A2B7型La0.75Mg0.25Ni3.5-xCrx(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCrx(x=0,0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B端Cr元素对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5合金是由La2Ni7相组成.随着Cr元素的加入,该类合金中出现LaNi5相及LaNi3相,且随着Cr含量的增加而增多.电化学测试表明,随Cr含量的增加,合金电极活化次数变化不大,最大放电容量逐步降低,合金的最大放电容量由x=0.05时的383.43 mAh/g下降到x=0.3时的348.40 mAh/g;而合金的高倍率放电性能呈现先增后减的趋势,当电流密度为900 mA/g时,合金的高倍率放电性能由83.66%(x=0)增加到92.57%(x=0.05)然后减小到83.9%(x=0.3);循环稳定性先增加后下降,当x=0.1时合金电极的循环寿命达到最大(S100=74.71%).     

La1-x Cex Ni3．54 CO0．78 Mn0．35 A10．32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-x Cex Ni3．54 CO0．78 Mn0．35 A10．32（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-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310．1mAh／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z的增大先增大后减小．     

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。     

铸态及快淬态La2Mg(Ni0.85Co0.15)9Crx(x=0～0.4)贮氢合金的电化学性能

为了提高La-Mg-Ni系(PuNi3型)贮氢合金的电化学循环稳定性,在La2Mg(Ni0.85Co0.15)9合金中加入微量Cr,用铸造及快淬工艺制备了La2Mg(Ni0.85Co0.15)9Crx(x=0,0.1,0.2,0.3,0.4)贮氢合金.研究了Cr含量对铸态及快淬态合金微观结构及电化学性能的影响.XRD,SEM及TEM的分析结果表明,铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相(PuNi3型结构)、LaNi5相和一定量的LaNi2相.随Cr含量的增加,铸态合金中LaNi2相的量增加.电化学测试结果表明,Cr的加入提高了铸态及快淬态合金的循环稳定性,但使合金的容量下降.当Cr添加量从0增加到0.4时,铸态合金的容量从396.3 mAh/g下降到355.6 mAh/g,循环寿命从72次增加到97次;快淬态(30 m/s)合金的容量从364.2 mAh/g下降到334.2 mAh/g,循环寿命从100次增加到131次.Cr添加使铸态合金的放电电压特性和活化性能得到改善.     

(LaCa3)0.5-xMg1+4xNi9(x=0,0.02,0.04,0.06,0.08,0.1)合金微观结构及储氢性能研究

AB₃型La-Mg-Ni系列储氢合金由于储氢容量优异、放电容量高、活化快等优势受到储能领域的关注.采用真空感应熔炼法制备了(LaCa₃)_0.5-xMg_1+4xNi₉(x=0,0.02,0.04,0.06,0.08,0.1)合金,表征合金的微观结构并测试储氢合金性能差异,研究合金A侧元素比例对合金性能影响的内在机理.合金活化性能受Mg元素取代量的影响明显,活化吸放氢速率随着Mg质量分数的增加先增加后减小.随着Mg替代量的增加,合金的最大吸放氢容量分别由1.866%和1.311%提高到1.972%和1.732%,吸放氢焓变绝对值分别由15.71 kJ/mol和17.88 kJ/mol降低到8.88 kJ/mol和9.28 kJ/mol,其热稳定性降低,这对改善热力学性能有积极作用.     

LaNi_(3.15-x)Mn_xCo_(0.25)Al_(0.1)储氢合金结构及电化学性能

为了研究Mn替代Ni对AB3.5型储氢合金结构及电化学性能的影响,采用电弧炉熔炼制备LaNi3.15-xMnxCo0.25Al0.1合金。采用XRD、SEM等材料分析方法以及恒电流充放电等电化学测试技术,研究LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金的结构和电化学储氢性能。结果表明:LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金由多相组合形成,合金的主相为LaNi5和La2Ni7;随着Mn替代Ni含量的增加,LaNi5相中a轴和c轴以及晶胞体积增加;合金电极的最大放电容量有所升高,由x=0的238mA·h/g逐渐增加到x=0.3的277.1mA·h/g;高倍率性能随着Mn含量的增加先升高后降低,在x=0.2时合金的高倍率性能最佳。     

LaNi4.1-xCo0.6Mn0.3Alx储氢合金结构及电化学储氢性能研究

为改善LaNi4.1 Co0.6 Mn0.3储氢合金的性能,研究了系列LaNi4.1-xCo0.6Mn0.3Alx(x=0,0.15,0.3,0.45)合金的结构和电化学储氢性能.结果表明:制备的合金为典型CaCu5型AB5储氢合金,随着A1替代量增加,LaNi5相的晶胞参数a、c、c/a值和晶胞体积逐渐增大,相应合金的放电容量有所降低,但合金电极的循环稳定性和不可逆自放电和高温容量得到明显改善.60个循环后的容量保持率(S60)分别为58.79％ (x=0)、79.72％(x=0.3)、79.35％(x=0.45);合金电极不可逆容量损失率(贮存96 h)由14.41％(x=0)降到2.38％ (x=0.45).在323 K的放电容量由266.04mA·h/g(x=0)增加到302.4mA·h/g(x=0.15)、302.12mA·h/g(x=0.3)和299.88 mA·h/g(x=0.45).但Al替代Ni后,合金电极的交换电流密度I0和氢原子在合金内部的氢扩散系数DH降低,导致其高倍率放电性能变差.     

AlCrFeNi2Cu高熵合金组织及性能x

为了分析Cu元素添加对高熵合金显微组织与微观性能的影响,采用真空电弧熔炼炉制备AlCrFeNi₂Cu_{=1.2,1.4,1.6,1.8)高熵合金,并利用扫描电子显微镜、X射线衍射仪、硬度计和压缩试验机对高熵合金的显微组织和力学性能进行测试.结果表明,AlCrFeNi2Cu=1.2,1.4,1.6,1.8)高熵合金主要由简单FCC相(富Fe-Cr相)与BCC相(富Al-Ni相)组成.随着Cu含量的增加,FCC相数量增加,组织中枝晶变得致密,但当x增加到1.8时,晶粒又变得粗大起来.Cu元素主要富集于枝晶间,随着Cu含量的增加,Cu元素呈现聚集趋势并包裹着树枝晶,当x增至1.8时,上述偏聚包裹现象更为明显.高熵合金的压缩性能和硬度均随Cu元素的添加呈现先上升后下降的趋势.当x为1.6时,高熵合金综合性能最佳,其抗压强度、屈服强度、塑性应变量和维氏硬度分别为2 256 MPa、891 MPa、35.6%和372 HV.x(x}x(x     

CoFeNiMn(TixC100-x)0.25高熵合金的微观组织与力学性能

为改善CoFeNiMn高熵合金的力学性能,文中采用电弧熔炼和铜模喷铸法制备了不同Ti、C含量的CoFeNiMn(Ti_xC_100-x)_0.25 (x分别为20,30,40,60,70,80)高熵合金。利用X射线衍射仪(XRD)、扫描电镜(SEM)、万能试验机等检测并分析了CoFeNiMn(Ti_xC_100-x)_0.25合金的显微组织与力学性能。研究结果表明：当x=20时,合金组织呈典型的树枝状,未发现TiC颗粒存在;当x≥30后,合金结构由FCC和TiC两相所组成,TiC颗粒均匀的分布于合金内部;添加Ti、C元素后,CoFeNiMn(Ti_xC_100-x)_0.25合金仍然保持良好的塑性,随合金中x值的增加,合金的屈服强度在x=20时为302 MPa,x=30时增加至370 MPa, x=80时则减小至204 MP;而合金的硬度则先减小后增加,x=20时硬度为297 HV_0.3...     

La0.75Mg0.25Ni3.1-xCo0.3Al0.1Six（x=0.000.20）贮氢合金电化学性能研究

采用中频感应炉熔炼制备铸态La0.75Mg0.25Ni3.1-x Co0.3Al0.1Si x(x=0.00~0.2)合金,通过调控Si的成分,研究Si元素替代Ni对合金电化学性能的影响.研究表明,随着Si替代量增加,合金活化性能基本不变,最大电化学放电容量随Si含量的增加呈线性下降的关系,电化学放电平台压力逐渐降低,电化学循环稳定性得到有效提高.     

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.     

Electrochemical properties of Co-S/x wt.% AB_5 composite materials

The Co-S/x wt.% AB5(x=0,10,20,30) composite materials were prepared by simply mixing Co-S material fabricated by hydrothermal method and AB5 alloy.The structure and morphology of the composite materials were characterized by XRD and SEM,respectively.The electrochemical properties of the composite electrodes were studied by the galvanostatic charge,discharge test and electrochemical impedance spectroscopy.The results showed that the Co-S/20 wt.% AB5 composite electrode showed the highest discharge capacity and the best cycling stability.The existence of the AB5 alloy improved the electrochemical activity of composite electrodes,reduced the electrochemical polarization resistances and promoted the electrochemical conversion reaction between Co and Co(OH)2.In order to improve the utilization rate of active materials,0.01 mol/L Na2S2O3 was added into the electrolyte.The electrochemical properties of the composite electrode were significantly enhanced.After fifty cycles,the discharge capacity of the composite electrode increased from 407 to 481.7 m Ah/g and the capacity retention increased from 79.7% to 91.2%.     

Electrochemical Hydrogen Storage Performance of the Nanocrystalline and Amorphous Pr-Mg-Ni-based Alloys Synthesized by Mechanical Milling

The PrMg12-type composite alloy of PrMg₁₁Ni + x wt% Ni (x=100,200) with an amorphous and nanocrystalline microstructure were synthesized through the mechanical milling.Effects of milling duration and Ni content on the microstructures and electrochemical hydrogen storage performances of the ball-milled alloys were methodically studied.The ball-milled alloys obtain the optimum discharge capacities at the first cycle.Increasing Ni content dramatically enhances the electrochemical property of alloys.Milling time varying may obviously impact the electrochemical performance of these alloys.The discharge capacities show a significant upward trend with milling duration prolonging,but milling for a longer time more than 40 h induces a slight decrease in the discharge capacity of the x=200 alloy.As milling duration increases,the cycle stability clearly lowers,while it first declines and then augments under the same condition for the x=200 alloy.The high-rate discharge abilities of the ball-milled alloys show the optimum values with milling time varying.     

不同放电深度下LaNi3.8Co0.6Mn0.3Al0.3合金的电化学行为研究

为了分析储氢合金放电过程中的电化学反应与动力学变化规律,采用电化学交流阻抗分析方法研究 La-Ni3.8Co0.6Mn0.3Al0.3合金电极在不同放电深度下的电化学行为.结果表明:随着放电深度的增加,电极表面活性氢覆盖面积S 及内部金属颗粒间接触电阻Rpp逐渐降低,即电极的导电性增加;此外,交换电流密度Io也随放电深度增加而增大,意味着电极表面反应速率加快,同时氢扩散系数 DH 明显降低;合金电极动力学在放电前期主要由电极表面反应速率控制,后期由电极中氢原子在合金颗粒内部的氢扩散系数控制.     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg_(12)-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_(12)-type LaMg_(11)Ni + 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 H_2 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.     

超级电容器PANI/MnO2 复合材料电极的制备及性能研究

通过回收废旧三元锂电池正极材料中的Mn 制备超级电容器PANI/MnO₂ 复合电极材料, 实现废旧材料的资源化, 符合绿色化学的发展要求。主要探索了两种不同氧化剂(KMnO₄ 和APS) 对PANI/MnO₂ 复合材料形貌和电化学性能的影响, 由实验结果可知, 在KMnO₄ 氧化条件下制备的具有空隙的针棒状复合材料PANI/MnO₂ -1 的电化学性能明显略优。PANI/MnO₂ -1 作为电极时的比电容可达2 183 F/g, 充放电100 圈后比电容仍具有初始值的60.81%, 循环稳定性较好, 是一种性质优良的超级电容器电极材料。结果表明实验设计的废旧三元锂电池回收再利用方法切实可行, 为超级电容器PANI/MnO₂ 复合材料电极的制备提供了新的研究思路。