La0.7Zr0.1Mg0.2Ni3.4-xCoxFe0.1合金的制备与电化学性能研究

在氩气保护下采用电磁感应熔炼制备La0.7Zr0.1Mg0.2Ni3.4-xCoxFe0.1（x=0.15,0.25,0.35,0.45）合金,研究合金的相结构,以及Co元素部分取代Ni元素对合金的气态储氢性能和电化学性能的影响。结果表明,合金主要由LaNi5、LaNi2以及La2MgNi9相组成。合金电极的最大放电容量分别为346.7mAh/g（x=0.15）、320.3mAh/g（x=0.25）、363.0mAh/g（x=0.35）和313.3mAh/g（x=0.45）,经过65个充放电循环后,合金电极的容量保持率从63.0%（x=0.15）增加到80.2%（x=0.35）,然后再下降到75.0%（x=0.45）。La0.7Zr0.1Mg0.2Ni3.15Co0.25Fe0.1合金具有较高的高倍率放电性能（HRD1200%=67.3）和较大的极限电流密度（IL=386.8 mA/g）,显示出其良好的电化学动力学性能。     

Ti对La_(0.7-x)Ti_xMg_(0.3)Ni_(3.5)(x=0.00,0.05,0.10)合金电极电化学性能的影响

在氩气保护下用悬浮熔炼制备La0.7-xTixMg0.3Ni3.5(x=0.00,0.05,0.10)储氢合金,研究Ti含量对合金电极电化学性能的影响。X射线衍射(XRD)分析表明,合金相主要由LaNi5、LaMg2Ni9和La2Ni3相组成。当x=0.10时,合金中有TiNi3相产生,随着Ti含量的增加,LaNi5、LaMg2Ni9和La2Ni3相的晶胞体积减小。电化学性能测试表明,合金电极最大放电容量分别为370 mAh/g(x=0.00)、331 mAh/g(x=0.05)和252 mAh/g(x=0.10);合金电极循环伏安特性曲线氧化峰电位随着Ti含量的增加而降低,表明Ti的加入使合金电极易于发生氧化反应。     

La0.6CexNd0.4-xNi3.0Co0.2Al0.3(x=0~0.4)合金储氢性能研究

采用电弧炉熔炼方法制备La0.6CexNd0.4-xNi3.0Co0.2Al0.3(x=0～0.4)系列合金,并对合金的储氢性能和电化学性能进行测试。测试结果表明,合金在Ce=0时具有最高的电化学容量(284.2mAh/g)和储氢量(0.93wt%)。Ce的添加会降低合金放电容量,但是能够改善合金的循环稳定性能。     

La-Mg-Ni基合金储氢性能的研究

采用高频感应熔炼制备La0.7Ca0.3Ni2.8-xMgx(x=0.1、0.2、0.3、0.4)合金,进行X射线衍射(XRD)实验,气相储氢性能测试和电化学性能测试,分析Mg部分替代Ni对合金的储氢和电化学性能的影响。分析结果表明,合金具有多相结构,当x=0.1、0.3时,合金的主相是CaCu5-型结构的LaNi5相,当x=0.2、0.4时,合金的主相是AB2-型Laves相LaNi2相。随x=0.1、0.2、0.3、0.4合金电极的放电容量(mAh/g)依次为244.7、140.8、257.6、164。当x=0.1时,在2MPa氢压、25℃时,合金La0.7Ca0.3Ni2.7Mg0.1的储氢量达到1.1wt%。     

导电剂镍粉对La0.7Mg0.3Ni2.6Co0.7合金电极电化学性能的影响

采用放电容量、循环寿命、伏安特性、高倍率放电、交流阻抗等方法研究不同导电剂镍粉含量对La0.7Mg0.3Ni2.6Co0.7合金电极电化学性能的影响。结果表明:La0.7Mg0.3Ni2.6Co0.7+xwt%Ni(x=0.0,5.0,7.5,10.0,12.5)合金电极的放电容量分别为388.0、410.7、409.6、412.2、421.3 mAh/g,高倍率放电性能HRD1200从40.2%(x=0.0)增大到75.7%(x=12.5),同时合金电极的电荷转移阻抗明显降低,添加导电剂镍粉有利于电流在电极中分布趋于均匀化,增大了活性物质的填充量,促使合金电极的放电容量增加。电荷转移阻抗的降低有利于氢原子在合金内部扩散,从而有效地改善合金电极的高倍率放电性能。     

稀土Ce对无Co过计量比CaCu_5型合金贮氢和电化学性能的影响

采用单辊甩带快速凝固方法制备过化学计量比稀土贮氢合金La1-xCexNi4.17Mn0.93Al0.1Fe0.4(AB5.6型,x=0~0.5),研究Ce元素部分替代La后对合金微观结构、储氢及电化学性能的影响.XRD分析及储氢性能测试结果表明,快淬过化学计量比合金的相组织均为过饱和CaCu5型结构单相,合金晶胞体积与Ce质量分数基本呈线性关系,其中合金的储氢量随Ce质量分数的增加而减小,而吸放氢平台压力增高.电化学测试和分析结果表明,随Ce质量分数的增加,合金电极的活化性能和放电容量有所降低,但电极循环寿命得到明显提高.当x=0、0.5时,合金电极的最大放电容量为328.9、305.4 mAh/g;当x≥0.3时,经100次循环后,合金电极容量保持率S100由x=0时的80%提高至93%~96%;合金电极的高倍率放电性能(HRD)随Ce质量分数的增加呈先减小后增加的趋势.     

TiFe_(0.9-x)Ni_xZr_(0.1)Mn_(0.2)(x=0.1,0.2,0.3,0.4)合金的贮氢性能研究

采用高频感应熔炼法制备TiFe0.9-xNixZr0.1Mn0.2(x=0.1,0.2,0.3,0.4)合金,系统地研究Ni部分取代Fe对TiFe0.9-xNixZr0.1Mn0.2(x=0.1,0.2,0.3,0.4)合金相组成与贮氢性能的影响。XRD分析结果表明:合金主要由NiTi,FeTi和(Fe,Ni)相组成,在x=0.1~0.2时,有少量的FeZr2相,随着Ni含量的增加,FeZr2相消失,同时有TiMn2相产生。压强—成分—温度(PCT)测试结果表明,TiFe0.6Ni0.3Zr0.1Mn0.2合金的贮氢量最高,其吸氢量为1.46 wt%。电化学测试结果显示,合金电极放电容量随着Ni含量的增加而增大,TiFe0.8Ni0.1Zr0.1Mn0.2合金的放电容量为34 mAh/g,而TiFe0.5Ni0.4Zr0.1Mn0.2合金电极的放电容量则达156 mAh/g。     

La0.7Mg0.3Ni3.4-x(Al0.3Co0.4)0.2+x(x=0~0.3)合金电极电化学性能研究

在氩气保护下,采用悬浮熔炼法制备La0.7Mg0.3Ni3.4（Al0.3Co0.7）x（x=0,0.2,0.4,0.6）储氢合金,用X射线衍射仪测试相组成,并用MDI Jade 5.0软件分析相组成和晶胞参数,用开口三电极法测试电极电化学性能。结果表明,合金相主要由LaNi5、LaMg2Ni9、La2Ni7和LaNi2.28相组成,随着合金中Al和Co含量的增加,合金放氢平台压下降,最大吸氢量为1.43%（x=0）,合金电极最大放电容量Cmax为381mA.h.g-1（x=0）,合金电极100个充放循环后的容量保持率S100从53.0%（x=0）增加到57.1%（x=0.3）,循环稳定性增强。当x=0.1时,合金电极的电化学动力学性能较好。     

La-Ni-Al合金电极电化学性能研究

研究了两种不同配比La-Ni-Al的储氢合金电极的电化学性能。测试结果表明,LaNi4.061Al0.222储氢合金的最大放电容量为292mAh·g1(303 K),且具有较好的倍率性能。同时研究了Zr的添加对LaNi4.061Al0.222Zr(=0-0.2)储氢合金电极电化学性能的影响。结果表明,=0.2时,储氢合金电极具有最大的放电容量309.9mAH·g-1和高倍率放电性能。     

元素Mn、V对AB2型贮氢电极合金ZrCr0.7Ni1.3相结构和电化学性质的影响

研究了Mn、V部分替代ZrCr0.7Ni1.3合金中的Cr元素后对其相组成、晶格常数和电化学容量等方面的影响.结果表明:母体合金的主相由立方C15型Laves相和少量六方C14型Laves相组成并含有少量第二相Zr7Ni10.对于合金ZrCr0.7-xMxNi1.3(x=0.1～0.6)(M=Mn或V),在Mn、V单独替代时,随着Mn替代量的增加,第二相Zr7Ni10峰逐渐减弱,合金电化学容量先增加后降低,在x=0.2时放电容量最大;随着V含量的增加,合金的主相向C14型Laves相转化,而第二相Zr7Ni10峰消失,并出现新的第二相Zr9Ni11衍射峰,合金的电化学容量迅速降低;当Mn、V同时进行替代时,对于合金ZrCr0.7-x-yMnxVyNi1.3(x+y=0.2～0.4),其相组成和晶格常数的变化不大,但电化学容量却有较大变化,当合金成分为ZrCr0.4Mn0.1V0.2Ni1.3时,放电容量最高,为311 mAh/g.     

Hydrogen storage and low-temperature electrochemical performances of A2B7 type La-Mg-Ni-Co-Al-Mo alloys

The effect of Mo-addition on hydrogen storage and low-temperature electrochemical performances of La-Mg-Ni-Co-Al alloys is investigated. The alloys were synthetized via vacuum induction melting followed by annealing treatment at 1123 K for 8 h. The major phases in the annealed alloys are consisted of (La, Mg)2Ni7, (La, Mg)5Ni19 and LaNi5 phases. Mo-addition facilitates phase transformation of LaNi5 into (La, Mg)2Ni7 and (La, Mg)5Ni19 phases. Hydrogen absorption/desorption PCI curves indicates that the hydrogen storage capacity of the alloy increases remarkably with the addition of Mo. Furthermore, the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy shows excellent hydriding/dehydriding kinetics with a higher capacity, requiring only 100 s to reach its saturated hydrogen capacity of 1.58 wt% at low temperature of 303 K, and releasing 1.57 wt% hydrogen within 400 s at 338 K. Electrochemical experiments manifest that the Mo-added alloy electrode has perfect activation properties and the maximum discharge capacity. The low-temperature dischargeability shows that the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy exhibits the excellent low-temperature discharge performance, and the maximum discharge capacity is improved from 231.0 to 334.6 mAh/g at 253 K. The HRD property of the alloy electrode is enhanced, suggesting that Mo enhances the kinetic ability at low-temperature.     

热处理对贮氢电极合金La0.7Mg0.3Ni2.45Co0.75Mn0.1Al0.2的微结构与电化学性能的影响

研究了热处理时间对贮氢电极合金La0.7Mg0.3Ni2.45Co0.75Mn0.1Al0.2的微结构与电化学性能的影响。XRD分析结果表明,所有合金均由(La,Mg)Ni3与LaNi5两相构成,热处理并没有使该贮氢合金发生相变。电化学研究结果表明,随着热处理时间的延长,合金电极的最大放电容量与循环稳定性能均得到明显改善,而高倍率放电性能却逐渐恶化。     

Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-Mn_0.30Al_0.30)_x (x=0.68, 0.70, 0.72, 0.74, 0.76) alloys and Cu-substituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-y Cu_y Mn_0.30Al_0.30)_0.70 (y=0, 0.10, 0.30, 0.50) alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi₅ phase, a LaNi₃ phase, and a minor La₂Ni₇ phase; in addition, in the case of Cu-substitution, the Nd₂Ni₇ phase appears and the LaNi₃ phase vanishes. Thermodynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with increasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ameliorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.     

快淬Mg2Ni型合金的结构及贮氢动力学

用快淬技术制备Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金,用XRD,SEM和HRTEM分析合金的微观组织结构;测试合金的气态及电化学贮氢动力学。结果表明:快淬二元Mg2Ni合金具有典型的纳米晶结构,而快淬La替代合金明显地具有非晶结构,La替代Mg提高Mg2Ni型合金的非晶形成能力。La替代Mg明显地改变Mg2Ni型合金的相组成,当x=0.4时,合金的主相改变为(La,Mg)Ni3+LaMg3。快淬及La替代明显影响合金的气态及电化学贮氢动力学,La替代使合金的吸氢动力学先降低后增加,但使合金的气态脱氢及电化学贮氢动力学先增加后降低。快淬对合金气态及电化学贮氢动力学的影响与合金的成分相关,对于La0.4合金,合金的气态吸氢动力学随淬速的增加先增加后减小,其放氢动力学随淬速的增加而增加。     

锂离子电池正极材料LiFePO4的制备及电化学性能研究

∶采用高温固相法合成LiFePO4锂离子电池正极材料,为提高LiFePO4材料的电化学性能,对其进行Ti4 掺杂改性.用XRD、SEM等测试手段对材料进行表征,并对以Li1-xTixFePO4(x=0,0.01,0.03,0.05)为正极的电池进行电化学性能测试.研究表明,掺杂过程中,掺杂离子能与LiFePO4形成晶格完整、有序的单相固溶体;少量的掺杂离子还可以提高材料的电导率和电化学性能,特别是大电流放电性能,其中Li0.97Ti0.03FePO4性能最优,以0.2C5放电,首次放电质量比容量为132.0 mA.h/g,50次循环后仍保持为131.5 mA.h/g.     

稀土镧和钛取代镁基储氢合金电极电化学性能的研究

利用机械合金化方法制成了MgNi,Mg0.7Ti0.3Ni和Mg0.7Ti0.225 La0.075Ni非晶态镁基合金,XRD表明球磨100 h后已形成非晶;电化学容量测试表明:在此实验条件下添加Ti,La元素改善了电极的循环稳定性能.其中,La的取代提高了合金的抗腐蚀性能和合金的电化学氧化还原反应的可逆性能,进而提高...     

Microstructural evolution and performance of hydrogen storage and electrochemistry of Co-added La0.75Mg0.25Ni3.5−xCox (x = 0, 0.2, 0.5 at%) alloys

Microstructure, hydrogen storage and electrochemical performances of Co-added La_(0.75)Mg_(0.25)Ni_(3.5_x)Co_x(x = 0,0.2, 0.5 at%) alloys are studied. XRD and rietveld refinement results suggest that the samples are mainly composed of(LaMg)Ni_3,(LaMg)_2Ni_7 and LaNi_5 phases, Co substitution for Ni changes the phase abundance,but not the phase composition. With the rising of Co content, the amount of(LaMg)_2 Ni_7 phase decreases, but the amount of LaNi_5 phase increases, while the amount of(LaMg)Ni_3 phase firstly increases and then decreases.The alloys reversibly absorb and desorb hydrogen at 298 K smoothly. When Co content is 0.2 at%, the hydrogen absorption capacity reaches the maximum value of 1.14 H/M, and the absorption capacities reach 1.09 H/M and 1.03 H/M in the first minute at 298 K and 323 K, respectively. Electrochemical performance measurement results show that La_(0.75)Mg_(0.25)Ni_(3.5-x)Co_x alloys are completely activated within 2 cycles, and the cyclic stability of La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy approaches 63.7% after 100 charge/discharge cycles, which is higher than that(S_(100) = 60%) of La_(0.75)Mg_(0.25)Ni_(3.0)Co_(0.5) alloy. Thus, the La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy exhibits optimum comprehensive properties of hydrogen storage and electrochemistry.