纳米Co-Sn金属间化合物的合成、表征及电化学吸放锂行为

用溶剂热法合成了三种纳米尺寸的Co-Sn金属间化合物, 即CoSn2、CoSn和Co3Sn2, 并研究了它们作为锂离子二次电池新型负极材料的电化学性能. 合成的粉末经过了X射线衍射(XRD), 透射电镜(TEM)和场发射扫描电镜(FESEM)的表征. 研究发现, 这三种金属间化合物均显示出较高的充放电稳定性. 由于低的锂离子扩散速率, 在嵌锂过程中锂离子不能深入到晶粒内部, 导致它们的电化学活性较低, 尤其是Co3Sn2, 其首次充电容量仅为 93 mAh•g−1.     

Tb(Co_(1-x)Sn_x)_2合金的结构和磁热效应

通过X射线衍射和磁性测量研究了Tb(Co1-xSnx)2(x=0,0.025,0.050,0.075,0.100)合金的相结构和磁热性能。经分析可知Sn在TbCo2中的替代是有限的,X粉末衍射分析确定TbCo2具有MgCu2结构,其他样品由TbCo2,TbCo3和Tb5Sn3三相组成,TbCo2为主要相。随着Sn成分的增加,杂质相TbCo3和Tb5Sn3的含量增加,所有样品保持第二序磁相变。Sn的替代使磁相变的温度稍微有所提高,样品TbCo2的TC值为230 K,样品Tb(Co0.950Sn0.050)2的TC值为233 K,但Sn的成分继续增加,样品的TC值有所下降。在外加磁场2 T的作用下,样品Tb(Co1-xSnx)2(x=0,0.025,0.050,0.075)最大磁熵变值分别为3.44,2.29,1.64,1.16 J.kg-1.K-1。     

锂离子电池Sn30Co30C40三元合金负极材料的制备与性能研究

随着人们对高比能量锂离子电池需求的逐步增加,Sn基合金成为目前高比容量负极材料的研究热点.以低成本的金属氧化物、活性炭为原料经碳热还原法首先合成出中间产物CoSn2,再将Co、石墨引入,经高能球磨制备了Sn30Co30C40三元合金负极材料.材料呈现微米级颗粒形貌,其内部是由均匀分散于无定形碳中10 nm左右CoSn晶粒所组成.材料的比容量为550 mAh/g左右,首次效率为80%左右,循环稳定性好、倍率性能优越,是一种非常有发展前景的高比容量锂离子电池负极材料.     

电沉积法制备Sn-Co-C锂离子电池负极材料

本文分别采用柠檬酸和EDTA作为络合剂在CoCl2,SnCl4溶液中用电沉积方法制备Sn-Co合金电极,然后在相同条件下在镀液中加入硬碳制备Sn-Co-C复合电极.充放电测试结果显示EDTA作为络合剂时镀层循环性能明显好于柠檬酸,且比容量也较高.Sn-Co合金电极循环30次比容量保持率达91.6%,加入硬碳的Sn-Co-C复合电极比容量及循环性能较之Sn-Co合金电极都有了较大提高.电子探针结果表明EDTA作为络合剂的Sn-Co-C镀层中Sn、Co、C原子比例分别为61.8401%,22.3788%,12.5409%.SEM观察Sn-Co-C镀层表面为稳定的球状结构.     

电沉积法制备Sn-Co-C锂离子电池负极材料

本文分别采用柠檬酸和EDTA作为络合剂在CoCl2，SnCl4溶液中用电沉积方法制备Sn-Co合金电极，然后在相同条件下在镀液中加入硬碳制备Sn-Co-C复合电极。充放电测试结果显示EDTA作为络合剂时镀层循环性能明显好于柠檬酸，且比容量也较高。Sn-Co合金电极循环30次比容量保持率达91．6％，加入硬碳的Sn-Co-C复合电极比容量及循环性能较之Sn-Co合金电极都有了较大提高。电子探针结果表明EDTA作为络合剂的Sn-Co-C镀层中Sn、Co、C原子比例分别为61．8401％，22．3788％，12．5409％。SEM观察Sn-Co-C镀层表面为稳定的球状结构。     

钛和锆的添加对MgNi型合金电极电化学性能的影响

用机械球磨法（MA）成功合成了镁基储氢合金MgNi, Mg0.9Ti0.1Ni和Mg0.9Ti0.1Ni0.9Co0.1。研究了其结构和电化学性能。X射线衍射（XRD）和扫描电镜（SEM）结果表明合金为非晶结构，并有少量的Ni衍射峰存在。充放电测试结果表明这一系列合金具有很好的电化学活性。Ti和Co的替代使合金的循环稳定性好于MgNi合金。50周充放电循环后，Mg0.9Ti0.1Ni0.9Co0.1合金的放电容量明显好于MgNi合金，Mg0.9Ti0.1Ni0.9Co0.1的放电容量比MgNi合金高102.8%，比Mg0.9Ti0.1Ni合金高45.49%。在充放电循环过程中，合金电极容量衰减的主要原因是在合金电极表面Mg变成了Mg(OH)2。Tafel极化测试表明Ti和Co的添加可以提高合金电极在碱液中的抗腐蚀性能和提高合金电极的循环稳定性。EIS测试结果表明Ti和Co的替代可以明显提高MgNi型合金表面的电催化活性。     

三维多孔Sn-Co合金负极制备及其电化学性能研究

采用化学镀方法制备三维多孔铜.以其作为集流体,借助电沉积制备三维多孔Sn-Co合金电极.X-射线衍射(XRD),扫描电镜(SEM)分析表明,以多孔铜为集流体制备的SnCo合金电极主要存在CoSn2相和纯Sn相,为三维多孔结构.充放电结果显示,三维结构SnCo合金电极比平面铜集流体上镀得的SnCo合金电极表现出更优越的充放电性能.前者的首次放电(嵌锂)容量为636.3mAh/g,充电(脱锂)容量为528.7mAh/g,首次库仑效率为83.1%,70周后容量为529.5mAh·g-1,保持率为82.6%.此外,还应用电化学阻抗初步研究了三维Sn-Co合金电极在充放电过程发生的嵌脱锂过程.     

锂离子电池用SnZn/Cu薄膜负极材料的研究

合金型锂离子电池负极材料由于容量高、安全性好而备受关注. 采用磁控溅射法在铜箔上渡膜制备锡锌薄膜, 经热处理后得到合金薄膜电极. 薄膜热处理后, 表面活性层形成Cu3Sn中间合金. 合金薄膜是由尺寸在5 μm左右的合金颗粒构成, 而合金颗粒则由更小的尺寸在50 nm左右微粒组成, 该合金薄膜同时具有薄膜、中间合金和纳米结构材料的特征. 合金薄膜电极具有较高的充放电容量、良好的循环性能和非常高的充放电效率. 在0.01～1.0 V (vs. Li/Li＋)区间, 电极循环200周后放电容量保持在300 mAh•g－1以上, 与第一次脱锂容量相比较, 容量保持率高达91.9%, 充放电效率大于98.0%.     

锂离子电池正极材料LiMnPO4的合成与性能

对反应物与中间产物进行球磨,采用固相反应法分别在600 ℃和800 ℃合成了掺碳的橄榄石型LiMnPO4.通过XRD表征样品的晶体结构,采用SEM观察样品的微观形貌,利用电化学手段测试样品的充放电性能.结果表明,在对反应物球磨24 h、中间产物球磨12 h的条件下,在600 ℃烧结的样品含有杂相和烧结密实的大块状物.而在800 ℃下烧结可形成纯橄榄石结构的LiMnPO4,但颗粒较大.上述两种样品的电化学测试表明,它们难以充放电.而在反应物球磨36 h、中间产物球磨24 h的条件下,600 ℃烧结得到物相较纯,样品的粒径小且均匀,约100～200 nm,首次放电容量接近100 mAh•g－1.本研究表明,反应物或中间产物的混合程度以及烧结温度的选择是获得具有可逆充放电性能的纯橄榄石结构LiMnPO4的重要因素.     

B对Sn-Co合金结构及电化学性能的影响

采用固相法合成了Sn-Co/B复合材料, 考察了B对材料的结构和电化学性能的影响. XRD分析结果表明, Sn-Co合金由CoSn相组成, 添加B能使晶粒细化并且形成CoSn2. 恒流充放电测试表明, B的添加提高了Sn-Co合金的循环性能, 但使放电容量略有降低. 当B质量分数为4%时, Sn-Co/B复合物的首次放电容量为216 mA·h/g, 经过30次循环后容量保持率达82.9%, 表现出良好的结构稳定性.     

First-principles Study of Mechanical and Electronic Properties of Co-Sn Intermetallics for Lithium Ion Battery Anode

The equilibrium structures, formation energy, mechanical properties and electronic properties of Co-Sn intermetallics have been systemically studied by first-principles study. The results show that the CoSn phase is more thermodynamically stable than any other stoichiometry of Co-Sn intermetallics. With the increasing of Co content in Co-Sn intermetallics, the mechanical properties change into brittle behavior from ductility character. Adding proper amount of Co to Co-Sn intermetallics can improve the cycle performance for lithium ion battery anode. However, high Co content will lead to a poor cycle performance for Co-Sn intermetallics.     

Synthesis,Crystal Structure and Band Structure of Tb3Co4Sn（13）

A new intermetallic compound,Tb3Co4Sn13,has been synthesized by solid-state reaction of the corresponding pure elements in a welded tantalum tube at high temperature.Its crystal structure was established by single-crystal X-ray diffraction.Tb3Co4Sn13 crystallizes in cubic,space group Pm3n(No.223) with a = 9.5072(2) ,V = 859.33(3) 3,Z = 2,Mr = 2255.45,Dc = 8.717 g/cm3,μ = 34.369 mm-1,F(000) = 1906,and the final R = 0.0140 and wR = 0.0312 for 199 observed reflections with I > 2σ(I).The structure of Tb3Co4Sn13 belongs to the Yb3Rh4Sn13 type.It is isostructural with RE3Co4Sn13(RE = La,Ce),featuring a 3D [Co4Sn12] framework based on [CoSn6] trigonal prisms.The [CoSn6] trigonal prisms are interconnected via corner-sharing and Sn-Sn bonds to form a 3D [Co4Sn12] framework.The other Sn and Tb atoms are located in the spacers of the 3D framework.Band structure calculations indicate that Tb3Co4Sn13 is metallic.     

Importance of nanostructure for high capacity negative electrode materials for Li-ion batteries

Sn–Co–C alloys are currently used as negative electrode materials for Li-ion batteries. A comparison between sputter deposited and mechanically alloyed Sn–Co–C materials has revealed a difference in the achieved specific capacity of materials prepared by the two methods. Only the sputtered materials reached the expected capacity even though both types of materials showed similar X-ray diffraction patterns. The structure of these materials has been described as being grains of amorphous CoSn embedded in a carbon matrix. Here, the sizes of the CoSn grains were determined using small angle neutron scattering measurements on various Sn₃₀Co₃₀C₄₀ samples. Small grain sizes, on the order of 10 Å, were obtained for the sputtered samples while grain sizes between 55 and 100 Å were obtained for samples with the same composition but prepared by mechanical alloying methods. The inability of the mechanically prepared materials to achieve their theoretical capacity may be due to the larger size of the CoSn grains.     

Effects of Ti and Co on the Electrochemical Characteristics of MgNi-Based Alloy Electrodes

Mg-based hydrogen storage alloys MgNi, Mg0.9Ti0.1Ni and Mg0.9Ti0.1Ni0.9Co0.1 were successfully prepared by means of mechanical alloying （MA）. The structure and the electrochemical characteristics of these Mg-based materials were also studied. The results of X-ray diffraction （XRD） and scanning electron microscopy （SEM） show that the main phases of the alloys exhibit amorphous structures, and trace of Ni co-exists. The charge-discharge cycle tests indicate these alloys have good electrochemical active characteristics. And the cycle stability of Ti and Co doped alloy was better than that of MgNi alloy. After 50 cycle charge-discharge, the discharge capacity of the Mg0.9Ti0.1Ni0.9Co0.1 alloy was much better than that of MgNi and Mg0.9Ti0.1Ni alloys. The discharge capacity of Mg0.9Ti0.1Ni0.9Co0.1 was 102.8% higher than that of MgNi alloy, and 45.49% higher than that of the Mg0.9Ti0.1Ni alloy. During the process of charge-discharge cycle test, the main reason for the electrode capacity fading is the corrosion of Mg to Mg（OH）2 on the surface of alloys. The Tafel polarization test indicates Ti and Co improve the anticorrosion in an alkaline solution. The EIS results suggest that proper amount of Ti and Co doping improve the electrochemical catalytical activity on the Mg-based alloy surface significantly.     

Studies of the interfacial properties of an electroplated Sn thin film electrode/electrolyte using in situ MFTIRS and EQCM

Sn thin film electrodes were prepared by electroplating in an acidic sulfate bath containing SnSO4. During charge/discharge processes, the interfacial properties between a Sn thin film electrode and an electrolyte of 1 mol.L(-1) LiPF6 in a mixture of ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 vol %) were investigated by using cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), and in situ microscope Fourier transform infrared reflection spectroscopy (in situ MFTIRS). The processes of alloying/dealloying of lithium with Sn and the decomposition of the electrolyte on the Sn electrode were characterized quantitatively by surface mass change and at the molecule level. EQCM studies demonstrated that the mass accumulated per mole of electrons (mpe) was varied in different electrochemical processes. In the process of electrolyte decomposition, the measured mpe is smaller than the theoretical value, whereas it is higher than the theoretical value in the process of alloying/dealloying. The reduction products, ROCO2Li, of the electrolyte involved in charge/discharge processes were determined by in situ MFTIRS. The solvation/desolvation of lithium ion with solvent molecules, which is induced by the alloying/dealloying of lithium with Sn, was evidenced by shifts of relevant IR bands of C=O, C-O, and C-H. The current studies clearly revealed the details of interfacial reactions involved in lithium ion batteries employing a Sn thin film as the anode.     

Electrodeposition and electrochemical properties of novel ternary tin–cobalt–phosphorus alloy electrodes for lithium-ion batteries

Porous Sn–Co–P alloy with reticular structure were prepared by electroplating using copper foam as current collector. The structure and electrochemical performance of the electroplated porous Sn–Co–P alloy electrodes were investigated in detail. Experimental results illustrated that the porous Sn–Co–P alloy consists of mainly SnP_0.94 phase with a minor quantity of Sn and Co₃Sn₂. Galvanostatic charge–discharge tests of porous Sn–Co–P alloy electrodes confirmed its excellent performances: at 50th charge–discharge cycle, the discharge specific capacity is 503 mAh g^?1 and the columbic efficiency is as high as 99%. It has revealed that the porous and multi-phase composite structure of the alloy can restrain the pulverization of electrode in charge/discharge cycles, and accommodate partly the volume expansion and phase transition, resulting in good cycleability of the electrode.     

Mössbauer studes of electrocodeposited cobalt—Tin alloys

Cobalt—tin alloys electrocodeposited from a mildly alkaline sulfate bath were studied using¹¹⁹Sn absorption and⁵⁷Co Emission Mössbauer Spectroscopy. The Results reveal that dissolved tin and cubic CoSn (not appearing in the phase diagram) are the components obtained from fresh plating solutions. Upon exhaustion, the formation of Co₃Sn₂ is favoured, with the eventual deposition of cobalt particles as a separated phase. A precipitate is formed during bath operation which is richer in Sn(II), contrasting to the mother solution which is richer in Sn(IV).     

热处理对La4MgNi19储氢电极合金结构和性能的影响

以感应熔炼和不同的热处理工艺制备了La₄MgNi₁₉合金, 用X射线衍射(XRD)和电化学测试系统研究了该合金的相结构和电化学性能. 结构分析表明: 当热处理工艺为900 °C+水淬时, 合金主要由CaCu₅结构的LaNi₅相和少量未知相组成; 当热处理工艺为900 °C退火时, 合金主要由Pr₅Co₁₉、Ce₅Co₉结构的(La, Mg)₅Ni₁₉相及少量CaCu₅结构的LaNi₅相组成. 淬火和退火后合金的电化学循环稳定性(S₁₀₀)分别为49.7%及76.0%, 合金电极的电化学性能和相结构密切相关. 退火热处理有利于生成Pr₅Co₁₉、Ce₅Co₉型相. 在La-Mg-Ni 系储氢合金中, La₄MgNi₁₉合金电化学循环稳定性不及La₃MgNi₁₄合金.