend also exists in the electrochemical kinetics of the alloys, including the high rate discharge ability (HRD), hydrogen diffusion coefficient (D), limiting current density (I_L) and charge transfer rate.     

Synthesis and electrochemical performance of TiO2-B as anode material

TiO₂-B was synthesized by solid-state reaction. The structures, surface morphologies and electrochemical performances of TiO₂-B were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and electrochemical measurement, respectively. The effects of calcining temperature, molar ratio of K₂O to TiO₂ and calcining time on the characteristics of TiO₂-B were investigated. The results show that the calcining time exerts a significant influence on the electrochemical performances of TiO₂-B. The TiO₂-B is obtained with good crystal structure and suitable size by using K₂Ti₄O₉, which is prepared at 950°C for 24 h under the condition of x(K₂O)/x(TiO₂)=1:3.5. The TiO₂-B delivers all initial discharge capacity of 231.6 mA·h/g. And the rate capacity is 73.2 mA·h/g at 1 675 mA/g, which suggests that TiO₂-B is a promising anode material for the lithium ion batteries.     

Electrochemical performance of LiFePO4/（C＋Fe2P） composite cathode material synthesized by sol-gel method

A LiFePO4/(C+Fe2P) composite cathode material was prepared by a sol-gel method using Fe(NO3)3·9H2O,LiAc·H2O,NH4H2PO4 and citric acid as raw materials,and the physical properties and electrochemical performance of the composite cathode material were investigated by X-ray diffractometry(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM) and electrochemical tests.The Fe2P content,morphology and electrochemical performance of LiFePO4/(C+Fe2P) composite depend on the calcination tempera...     

Influence of Temperature on Electrochemical Performances of Rare Earth Based Hydrogen Storage Material

1 IntroductionRare earth-based hydrogenstorage alloys ofAB5typehave beenthe most major electrode material for small-sizeNi/MHbatteries because of their high discharge capacity,superior highrate capability andfavorable ratio of pricetoperformance. But their electrochemical performances be-come worse when the alloys are applied to large-size Ni/MHbatteries of electric vehicles .Thisfact may be due tothe rising of temperature inside the large batteries causedbythe high electric current of char…     

Preparation and mechanical behavior of Mg-based bulk metallic glasses and their matrix composite

Mg87-xCuxDy13(x=22,27,32) bulk metallic glasses (BGMs) with a diameter of 6-8 mm and in-situ Mg phase reinforced Mg70Cu17Dy13 BMG matrix composite with a diameter of 3 mm have been prepared by copper mould casting. The glass forming ability (GFA) of Mg-Cu-Dy alloys have been investigated by differential scanning calorimetry (DSC) and X-Ray diffraction (XRD) and tne mechanical properties have been measured. Results show that Mg87-xCuxDy13(x=22,27,32) alloys in the Mg-Cu-Dy alloy system exhibit excellent GFA, and Mg60Cu27Dy13 alloy has the largest GFA among these alloys. And In-situ Mg phase reinforced Mg70Cu17Dy13 BMG matrix composite exhibits some work hardening and a high fracture compressive strength of 702.38 MPa and some plastic strain of 0.81%. The improvement of the mechanical properties is attributed to the fact that the Mg phase distributed in the amorphous matrix of the alloy has some effective load bearing and plastic deformation ability to restrict the expanding of shear bands and cracks and produce its own plastic deformation.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Nanostructure and formation mechanism of Pt-WO<Subscript>3</Subscript>/C nanocatalyst by ethylene glycol method

Pt-WO3 nanoparticles uniformly dispersed on Vulcan XC-72R carbon black were prepared by an ethylene glycol method.The morphology,composition,nanostructure,electrochemical characteristics and electrocatalytic activity were characterized,and the formation mechanism was investigated.The average particle size was 2.3 nm,the same as that of Pt/C catalyst.The W/Pt atomic ratio was 1/20,much lower than the design of 1/3.The deposition of WO3·xH2O nanoparticles on Vulcan XC-72R carbon black was found to be very difficult by TEM.From XPS and XRD,the Pt nanoparticles were formed in the colloidal solution of Na2WO4,the EG insoluble Na2WO4 resulted in the decreased relative crystallinity and increased crystalline lattice constant compared with those of Pt/C catalyst and,subsequently,the higher specific electrocatalytic activity as determined by CV.The Pt-mass and Pt-electrochemically-active-specific-surface-area based anodic peak current densities for ethanol oxidation were 422.2 mA·mg-1Pt and 0.43 mA·cm-2Pt,1.2 and 1.1 times higher than those of Pt/C catalyst,respectively.     

NaCl 溶液中回收AZ31 镁合金的腐蚀和电化学特性

利用熔炼工艺,将回收镁合金型材(RMA)进行了制备。在回收过程中,添加适量的Al、MnCl_2,最终得到合金AZ31,其中各元素质量分数如下:Al 3.31%、Zn 0.82%、Mn 0.27%、Fe 0.002%、Cu 0.004%、Ni 0.000 7%,剩余为Mg。研究了RMA的结构、在NaCl溶液中的腐蚀和电化学特性,并与商业化镁合金(CMA)进行了对比。X射线衍射仪和金相显微镜表明, RMA和CMA主要由镁基底组成,另外还有少量的Mg_(17)Al_(12)第二相。在NaCl溶液中进行的腐蚀试验和电化学特性研究表明, RMA抗腐蚀特性差于CMA,这可能与RMA中有更多的第二相有关。将两种合金作为镁电池原型器件的负极材料,进行放电性能测试。结果表明, RMA的放电时间和放电容量优于CMA。当NaCl电解质溶液浓度从0.6 mol/L增加至0.9 mol/L时,两种合金材料的放电时间和放电容量都得到了增加。     

Crystallization of amorphous Ni-Zr alloys during heating with molecular dynamics simulations

The heating processes of amorphous Ni_xZr_100-x(x=10, 16.7, 33.3) alloys were investigated with molecular dynamics simulations. The simulation results show that the crystallization of amorphous alloys during heating is controlled by the heating rate and the alloy's composition. The slower heating rate depresses the crystallizing temperatures and the melting temperatures of the amorphous alloys. Crystallization can be eliminated at rapid heating rates, the critical value of which decreases with increasing Ni content of the studied amorphous Ni-Zr alloys. Different crystalline structures formed during crystallizing depend on the heating rate, and the transition between crystalline structures was observed in the heating processes.     

Structural evolution and stability of mechanically alloyed Fe-Ni nanocrystalline

The structural evolution and stability of Fe100-xNix(x=10, 20, 35, 50) alloys prepared by mechanical alloying were investigated through X-ray diffraction analysis and transmission electron microscopy. The intrinsic conditions of preparation determining phase stability in nanocrystalline were clarified. After being milled for 120 h, the powders of Fe90Ni10 and Fe80Ni20 consist of a single α(bcc) phase, Fe30Ni30 powders are a single γ(fcc), and for Fe65Ni35 powders there is co-existence of α and γ phases. The as-milled Fe80Ni20 powders annealed at 680 ℃ exhibits the stability of high-temperature γ phase at room temperature, which is consistent with the theoretical prediction.     

C-ZIF-8基PtNi催化剂制备及其甲醇电催化氧化性能

制备具有高活性和稳定性的铂基催化剂材料对于直接甲醇燃料电池(direct methanol fuel cells,DMFCs)的商业化进程具有显著的意义。以沸石咪唑骨架(zeolite imidazole framework,ZIF-8)为前驱体,通过高温碳化制备出一种优异的金属有机框架(metal organic frameworks,MOFs)衍生的碳材料作为载体,同时引入过渡金属Ni得到一种新型双金属催化剂Pt_xNi_10-x/C-ZIF-8。采用XRD、BET、FT-IR、Raman、SEM和TEM等方法表征Pt_x Ni_10-x/C-ZIF-8复合材料的形貌、组成和表面结构等,并通过循环伏安法,计时电流法(i-t)等电化学方法对Pt_x Ni_10-x/C-ZIF-8复合材料的电催化性能进行测试。研究结果表明,在1 mol/L KOH+1 mol/L CH₃OH溶液中,Pt₈Ni₂/C-Z...     

Structure and migration characteristic of heterointerfaces during the phase transformation from L1<Subscript>2</Subscript> to DO<Subscript>22</Subscript> phase

Based on the microscopic phase-field model, the structure and migration characteristic of ordered domain interfaces formed between DO₂₂ and L1₂ phase are investigated, and the atomistic mechanism of phase transformation from L1₂ (Ni₃Al) to DO₂₂ (Ni₃V) in Ni₇₅Al _x V_25−x alloys are explored, using the simulated microstructure evolution pictures and the occupation probability evolution of alloy elements at the interface. The results show that five kinds of heterointerfaces are formed between DO₂₂ and L1₂ phase and four of them can migrate during the phase transformation from L1₂ to DO₂₂ except the interface (002)_D//(001)_L. The structure of interface (100)_D//(200)_L and interface (100)_D//(200)_L·1/2[001] remain the same before and after migration, while the interface (002)_D//(002)_L is formed after the migration of interface (002)_D//(002)_L·1/2[100] and vice versa. These two kinds of interface appear alternatively. The jump and substitute of atoms selects the optimization way to induce the migration of interface during the phase transformation, and the number of atoms needing to jump during the migration is the least among all of the possible atom jump modes.     

锂离子电池负极材料多孔硅/硅铁合金的制备及性能

为改善锂离子电池硅负极材料的电化学性能,利用镁热还原法制备了不同铁掺杂量的多孔硅/硅铁合金复合材料,并对其结构以及在锂离子电池中的充放电性能进行了研究.材料均呈现多孔结构,硅铁合金均匀分布在孔道内部.多孔硅/硅铁合金复合材料具有较好的循环稳定性,在0.1C倍率下循环100圈后可逆容量为1 133.5 m A·h/g,容量保持率为66%;在1C倍率下可逆容量仍可以达到776.9 m A·h/g.     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg<Subscript>12</Subscript>-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg₁₂-type LaMg₁₁Ni + x wt% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter (DSC) connected with a H₂ detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability (HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.     

Simulation of the precipitation process of Ni75AixV25-x alloys incorporated in the microelasticity field

The microelasticity field was incorporated into the microscopic phase-field equation for the ternary alloy systems, the morphology evolution and coarsening behavior of the Ni75AixV25-x alloy were simulated. The γ phase precipitates initially for Ni75Al7aV17.9 and Ni75Al5.5V19.5 alloys and the two phases transform from the equiaxed or strip-like to the quadrate as the growth and coarsening processes. For the anisotropic elasticity interaction of the system, the orientation of γ is along the 〈001〉 directions and the θ phase is along the short axis direction of [10]. Analysis of the structure and the pair-correlation functions indicate that the average precipitate length scale of the particles increases at the late-stage coarsening, and the dynamical scaling behavior is obeyed.     

Melt-spun Al<Subscript>70−<Emphasis Type="Italic">X</Emphasis></Subscript>Si<Subscript>30</Subscript>Mn<Subscript><Emphasis Type="Italic">X</Emphasis></Subscript> (<Emphasis Type="Italic">X</Emphasis>=0, 3, 5, 7, 10) anode in lithium-ion batteries

Al_70−X Si₃₀Mn _X (X=0, 3, 5, 7, 10, mol%) ribbons were prepared by melt spinning. A supersaturated solid solution of Si and Mn in fcc Al and some microstructures consisting of nano grains were obtained. Some alloys with nano-sized grains exhibited high discharge capacities and favorable cycle properties. The capacity of more than 400 mAh/g could be obtained in melt-spun Al₆₇Si₃₀Mn₃ alloy after 20 cycles and more than 300 mAh/g after 40 cycles. Li/Si and Li/Al compounds in the anodes of pure Al and pure Si were not detected in Al-Si-Mn alloys inserted by Li. It is considered that the formation of the supersaturated solid solution and refinement of microstructures have prevented the alloys from the forming the compounds with superfluous Li. As a result, the electrochemical properties have been improved. Supported by the National Natural Science Foundation of China (Grant No. 50371066)