稀土—镁储氢合金的四氢呋喃球磨改性研究
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摘要
本文首先全面评述了国内外关于镁基储氢合金的研究进展，在此基础上，选取了REMg_(11)Ni(RE=La，Ce)和CeMg_(12)两种重要的稀土—镁基储氢合金为研究对象，在四氢呋喃中对合金进行球磨改性处理，研究了改性处理对合金相结构、微观形貌、表面状态和吸放氢动力学性能的影响及相关机制。
研究表明，在四氢呋喃中机械球磨改性的REMg_(11)Ni(RE=La、Ce)和CeMg_(12)合金XRD衍射峰出现了明显的宽化和减弱，并随着球磨时间的增加而愈发明显。LaMg_(11)Ni的微观形貌显示粒子的体积逐渐变小，合金颗粒的尖锐度随球磨时间的增加而降低。球磨改性也降低了CeMg_(12)合金试样亚粒子颗粒大小。
改性后的LaMg_(11)Ni和CeMg_(12)合金表面AES深度分析结果表明，球磨试样最表面RE成分浓度没有明显降低，也无其它合金成分元素的富集，表面的氧化膜发生了变化，改性合金表面的氧化镁层深入合金内表面。根据XPS表面分析，合金的最表面由氢氧化物组成，原表面致密的氧化物层发生的变化有利于吸放氢动力学性能的改善，同时，四氢呋喃球磨过程导致合金表面与有机物中的碳原子发生电荷转移，显著提高了表面活性。
活化性能及吸氢动力学性能测试表明，经过THF球磨改性后，试样的表面活性大为改善，并随着球磨时间的增加合金的活化性能和吸氢动力学性能随之提高，吸氢量和放氢性能也相应改善。球磨20h的LaMg_(11)Ni、CeMg_(11)Ni和CeMg_(12)合金试样在448K、3.2MPa氢压下一次吸放氢即可活化，吸氢量分别达到3.5wt％、4.3wt％和5.3wt％，即使在室温条件下吸氢量也分别达到了2.0wt％、1.5wt％和0.98wt％。THF中球磨20h的CeMg_(12)合金试样在600K，30分钟内放氢量达到5.0wt％，为饱和吸氢量的90％以上。
In this thesis, the research and development on Mg-based hydrogen storage alloys (HSAs) have been reviewed. REMguNi (RE=La, Ce) and CeMg12 alloys were modified by mechanical grinding in tetrahydrofuran (THF). The influences of mechanical grinding (MG) modification on the structure, morphology, surface state and hydriding properties of these two series of Mg-based hydrogen storage alloys have been investigated and the related mechanisms have been discussed.
XRD analysis results indicated that the diffraction peaks were all weakened and broadened with increased milling time. SEM observation results showed that the particle sizes of the alloys reduced and the sharpness of the alloy particles decreased with increasing milling time.
From AES depth profiles analysis, no significant change of RE concentration and no enrichment of alloying elements were formed. XPS analysis results indicated that the surface oxides were changed into hydroxides after modification. It was believed that the improvement of the activation and hydriding properties of the modified alloys was mainly caused by the change of the structure of the surface. The surface activity of hydrogen storage alloys was improved by the charge transfer between the surface element of alloys and the carbon atoms of THF during mechanical milling.
The activation properties and hydriding behaviors are remarkably improved after MG modification in THF. Under the conditions of 448K and 3.2MPa, no activation process is needed for LaMgnNi, CeMgnNi and CeMgi2, which were milled in THF for 20h, and the hydrogen absorption amounts reached 3.5wt%, 4.3wt% and 5.3wt% separately. Even at room temperature the three modified alloys can absorb hydrogen to 2.0wt%, 1.5wt% and 0.98wt%. The desorption rates are also improved significantly by the MG modification in THF. For the CeMgi2 alloys modified in THF for 20h, 5.0wt% of hydrogen was released at look within 30min at 600K, which was more than 90 percent of the absorbed hydrogen.
研究表明，在四氢呋喃中机械球磨改性的REMg_(11)Ni(RE=La、Ce)和CeMg_(12)合金XRD衍射峰出现了明显的宽化和减弱，并随着球磨时间的增加而愈发明显。LaMg_(11)Ni的微观形貌显示粒子的体积逐渐变小，合金颗粒的尖锐度随球磨时间的增加而降低。球磨改性也降低了CeMg_(12)合金试样亚粒子颗粒大小。
改性后的LaMg_(11)Ni和CeMg_(12)合金表面AES深度分析结果表明，球磨试样最表面RE成分浓度没有明显降低，也无其它合金成分元素的富集，表面的氧化膜发生了变化，改性合金表面的氧化镁层深入合金内表面。根据XPS表面分析，合金的最表面由氢氧化物组成，原表面致密的氧化物层发生的变化有利于吸放氢动力学性能的改善，同时，四氢呋喃球磨过程导致合金表面与有机物中的碳原子发生电荷转移，显著提高了表面活性。
活化性能及吸氢动力学性能测试表明，经过THF球磨改性后，试样的表面活性大为改善，并随着球磨时间的增加合金的活化性能和吸氢动力学性能随之提高，吸氢量和放氢性能也相应改善。球磨20h的LaMg_(11)Ni、CeMg_(11)Ni和CeMg_(12)合金试样在448K、3.2MPa氢压下一次吸放氢即可活化，吸氢量分别达到3.5wt％、4.3wt％和5.3wt％，即使在室温条件下吸氢量也分别达到了2.0wt％、1.5wt％和0.98wt％。THF中球磨20h的CeMg_(12)合金试样在600K，30分钟内放氢量达到5.0wt％，为饱和吸氢量的90％以上。
In this thesis, the research and development on Mg-based hydrogen storage alloys (HSAs) have been reviewed. REMguNi (RE=La, Ce) and CeMg12 alloys were modified by mechanical grinding in tetrahydrofuran (THF). The influences of mechanical grinding (MG) modification on the structure, morphology, surface state and hydriding properties of these two series of Mg-based hydrogen storage alloys have been investigated and the related mechanisms have been discussed.
XRD analysis results indicated that the diffraction peaks were all weakened and broadened with increased milling time. SEM observation results showed that the particle sizes of the alloys reduced and the sharpness of the alloy particles decreased with increasing milling time.
From AES depth profiles analysis, no significant change of RE concentration and no enrichment of alloying elements were formed. XPS analysis results indicated that the surface oxides were changed into hydroxides after modification. It was believed that the improvement of the activation and hydriding properties of the modified alloys was mainly caused by the change of the structure of the surface. The surface activity of hydrogen storage alloys was improved by the charge transfer between the surface element of alloys and the carbon atoms of THF during mechanical milling.
The activation properties and hydriding behaviors are remarkably improved after MG modification in THF. Under the conditions of 448K and 3.2MPa, no activation process is needed for LaMgnNi, CeMgnNi and CeMgi2, which were milled in THF for 20h, and the hydrogen absorption amounts reached 3.5wt%, 4.3wt% and 5.3wt% separately. Even at room temperature the three modified alloys can absorb hydrogen to 2.0wt%, 1.5wt% and 0.98wt%. The desorption rates are also improved significantly by the MG modification in THF. For the CeMgi2 alloys modified in THF for 20h, 5.0wt% of hydrogen was released at look within 30min at 600K, which was more than 90 percent of the absorbed hydrogen.
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