化学镀镍对A2B7型贮氢合金电极电化学性能的影响

本文对气态粉化后A2B7型贮氢合金La0.75Mg0.25Ni3.44Al0.06进行化学镀不同厚度Ni包覆处理.通过SEM观察,结果表明,包覆处理后镀层镍为球形颗粒且均匀弥散于合金表面.电化学测试结果表明,表面包覆镍处理的A2B7型合金电极放电容量有所降低,而循环稳定性有所提高.线性极化扫描和电化学阻抗谱等分析结果表明,表面包覆Ni处理后增大了合金电极的交换电流密度(I0),减小了电化学阻抗,改善了合金电极的动力学性能.     

锂离子导体包覆镍锰酸锂正极材料的制备及其电化学性能

采用原位包覆法制备表面包覆Li1.3Al0.3Ti1.7(PO4)3(LATP)的Li Ni0.5Mn1.5O4(LNMO),即LNMO@LATP正极材料。采用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及电化学测试等手段对其物相结构、表面形貌及电化学性能进行研究。结果表明:LATP以无定型态紧密包覆于Li Ni0.5Mn1.5O4的表面,包覆层厚度约为5 nm。由于LATP包覆层具有保护电极材料表面和提高锂离子导电的双重作用,减少了电极过程的副反应,降低了电化学极化,提供了更多的锂离子扩散通道,导致LNMO@LATP具有比LNMO更稳定的循环性能和更好的倍率性能,特别是在高温的情况下。室温下在0.2C放电时,LNMO@LATP和LNMO的首次放电容量分别为141.5和142.6m A·h/g,经80次循环后,二者放电容量保持率分别达到99.2%和98.0%;而在10.0C放电时,LNMO@LATP和LNMO的首次放电容量分别为93.5和70.6 m A·h/g,经80次循环后,二者放电容量保持率分别达到66.1%和49.5%。当循环温度提高到55℃时,LNMO@LATP和LNMO在0.2C循环80次后的放电容量保持率分别为95.5%和79.2%;而在10.0C放电循环80次后,放电容量保持率分别为88.0%和51.0%。     

含Sc镁镍储氢合金的电化学性能

采用机械合金化方法制备Mg1-xScxNi(x=0,0.01)系列储氢合金.XRD结构分析表明,该系列合金为非晶态合金.XPS分析结果表明,加入微量Sc可以有效地抑制合金表面的氧化程度和提高合金表面Ni与Mg的原子个数比.电化学测试结果表明,微量Sc改善了合金电极的电化学性能,Mg0.99Sc0.01Ni合金电极的放电容量、容量保持率S10、高倍率放电能力HRD200、交换电流密度I0和极限电流密度,IL分别较MgNi合金电极提高10.5%、14.7%、30.4%、202.7%和77.8%.     

表面复合处理对AB5合金的高倍率和低温放电性能的影响

为了进一步提高贮氢合金的高倍率和低温放电等电化学性能,采用在有机酸中添加金属离子M2 (Ni2 、Co2 、Cu2 )及还原剂的方法,对商品AB5型贮氢合金粉末进行表面复合处理,实现了有机酸处理和表面微包覆一步完成.结果表明,经表面复合处理后的贮氢合金电极在2400mA/g放电电流密度下的HRD由21.9%提高到38.1%,在-35℃下的放电容量由54mA·h/g提高到170mA·h/g.表面复合处理显著改善了AB5贮氢合金的电化学性能,是一种方便有效的表面改性处理方法.     

Electrochemical Properties of the Amorphous Ti3Ni2 Alloy in Ni/MH Batteries

采用机械球磨晶态Ti3Ni2 (Ti2Ni/TiNi)合金的方法制备非晶态的Ti3Ni2合金,并研究其电化学性能.充放电测试结果显示,非晶态Ti3Ni2合金成功地解决了晶态Ti3Ni2合金在高温下(333 K)循环寿命极短的缺点.在333K循环19次后,相对于晶态Ti3Ni2合金较低的容量保持率(39.47％),其非晶态合金有效的将容量保持率提高到88.83％.通过Tafel极化,线性极化以及交流阻抗测试,发现这种改善源于非晶态Ti3Ni2合金的耐蚀性远优于其晶态合金.     

磁热处理对La—Mg—Ni-Co合金微结构与电化学性能的影响

考察La0.67Mg0.33Ni2.5Co0.5合金分别在铸态、热处理及磁热处理3种状态下的微结构及其电化学性能.通过XRD衍射及SEM分析贮氢合金的物相组成和电极合金循环后的形貌,研究Co部分替代Ni以及有无外加磁场下热处理对合金微结构与电化学性能的作用规律.结果表明:经Co部分取代的La-Mg-Ni铸态合金经过50次循环后,放电容量保持率从64.46%提高到74.80%;经磁热处理后,La0.67Mg0.33Ni2.5Co0.5合金的最大放电容量为324.80mA·h/g,较常规热处理合金的容量提高了10.59%,放电容量保持率为83.07%,其放电平台更为宽广且平坦:磁热处理的引入进一步降低贮氢合金电极的极化电阻,改善合金电极动力学性能.     

Ni对非晶态Co-B合金电化学储氢性能的影响

通过化学还原共沉积法引入元素Ni制备了三元非晶态Co-Ni-B合金,并研究了元素Ni对非晶Co-B合金电化学储氢性能的影响。结果表明,含镍23.8at%非晶态Ni-Co-B合金的可逆放电容量约为250mAh/g,较非晶Co-B合金下降约20mAh/g,但循环稳定性二者相同,即在650mA/g的高电流密度下循环60次容量几乎保持不变。但进一步增加Ni含量,含镍35.8at%的非晶态Ni-Co-B合金的放电容量和循环稳定性都较不掺杂时发生大幅下降。但是,元素Ni的引入能有效抑制高电流密度充电过程中Co-B合金表面大量氢气的析出,减小电极放电电压平台和容量在循环过程中的波动。这可能得益于以下2个原因:(1)非晶Ni-Co-B合金对水分解的电催化活性降低;(2)吸附态氢原子在非晶Ni-Co-B合金基体中的扩散速度高于在Co-B合金中的扩散速度。     

磁热处理对La-Mg-Ni-Cu合金相结构与电化学性能的影响

考察了La0.67Mg0.33Ni2.5Cu0.5合金分别在铸态、热处理后及磁热处理后3种状态下的相结构及其电化学性能.并通过XRD分析合金物相组成及SEM观察合金组织形貌,研究了Cu部分取代Ni以及有无外加磁场下热处理对合金相结构与电化学性能的作用规律.结果表明,La0.67Mg0.33Ni2.5Cu0.5铸态合金经过50次循环后,放电容量保持率从64.40%提高到72.44%;经磁热处理的La0.67Mg0.33Ni2.5Cu0.5合金最大放电容量为328.2 mAh/g,较常规热处理合金的容量提高了31.51%, 50次循环后的容量保持率为75.89%.其放电平台更为宽广且平坦;极限电流显著增大,氢在合金体相中的扩散速度加快.     

Ni对复合储氢合金电化学性能的影响

采用二步重熔法制备了Mm0.3Ml0.7Ni3.55Co0.75Mn0.4Al0.3/5％Mg2Ni复合材料.通过电池程控测试仪测定了Ni添加对复合储氢合金Mm0.3Ml0.7Ni3.55Co075Mn0.4Al0.3/5％Mg2Ni电化学性能的影响.结果表明,添加Ni粉的合金电极经两个循环就可达到最大的放电容量,而未添加Ni的储氢合金电极需要13个循环才能够活化;当羟基镍粉由100％增加到200％时,合金的最大放电容量增幅分别达到7％、11.8％;在大电流放电试验中,添加Ni粉的合金电极呈良好的高倍率放电性能.     

Mg_3MnNi_(2-x)Co_x(x=0～0.2)储氢合金的相结构及电化学性能研究

为了研究Mg3MnNi2储氢合金的电化学储氢性能,实验采用Co元素部分取代Mg3MnNi2合金中的Ni,用固相扩散法制备出Mg3MnNi2-xCox(x=0~0.2)系列合金,并分析其相结构,以及测试合金的电化学性能和动力学性能。结果表明:Co元素的添加并不改变合金的主相,Co替代Ni明显改善了合金的放电容量、循环稳定性以及动力学性能等,其中当Co的含量从0增加到0.2时,合金的最大放电容量达到最大值282.36mA·h/g,20次循环后容量保持率仍有74.7%,而且动力学性能也是最优,高倍率放电性能ηHRD从66.4%增长到73.3%。这主要是Co替代Ni能够降低生成氢化物的稳定性,提高合金的抗粉化能力,以及降低合金的极化电阻。     

Electrochemical properties of CeMg_(11)Ni+x% Ni composites (x=0,50, 100 and 200) prepared by ball-milling

1　INTRODUCTIONMagnesium and magnesium based alloys arepromising hydrogen storage materials because oftheir absorbability of hydrogen in large quantities,low specific gravity, rich mineral resources, lowmaterial cost and so on. Nevertheless, their hy drides are too stable to be used at room tempera ture[1]. It seems impossible for application of crys talline Mg based alloys in nickel hydrogen batter ies.It is well known that amorphous alloys havemany advanta…     

Oxidation resistance of B2 rare earth–magnesium intermetallic compounds

The oxidation behaviors of YMg and CeMg were measured in flowing air using the thermal gravimetric analysis technique. Negligible oxidation is observed at room temperature in both compounds. At elevated temperatures, the rare earth metals oxidize preferentially, while the underlying materials transform into Mg-rich intermetallics before the Mg oxidizes to MgO. The oxidation resistance of YMg is several orders of magnitude greater than that of CeMg. The oxidation of YMg follows parabolic kinetics with an activation energy of 104 kJ/mol while that of CeMg obeys a linear law with an activation energy of 136 kJ/mol.     

Electrochemical hydrogen storage of NdMg12–Ni composites modified with carbon nanotubes and BN particles

In this work, the electrochemical performance of NdMg₁₂–Ni composite electrode in alkaline solution and the effect of the surface modification with carbon nanotubes (CNTs) and boron nitride (BN) particles on the NdMg₁₂–Ni composite were investigated. The NdMg₁₂ alloy was synthesized by a salt-cover-melting and a subsequent quenching process. The NdMg₁₂–Ni–BN and NdMg₁₂–Ni–CNTs composites were prepared by ball-milling NdMg₁₂ alloy, Ni powders and CNTs or BN particles. It is found that CNTs or BN particles are mainly attached onto the surface of the NdMg₁₂–Ni composite after the ball-milling process. The electrochemical experiment results indicate that the NdMg₁₂–Ni composites modified with CNTs or BN particles have the improved electrochemical performance. In particular, the NdMg₁₂–Ni–5 wt.% CNTs and NdMg₁₂–Ni–3 wt.% BN composites have the higher initial discharge capacity of 416.6 mAh/g and 442.9 mAh/g, respectively, larger than the original NdMg₁₂–Ni composite. The large amount of grain boundaries and crystalline defects, induced during the ball-milling process, can accelerate the bulk hydrogen diffusion and provide more surface active sites for the electrochemical reaction of the composites. However, the cycle stability of the composites modified by CNTs or BN particles is still not satisfactory for the practical application.     

热循环对20％／SiCW／6061Al复合材料尺寸稳定性的影响

通过测量20％（体积分数）SiCW/6061Al复合材料热循环（25℃→300℃→25℃）的尺寸变化,研究了复合材料的热循环尺寸稳定性。结果表明,复合材料尺寸稳定性直接与晶须的限向方式有关。如果晶须取向为混乱分布,热循环后复合材料的尺寸变化不明显。当晶须取向为定向排列时,热循环可造成复合材料的沿晶须方向的尺寸增大,同时垂直晶须方向尺寸减小。     

SiCP/Al复合材料温度变化引致尺寸不稳定性的研究

研究了ＳｉＣｐ／Ａｌ系复合材料经不同热处理后在温度反复变化时的尺寸稳定性，结果表明，在温度反复循环后会产生累积残余应变εｅｒ，随循环次数的增多，εｃｒ减小，尺寸趋于稳定，预处理对热循环累积残余应变有影响，退火态εｃｒ最大，时效态次之，而预循环态最小。复合材料中颗粒尺寸越大，颗粒体积分数越高以及基体越硬均对抵抗环境温度变化尺寸稳定性有利。与均质的纯铝相比较，复合材料的热循环累积残余应变较大，抵抗温度     

低温循环过程中SiCw／6061Al复合材料残余应力的变化规律

研究了低温循环过程中压铸态ＳｉＣｗ／６０６１Ａｌ复合材料残余应力的变化零乱低温循环的降温阶段,复合材料基体经历错配拉伸塑性变形过程在升温阶段基体国卸载过程。经过一次低温循环后,残余应力有所降低。如果进行两次低循环自理只有当第二次循环下降温度低于第一次时,才能再次降低复合材料残余应力。     

Tin oxide-graphite composite for lithium storage material in lithium-ion batteries

A SnO-graphite composite material, which can deliver high capacities and good cycling stability compared with unsupported SnO, was described. This material prepared via chemical co-precipitation reaction in the presence of graphite consists of high dispersion of SnO with a size of about several hundred nanometers in the graphite. The phase structure was analyzed by X-ray diffraction (XRD). The morphology and the element distribution were examined by scanning electron microscopy (SEM) equipped with energy spectrum. The results show that the SnO-graphite composites produced by slowly hydrolysis have higher rechargeable capacities than pure graphite and better cycling performance than SnO.     

锂离子电池硅/石墨/无定形碳复合阳极材料的制备及电化学性能表征

提出并制备了一种优化结构的硅/石墨/无定形碳复合材料,材料主要通过对硅、石墨和蔗糖的混合物进行超细粉碎和热解制备,硅基材料的电化学性能得到有效改善。研究了硅/石墨/无定形碳材料的形貌、电化学性能、循环稳定性,并对硅含量进行了优化。结果表明,将纳米硅材料负载在石墨碳基体上,结合高温热解技术,可以有效提高阳极材料的电化学性能。以石墨为缓冲基体、具备导电网络和非晶碳涂层的硅/石墨/无定形碳材料表现出良好的电化学性能。硅/石墨/无定形碳材料的非晶碳涂层可以明显降低硅与电解液之间接触损耗的可能性,并通过释放硅体积变化产生的应力来帮助保持材料的稳定性。     

微纳米结构MnO/C材料的制备与储锂性能研究

以醋酸锰、乙二醇、草酸二水化合物为原料,以聚乙烯吡咯烷酮(PVP)、葡萄糖、间苯二酚为碳源,通过沉淀法辅以热处理,制备出了碳包覆的微纳米结构MnO/C复合材料。利用XRD、SEM、TEM和电化学测试研究MnO/C复合材料的结构、形貌和电化学性能。研究结果表明,以PVP为碳源通过沉淀法制备的MnO/C材料具有微纳米复合结构且材料表面均匀包覆3 nm左右的碳层。该材料作为锂电负极材料在100 m A/g的恒流充放电下循环50次可逆容量达到586 mAh/g,并且经过大电流充放电后仍然表现了优异的结构稳定性。     

Bending-fatigue behavior of bulk metallic glasses and their composites

Amorphous alloys with high glass-forming ability and thermal stability were discovered in the 1990s. In the following years, the alloy design increased the critical casting thickness to several centimeters, and a homogeneous dispersion of nanoscale particles was found to improve the ductility. Therefore, bulk metallic glasses (BMGs) are being studied widely because of their potential as structural materials. The fatigue behavior is an important characteristic of structural materials. The current review documents the bending-fatigue studies of BMGs and their composites. The fatigue characteristics of these alloys in different loading conditions and environments are summarized and compared in this paper. The factors affecting the fatigue behavior of BMGs and their composites are discussed. The mechanisms of fatigue-crack initiation and propagation in BMGs are addressed in this review. In order to broaden the scope of applications of BMGs, a fundamental understanding of the fatigue behavior is critical for the design of new alloy systems and the development of the processing techniques.