Microstructure and electrochemical properties of ball-milled AB5+x%VFe alloys
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摘要: 采用机械球磨方法制备了MlNi3.55Co0.75Mn0.4Al0.3+x%VFe（质量分数，x=5，10，15，20）储氢合金，研究了合金晶体结构和电化学性能。微结构分析表明，主相AB5晶胞参数a及体积V随球磨时间增加而增加。电化学研究表明，合金的最大容量Cmax及氢扩散系数D随x增加先增加后减少， x=10时达到最大值，分别为310 mAh/g和 7.6×10−11 cm2/s。对合金进行了循环稳定性测试，结果表明，MlNi3.55Co0.75Mn0.4Al0.3+10%VFe球磨10 h的合金在100次循环后放电容量保持率为98%。Abstract: The MlNi3.55Co0.75Mn0.4Al0.3+x%VFe(x=5, 10, 15, 20) composite hydrogen storage alloys were synthesized by mechanical ball-milling. The microstructure and electrochemical properties of the composites were investigated. The microstructure analysis indicates that the parameters a and V of the main phase increase with the increase of milling time. The electrochemical analysis indicates that, with increasing VFe content x, the maximum capacity Cmax and the hydrogen diffusion coefficient D of the alloy first increase and then decrease, and reach the maximum of 310 mAh/g and 7.6×10−11 cm2/s with x=10. The cycle stability test was carried out on the alloy, and the results show that the discharge capacity retention rate of MlNi3.55Co0.75Mn0.4Al0.3+10%VFe ball-milled for 10 h was 98% after 100 cycles.
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Key words:
- hydrogen storage alloy /
- AB5 alloy /
- 80VFe /
- ball milling /
- electrochemical properties
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图 3 AB5+x%VFe复合储氢合金SEM图像
Figure 3. SEM images of ball-milled (15 h) MlNi3.55Co0.75Mn0.4Al0.3+x%VFe composites
图 4 AB5+10%VFe储氢合金电子显微镜图像
Figure 4. SEM images of ball-milled MlNi3.55Co0.75Mn0.4Al0.3+10%VFe composites for different time
图 5 AB5+10%VFe球磨15 h复合型储氢合金SEM及EDS分析
Figure 5. SEM images and EDS spectra of ball-milled (15 h) MlNi3.55Co0.75Mn0.4Al0.3+10%VFe composites
图 9 合金样品100次循环的容量保持率
Figure 9. Discharge capacity retention of the alloys after 100 charge-discharge cycles
表 1 AB5+xVFe合金的晶胞参数
Table 1. Lattice parameters of AB5+xVFe alloy
x/% t/h a/nm c/nm V/nm3 c/a 原合金 0.4921(9) 0.4276(5) 0.089721(3) 0.868(1) 5 0 0.4920(5) 0.4275(6) 0.089649(1) 0.868(1) 5 5 0.4923(1) 0.4274(5) 0.089717(2) 0.868(1) 5 10 0.4930(1) 0.4274(1) 0.089965(6) 0.866(3) 5 15 0.4930(5) 0.4274(2) 0.089984(4) 0.866(1) 5 20 0.5041(1) 0.4273(8) 0.094054(1) 0.847(8) 10 0 0.4918(9) 0.4274(5) 0.089567(8) 0.869(1) 10 5 0.4923(2) 0.4274(5) 0.090089(3) 0.868(2) 10 10 0.4924(2) 0.4275(4) 0.089760(9) 0.868(2) 10 15 0.4927(7) 0.4275(1) 0.089899(1) 0.867(5) 10 20 0.5056(2) 0.4280(1) 0.094761(7) 0.868(1) 15 0 0.4919(5) 0.4275(5) 0.089610(6) 0.869(1) 15 5 0.4925(6) 0.4273(6) 0.089793(1) 0.867(6) 15 10 0.4926(1) 0.4276(4) 0.089866(5) 0.868(1) 15 15 0.4931(1) 0.4280(4) 0.090133(2) 0.868(1) 15 20 0.5070(1) 0.4226(5) 0.094086(1) 0.833(6) 
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表 2 AB5+10%VFe球磨15 h的EDS结果
Table 2. EDS results of AB5+10%VFe ball-milled 15 h
元素 复合相 基体相 w/% y/% w/% y/% La 8.95 3.66 28.76 11.49 Ni 17.44 16.87 48.63 45.96 Co 3.27 3.15 10.32 9.71 Mn 4.21 4.35 4.21 4.26 Al 1.17 2.46 3.40 6.98 V 33.56 37.40 Fe 28.76 29.23
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