机械球磨Mg2Ni0．95Sn0．05＋x％Ni非晶复合物的微结构和电化学性能

用机械球磨法合成了Mg2Ni0．95Sn0．05＋x％Ni（质量分数，x=25，50，75，100，125）非晶复合物，研究了其微结构和电化学性能。微结构分析表明，不添加Ni粉的Mg2Ni0．95Sn0．05合金经100h球磨后仍然难以形成非晶结构，加入镍粉有助于非晶结构的形成。电化学研究表明，铸态最大放电容量仅为16mAh／g，球磨100h后容量改善不明显；加入Ni粉球磨后，容量大幅上升，随着Ni添加量的增加，复合物最大放电容量先增后减，在x=75时达到最大值625.6mAh／g。把x=50时的复合物，延长球磨时间t，复合物最大放电容量提高，当t=200h时达到670mAh／g。     

Microstructure and electrochemical properties of mechanically ground Ce2Mg17 + x wt.% Ni (x = 0, 50, 100, 200) composites

The effects of mechanical grinding with or without nickel powder on microstructure and electrochemical properties of Ce₂Mg₁₇ hydrogen storage alloy in 6 M KOH solution were investigated. The microstructure and electrochemical properties depend greatly on the amount of nickel powder introduced during mechanical grinding. For the alloy ball-milled with nickel powder, the more nickel powder added, the more advantageous it is for the formation of a homogeneous amorphous structure, and the larger discharge capacity obtained. After 90 h ball-milling, the Ce₂Mg₁₇ + 200 wt.% Ni composite exhibited a large discharge capacity of 1014 mAh g(Ce₂Mg₁₇)⁻¹[338 mAh g(Ce₂Mg₁₇ + 200 wt.% Ni)⁻¹] at 303 K. The improvement of electrochemical capacity can be attributed to the formation of a homogeneous amorphous structure as well as the modification of the surface state by Ni addition.     

Effects of surface modification on the electrode behavior of ball-milled La2Mg17 + 200 wt% Ni composite in alkaline solution

The ball-milled La₂Mg₁₇ + 200 wt% Ni composite is modified with graphite, aluminum, cobalt, titanium and nickel (weight ratio: 5 wt%) by ball-milling for 90 min. The microstructures of the obtained materials were examined by X-ray diffraction and SEM. The electrochemical properties of the obtained materials were measured and compared with those of the original ball-milled composite. It was found that the maximum discharge capacity and high-rate dischargeability of the composites after surface modification by graphite, Co and Ni increased to some extent due to the electrocatalytic activity of the coating element and the decrease of electrochemical reaction resistance on the alloy surface, but the effect of Al and Ti was just on the contrary. On the other hand, the cycling stability of the composites modified with Al, Ti and Ni all improved, and the modification with Ti was the most effective in improving the cycle life. But the modification with graphite, Co led to the worsening of the cycling stability to different degree, especially the modification with graphite.     

表面包覆对非晶态CeMg12合金电化学性能的影响

采用在CeMg12中添加镍粉球磨制备非晶态合金,并研究化学镀表面包覆Ni对其电化学性能的影响.结果表明,非晶态CeMg12具有很高的电化学放电容量,CeMg12+200%Ni(质量分数)球磨50 h后复合电极材料电化学容量达到1209.6 mAh/g,但是电化学循环稳定性较差,10次循环保持率为37.26%.通过化学镀镍进行表面包覆能明显提高合金的综合电化学性能.化学镀表面包覆Ni后,合金10个循环的保持率上升到69.67%:同时由于添加的Ni和包覆Ni的共同催化作用,合金高倍率性能也得到了相应的提高,HRD900由原来的54.2%提升到72.4%;但是由于化学镀过程中部分合金被氧化,使复合合金的最大放电容量略有下降.     

SnO2/Ni复合锂离子电池负极材料的制备及其电化学性能

采用机械球磨法将纳米SnO2和Ni粉末复合,作为锂离子电池负极材料。采用XRD、SEM、TEM和EDS分析球磨过程中材料结构和形貌的变化。对SnO2/Ni复合负极材料的首次库仑效率、循环稳定性及CV曲线等进行测试分析。结果表明:将复合粉末球磨适当时间后,SnO2和Ni可形成结合充分、颗粒尺寸细小、分布均匀的复合材料;SnO2和Ni的复合可有效提高SnO2的首次库仑效率和循环稳定性;SnO2/Ni复合负极材料的循环稳定性随球磨时间的延长而增加,但电极的首次库仑效率随球磨时间的延长呈先增加后下降的趋势;Ni的引入有效减小了SnO2在首次充放电循环过程中生成Li2O的不可逆反应程度,并在随后的循环过程中部分以Li-O化合物的形式进行可逆反应。     

Hydrogen Storage Performances of Nanocrystalline and Amorphous NdMg_(11)Ni+x wt% Ni (x=100, 200) Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous NdMg_(12)-type NdMg_(11)Ni+x wt% Ni( x = 100, 200) alloys were successfully prepared through ball milling(BM). The microstructures and electrochemical properties were systematically studied to get a more comprehensive understanding of the sample alloys. The maximum discharging capacity could be obtained at only two cycles, indicating that as-milled alloys have superior activation capability. The more the Ni content, the better the electrochemical properties of the as-milled samples. To be specific, the discharge capacities of x = 100 and x = 200(BM 20 h) samples are 128.2 and 1030.6 mAh/g at 60 mAh/g current density, respectively, revealing that enhancement of Ni content could significantly improve the discharging capacities of the samples. Additionally, milling duration obviously influences the electrochemical properties of the samples. The discharging capacity always rises with milling duration prolonging for the x = 100 sample,but that of the( x = 200) sample shows a trend of first augment and then decrease. The cycling stability of the( x = 100) alloy clearly decreases with extending milling duration, whereas that of the( x = 200) alloy first declines and then augments under the same conditions. In addition, the high rate discharge(HRD) abilities of the sample display the maximal values as milling duration changes. The HRD(HRD = C_(300)/C_(60)× 100%) values of the as-milled alloys( x = 100, 200) are 80.24% and 85.17%,respectively.     

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.     

Influence of crystallinity on the structural and hydrogenation properties of Mg2X phases (X=Ni,Si, Ge,Sn)

The hydrogen storage properties of nanocrystallized Mg₂Ni prepared by ball-milling have been studied. Hydrogenation at 200 °C leads to the formation of the monoclinic low-temperature phase Mg₂NiH₄ containing a much larger amount of microtwinning than the hydride obtained by hydrogenation of well-crystallized Mg₂Ni at the same temperature. The large amount of defects and dislocations present in the ball-milled alloys seems to favour the formation of microtwinning upon hydrogenation. Additionally, Mg₂X compounds (X=Si, Ge, Sn) have been prepared by powder metallurgy and ball-milling. Cubic phases with antifluorite structure are obtained, except for Mg₂Sn, for which a metastable rhombohedral phase is synthesized by ball-milling. Mg₂Si decomposes into MgH₂ and Si when ball-milled under hydrogen atmosphere, whereas Mg₂Ge and Mg₂Sn do not absorb hydrogen and are not decomposed.     

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.     

Cu粉复合球磨处理对Ⅴ基固溶体型贮氢合金电化学性能的影响

研究了V基固溶体型贮氢合金(TiV211Ni013和TiV211Ni015)与Cu粉进行复合球磨处理对其相结构及电化学性能的影响。X射线衍射和扫描电镜分析表明,铸态合金均由体心立方(bcc)结构的V基固溶体主相和bcc结构的TiNi基第二相组成;当与Cu粉复合球磨处理后,合金均变成由V基固溶体主相和体心四方(bct)结构的CuNi2Ti第二相组成,且合金颗粒的表面状态发生改变。电化学测试表明,球磨处理后合金电极的最大放电容量增加了25～39mA·h/g,100次循环容量保持率大幅提高,循环稳定性得到显著改善。结果表明,Cu粉复合球磨处理是通过同时改变V基合金的第二相成分和晶体结构以及合金颗粒的表面状态来改善合金的电极性能,这与其他传统球磨方式仅通过改变合金的表面状态来改善电极性能的作用机制有所不同。     

纳米化对Mg2Ni/MmNi5-x(CoAlMn)x复合储氢合金电极特性的影响

用高能球磨方法制备了Mg2Ni/MmNi5-x(CoAlMn) x复合储氢合金，并用化学镀对其进行包覆处理，X射线衍射（XRD）和扫描电镜（SEM)别证实复合合金具有团粒结构的特征，并在适当的球磨条件下达到纳米复合，本研究有模拟电池法分析了不同晶粒尺寸的单相和复合合金的电极特性，对于单相Mg2Ni和MmNi5-x(CoAlMn)x合金，球磨分别导致其放电容量增加加和降低，对纳米复合储氢合金而言，其放电容量并不是其组成合金的容理的简单加和，而是存在复合增强效应，当复合合金中组元相的晶尺寸小于100nm时，具有明显的复合增强效应。     

高能球磨法制备的碳纳米管增强铝基复合材料的微观组织和力学性能

采用高能球磨法制备了不同体积分数的碳纳米管(CNT)与Al粉的混合粉末,用粉末冶金工艺制备了CNT/A1复合材料.微观结构分析表明.球磨可以分散一定含量的CNT到Al基体中,并与其产生良好结合.在适当的球磨工艺下.球磨不会造成CNT的严重损伤.拉伸实验表明,CNT体积分数为1.5%时,力学性能达到了最高值,屈服强度相对于纯A1基体提高了53.6%.而CNT体积分数为3%时,形成了大量的CNT团聚,力学性能迅速下降.CNT/A1复合材料的主要强化机制为细晶强化和载荷传递.     

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。     

Electrochemical characteristics of amorphous MgTixNi （x = 0,0.1, and 0.2） hydrogen storage alloys

MgTi _x Ni (x = 0, 0.1, and 0.2) alloys were successfully prepared by mechanical alloying (MA), and the influence of milling time on the electrochemical characteristics of the electrodes was discussed. MgTi _x Ni alloys after 90 h milling displayed the best electrochemical performance. The X-ray diffraction patterns showed that the alloy ball-milled for 90 h was amorphous with a widened diffraction peak. The charge-discharge tests indicated that these alloys had good electrochemical activation properties, and the MgTi_0.2Ni alloy electrode exhibited the best cycle performance. The initial discharge capacity of the MgTi_0.2Ni alloy reached up to 401.1 mAh·g⁻¹, and the retention rate of capacity was 31.0% after 30 cycles, much higher than that of MgNi (17.3%). The Tafel polarization curves revealed that Ti addition could enhance the anticorrosion performance of these alloys in alkali solution, which was responsible for the ameliorated cyclic stability of these alloy electrodes.     

Discharge Capacities of Mg1?x Nd x Ni (x?=?0, 0.05, 0.1, 0.2) Alloys Prepared by Mechanical Alloying

In this study, the Mg_1?x Nd _x Ni (x?=?0, 0.05, 0.1, and 0.2) alloys were prepared by mechanical alloying (MA), and their electrochemical properties were measured by simulated battery test. It is observed that the introduction of Nd can accelerate the formation of the amorphous structure of MgNi alloy. With the increasing milling time from 40 to 60?h, the initial discharge capacity of Mg_1?x Nd _x Ni (x?=?0, 0.05, 0.10, and 0.20) alloys increases gradually, while during the milling time from 60 to 70?h, it decreases. The maximum capacity of the Mg_1?x Nd _x Ni alloys is gradually reduced with increasing Nd content x. With the milling time t?=?60?h and x?=?0, the discharge capacity is increased up to 378.2?mAh/g. Experimental results show that partial substitution of Mg with Nd can improve cyclic stability of the amorphous MgNi sample at the expense of a reduction in the initial capacity.     

Enhanced Electrochemical Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Mg20Ni10-xCox (x=0-4) Alloys by Melt Spinning

In order to improve the electrochemical hydrogen storage performances of the Mg2Ni-type alloys, Ni in the alloy was partially substituted by element Co. The nanocrystalline and amorphous Mg20Ni10-xCox (x=0, 1, 2, 3, 4) alloys were prepared by melt-spinning technology. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The electrochemical hydrogen storage characteristics of the alloys were measured. The results show that the substitution of Co for Ni leads to the formation of secondary phase MgCo2 without altering the major phase of Mg2Ni. No amorphous phase is detected in the as-spun alloy (x=0), whereas the as-spun alloy (x=4) holds a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni significantly increases the glass forming ability of the Mg2Ni-type alloy. The substitution of Co for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, including the discharge capacity and the cycle stability, for which the increased glass forming ability by Co substitution is mainly responsible     

Mg-Ni-Y-La非晶合金微观结构转变及电化学性能研究（英文）EI北大核心CSCD

采用铜模喷铸法制备了Mg60Ni23.6Y0.5La15.9块体非晶合金,并对其微观组织结构及电化学性能进行了研究。用XRD和SEM对Mg60Ni23.6Y0.5La15.9非晶合金在充放电过程中的微观结构进行分析。采用自动充放电测试系统对Mg60Ni23.6Y0.5La15.9非晶合金电化学性能进行了测试。结果表明:在吸氢放氢过程中合金的非晶态结构逐步转变为晶态,并且随着循环的进行逐渐形成了Mg2Ni H4、Mg2Ni和Mg(OH)2相。电化学性能测试结果表明:Mg60Ni23.6Y0.5La15.9非晶合金电极的放电容量变化过程可以分为4个阶段,其最大放电容量达到410.5m Ah/g,从而说明非晶结构有可能是非晶电极达到最大放电容量的关键因素。     

快淬纳米晶和非晶Mg_(20)Ni_(10-x)Co_x(x=0～4)合金的贮氢性能(英文)EI北大核心CSCD

为了改善Mg2Ni型合金的贮氢性能,采用Co部分替代合金中的Ni以及快淬工艺制备了纳米晶和非晶态Mg20Ni10-xCox(x=0,1,2,3,4)贮氢合金。用XRD、SEM、HRTEM分析了铸态及快淬态合金的微观结构,并测试了合金的气态吸/放氢动力学及电化学贮氢性能。结果表明,在快淬无Co合金中没有形成非晶相,但快淬含Co合金中形成一定量的非晶相。Co替代Ni及快淬处理显著地改善了合金的气态吸放氢性能。同时,Co替代Ni也显著地提高了快淬态合金的放电容量和电化学循环稳定性。     

Phase-structure and Hydrogen Storage Behaviors of Mg+10% Ni2P Composite Prepared by Reactive Ball-Milling

采用反应球磨法制备了Mg+10%Ni2P(质量分数,下同)新型复合物,对比研究了球磨复合物和球磨纯镁的相结构与储氢性能。研究表明:在纯Mg中添加10%的Ni2P进行复合球磨,可以明显提高其吸/放氢性能。此外,添加Ni2P球磨明显地改善了镁的循环放氢性能。复合物的晶粒尺寸随着球磨时间的增加而减小;添加Ni2P能有效地抑制Mg/MgH2在吸/放氢过程中产生团聚;在Mg中添加Ni2P球磨能降低体系的放氢反应温度。     

Hydrogen storage behavior of nanocrystalline and amorphous La–Mg–Ni-based LaMg12-type alloys synthesized by mechanical milling

Nanocrystalline and amorphous LaMg₁₁Ni+x% Ni (x=100, 200, mass fraction) alloys were synthesized by mechanical milling. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. The gaseous hydrogen absorption and desorption properties were investigated by Sievert's apparatus and differential scanning calorimeter (DSC) connected with a H₂ detector. The results indicated that increasing Ni content significantly improves the gaseous and electrochemical hydrogen storage performances of the as-milled alloys. The gaseous hydrogen absorption capacities and absorption rates of the as-milled alloys have the maximum values with the variation of the milling time. But the hydrogen desorption kinetics of the alloys always increases with the extending of milling time. In addition, the electrochemical discharge capacity and high rate discharge (HRD) ability of the as-milled alloys both increase first and then decrease with milling time prolonging.