Co部分替代Ni对La_(0.4)Er_(0.4)Mg_(0.2)Ni_(3.3-x)Co_xAl_(0.2)(0.1≤x≤0.4)储氢合金结构和电化学性能的影响

为了改善储氢合金La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)的结构和综合电化学性能,采用Co部分替代Ni的方法,实验采用高频感应炉制备La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)储氢合金。通过X射线衍射技术和电化学测量方法研究储氢合金的晶体结构和电化学性能。XRD图谱显示样品储氢合金主要由LaNi5和La2Ni7相组成,电化学实验表明,随着Co含量的增高,储氢合金电极的最大放电容量和50次循环后的容量保持率S50基本呈现增加状态,放电容量从x=0.1时的225mA·h/g升高到x=0.4时的254.9mA·h/g,容量保持率S50从57.11%(x=0.1)增加到66.10%(x=0.4),但高倍率性能不断下降。通过交流阻抗(EIS)和线性扫描(LS)对Co替代Ni的合金动力学性能分析发现,Co替代Ni后合金的表面电荷转移能力先降低后升高。     

硼对稀土系AB5型贮氢合金电化学容量及循环寿命的影响

为了提高低钴AB5型贮氢合金的电化学循环稳定性，在MmNi3．8Co0.4Mn0.6Al0．2贮氢合金中加微量的硼．用真空快淬工艺制备了稀土系低钴AB5型MmNi3．8Co0．4Mn0．6Al0．2Bx(x=0，0．1，0．2，0．3，0．4)贮氢合金，分析测试了铸态及快淬态合金的电化学性能及微观结构，研究了硼对铸态及快淬态合金电化学容量及循环寿命的影响．结果表明，硼使铸态及快淬态MmNi3.8Co0.4Mn0．6Al0．2贮氢合金的电化学容量不同程度地降低，但使电化学循环稳定性大幅度提高．硼对电化学性能的影响主要是促进非晶相的形成．     

Effect of VFe addition on hydrogen storage behavior of TiMn1.5-based alloys

The hydrogen absorption and desorption behavior of TiMn1.25Cr0.25 alloys with VFe substitution for partial Mn was investigated at 273, 293 and 313 K. It is found that VFe substitution increases their hydrogen storage capacity, decreases the plateau pressure and the hysteresis factor of their pressure-composition-temperature (PCT) curves. After annealing treatment at 1223 K for 6 h, TiMn0.95Cr0.25(VFe)0.3 alloy exhibits a lower hydrogen desorption plateau pressure (0.27 MPa at 313 K) and a smaller hysteresis factor (0.13 at 313 K); the maximum and effective hydrogen storage capacities (mass fraction) are 2.03% and 1.12% respectively, which can satisfy the demand of hydrogen storage tanks for proton exchange membrane fuel cells (PEMFC).     

Soft chemical synthesis and electrochemical properties of tin oxide-based materials as anodes for lithium ion batteries

1　INTRODUCTIONWiththedevelopmentoflithiumionbatteries ,thereisanincreasingdemandforelectrodematerialspossessinghighcapacity .Muchresearchwasunder takentosearchfornewanodematerialsin placeofcarbon (theoreticalmaximumcapacityof 372mA·h·g- 1)toimproveenergydensityforrechargeablelithi umionbatteries[110 ] .Notably ,tinoxide basedmate rials ,aspossiblecandidatesforthenextgenerationanodematerialsforLi ionbatteriesduetotheirhighlithiumstoragecapacityandlow potentialoflithiumionintercalation ,…     

Influence of Doped Elements on Electrochemical High Temperature Performance of La-riched Hydrogen Storage Material

1　IntroductionNi MHrechargeablebatterieshavebeenpromisingbatteriesforelectricvehiclesbecauseoftheirhighratioofpricetoperformance .However ,arapiddecayofthehydro genstoragematerialsoccurswhentheyareappliedtobat teriesforelectrics .Thecapacitydecaymaybecausedbytherisingoftemperatureinbatterieswhentheyarechargedanddischargedatahighcurrent.Itwasfoundthattheelectrochemicalperformancesofhydrogenstoragematerialsbecameworseathightemperatures .Itisexpectedthatthechangeinchemicalcomposi tionoftheallo…     

从废渣中提取的稀土镍钴合金储氢性能的研究

采用水浴—合金置换—电弧渣金熔分三步法从储氢合金冶炼废渣中提取稀土镍钴合金,以此为母合金,依据设计的成分,配入纯金属,电弧熔炼配制成新的储氢合金,测试其储氢性能,结果表明,回收后储氢合金的电化学容量达到315 mAh/g,接近标准储氢合金粉;气固吸氢量为1.403%,PCT曲线平台明显,且平台比较宽,表明吸氢量大;当合金容量衰减到初始容量的80%时,其循环次数为158次.     

新法回收废储氢合金性能的研究

针对废储氢合金粉回收提出一种全新的方法,即提炼和冶炼相结合的方法,并研究提炼后的中间合金及再生新合金的性能.经测试,回收后储氢合金的电化学容量达到282 mAh/g,PCT测试固气吸氢量为1.032%(质量分数),X射线测得主体相为CaCu5型六方结构,但其中含有微量杂质相,这有待于对中间合金的提炼工艺做进一步的研究.总之,利用此种方法得到回收后储氢合金的性能与原合金相近,是一种具有广阔发展前景的回收方法.     

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…     

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.     

Application of thermal electrochemical equation to metal-hydride half-cell system

1 INTRODUCTIONNickel-metal hydride ( Ni/ MH) battery be-came the principal power of electronic vehicle be-cause of its excellent characteristics such as highenergy density , high power , no memory effect ,long service life and wide temperature perform-ance . The hydrogen storage alloy is the key mate-rial of Ni/ MH dynamical battery , a mass of re-search work such as the technique of preparation,the performance of thermodynamics , kinetics andelectrochemistry were accomplished in recenty…     

不同热处理工艺制备WO3电致变色薄膜及性能研究

采用溶胶凝胶-钨粉过氧化法制备了氧化钨电致变色薄膜,并对其进行了不同温度的热处理,通过对电致变色原理的分析,研究讨论了不同热处理工艺对氧化钨薄膜微观形貌和电致变色性能的影响.采用X射线衍射、扫描电子显微镜、紫外-可见分光光度计、电化学工作站对薄膜的微观结构、离子储存、离子扩散速率和光谱调制能力进行了表征和分析.结果表明：适当的热处理温度可以形成较低缺陷的非晶薄膜,此时薄膜具有优越的离子储存和扩散能力,从而具有较大的可见光调节范围;热处理温度为300,℃时,薄膜表现出较好的电致变色性能.     

快凝合金La(NiMn)5.6的贮氢性能

借助X-ray及吸放氢性能测试装置研究了非化学计量比快凝合金La(NiMn)5.6的结构和贮氢性能以及A端、B端元素替代对合金的影响,测试了不同温度下合金的PCT曲线.结果表明,快速凝固(35 m/s)条件下合金La(NiMn)5.6均可获得过饱和CaCu5型单相组织.A端以Ce取代La,使平台压力增大,最大吸氢量减小,但滞后降低;B端以Sn取代Ni,改善了合金的活化特性,并使平台降低,吸放氢滞后减小.     

Influences of melt spinning on electrochemical hydrogen storage performance of nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the electrochemical hydrogen storage performance of the Mg₂Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg₂Ni-type Mg_20−x La _x Ni₁₀ (x=0, 2) alloys were synthesized by melt-spinning technique. The microstructures of the as-spun alloys were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical hydrogen storage properties of the experimental alloys were tested. The results show that no amorphous phase is detected in the as-spun Mg₂₀Ni₁₀ alloy, but the as-spun Mg₁₈La₂Ni₁₀ alloy holds a major amorphous phase. As La content increases from 0 to 2, the maximum discharge capacity of the as-spun (20 m/s) alloys rises from 96.5 to 387.1 mA·h/g, and the capacity retaining rate (S ₂₀) at the 20th cycle grows from 31.3% to 71.7%. Melt-spinning engenders an impactful effect on the electrochemical hydrogen storage performances of the alloys. With the increase in the spinning rate from 0 to 30 m/s, the maximum discharge capacity increases from 30.3 to 135.5 mA·h/g for the Mg₂₀Ni₁₀ alloy, and from 197.2 to 406.5 mA·h/g for the Mg₁₈La₂Ni₁₀ alloy. The capacity retaining rate (S ₂₀) of the Mg₂₀Ni₁₀ alloy at the 20th cycle slightly falls from 36.7% to 27.1%, but it markedly mounts up from 37.3% to 78.3% for the Mg₁₈La₂Ni₁₀ alloy.     

贮氢合金La-Mg-Ni系的贮氢性能

借助X-ray及吸氢性能测试装置研究了AB3型La-Mg-Ni系贮氢合金的结构和贮氢性能,测试了不同温度下合金的PCT曲线.结果表明,La-Mg-Ni系贮氢合金可获得(La,Mg)Ni3相组织;加Co,改善了合金的特性,并使平台压力降低.     

La1-xCexNi3.54Co0.78Mn0.35Al0.32贮氢合金相结构和电化学性能的研究

采用真空电弧熔炼和热处理方法制备了La1-xCexNi3.54Co0.78Mn0.35Al0.32(x=0.1,0.2,0.3,0.4,0.5,0.6)贮氢合金.X射线衍射(XRD)分析表明,合金含有单一CaCu5型六方结构相.电化学性能测试表明,随着x的增加,合金的最大放电容量从348.1mAh/g(x=0.1)单调地减小到310.1 mAh/g(x=0.6);HRD1200先从28.6%(x=0.1)增加到65.4%(x=0.5)然后降低到60.1%(x=0.6),归因于合金表面的电催化活性和合金体内氢原子扩散速率均随x的增大先增大后减小.     

Gaseous sorption and electrochemical properties of rare-earth hydrogen storage alloys and their representative applications: A review of recent progress

The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.     

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.     

La0.67Mg0.33Ni2.5Cu0.5贮氢合金磁热处理工艺的正交设计

利用L9（34）正交表安排实验,考察磁热处理的温度、时间及磁感应强度对La0.67Mg0.33N i2.5Cu0.5合金的吸放氢反应热力学和动力学的影响,结合极差分析和方差分析研究了各因素对考核指标的显著性影响,并得到合金磁热处理的优化工艺：热处理温度850℃,处理时间1 h和磁感应强度4 T.在此条件下处理后的合金,吸放氢的质量分数分别为1.33%和1.14%,焓变为-59.69 kJ/mol,吸热峰顶所对应的温度为86.3℃,吸放氢特征时间（tξ=0.875）分别为11.2和108.7 s.结果表明,该合金与其它工艺下的样品相比,吸氢量最大,放氢后物相结构最稳定,吸热峰顶所对应的温度最低,吸放氢速度最快.     

Effects of dispersant on performance of Ni-Zn batteries

A new additive of sodium hexametaphosphate (SHMP) was introduced to the paste of zinc electrode, with the purpose of preventing the zinc active materials from agglomerating and improving the stability of batteries. The properties of the zinc electrodes were characterized by scanning electron microscopy (SEM), constant current charge/discharge measurement, self-discharge test and hydrogen collection experiment. The photographs of zinc electrode show that SHMP can significantly break up the agglomeration, uniformize the particle distribution and increase the surface area, which are advantageous to improve the electrochemical performance of zinc electrode. The experimental battery shows a 97 times cycling life and a 30.2% remaining capacity after 4 d storage. The hydrogen collection experimental results indicate that the SHMP can decrease the ratio of hydrogen evolution. Therefore, the corrosion of zinc electrode is suppressed and the charge/discharge efficiency is enhanced.     

镁离子掺杂对LiFePO4材料性能的影响

为了提高LiFePO4的电化学性能,用Mg2 对LiFePO4进行掺杂,以Li3PO4为锂源、Mg(OH)2为掺杂源,采用固相法合成锂离子电池正极材料Li1-xMgxFePO4(x=0.005、0.01、0.02和0.03).通过X射线衍射分析及电化学测试,研究了Mg掺杂对材料的结构和电化学性能的影响.实验研究表明,掺入少量的Mg2 ,可以减小晶胞体积,提高LiFePO4的循环性能和比容量.当Mg的掺入量为2 mol%时,以0.1C倍率充放电,Li0.98Mg0.02FePO4最大放电容量为123.6 mAh/g.