D0:10.13374h.issn1001-053x.2011.07.012 第33卷第7期 北京科技大学学报 Vol.33 No.7 2011年7月 Journal of University of Science and Technology Beijing Jul.2011 低温球磨制备Mg4%Ni-1%NO储氢材料及其性能 李平)区王腾” 范丽珍) DIN Rafi-ud'2)曲选辉D 1)北京科技大学材料科学与工程学院，北京100083 2)巴基斯坦核科学与技术研究所化学部，伊斯兰堡，巴基斯坦 ☒通信作者，E-mail:liping@ustb.cdu.cm 摘要采用低温球磨技术制备了Mg4%N-1%NO储氢材料，主要研究低温球磨时间对材料形貌结构以及储氢性能的影 响.采用扫描电子显微镜(SEM)和X射线衍射(XRD)分析材料的形貌和相组成，采用压力一组成一温度(PC一T)设备研究材 料的储氢性能.结果表明：分别经过2、4和7h球磨后，材料的相组成没有发生明显改变，只有极少量的MgN合金相生成. 随着球磨时间的延长，材料的平均粒度逐渐下降，作为催化剂的N、O相逐渐揉进基体内部.伴随着上述变化，材料的活化 性能、吸氢性能逐渐提高，球磨到7h后材料仅需活化1次即可达到最大吸放氢速率，初始吸氢温度降为60℃，在4.0MP初 始氢压和200℃下吸氢量为6.4%（质量分数），60s即可完成饱和吸氢量的80%，10mn内完成饱和吸氢量的90%：材料的放 氢性能则在球磨4h后已经基本保持不变，0.1MPa下初始放氢温度为310℃，在350℃、0.1MPa下材料可在500s内释放饱和 储氢量的80% 关键词储氢材料：镁：低温球磨；储氢性能 分类号TG139.7:TG146.22 Preparation and performance of Mg4%Ni-1%NiO hydrogen storage materials by cryomilling LI Ping,WANG Teng",FAN Li-zhen,DIN Rafi-ud2,QU Xuan-hui 1)School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China 2)Chemistry Division,Pakistan Institute of Nuclear Science and Technology,Nilore Islamabad,Pakistan Corresponding author,E-mail:liping@ustb.edu.cn ABSTRACT A novel material Mg-4%Ni-1%NiO for hydrogen storage applications was fabricated by mechanical milling at cryogenic temperature (cryomilling).The effects of ball milling time on the structure morphology and the hydrogen storage performance of the newly developed materials were investigated at cryogenic temperature.The phase structure and surface morphology were analyzed by X-ray diffraction (XRD)and scanning electron microscopy (SEM).The hydrogenation and dehydrogenation characteristics were stud- ied by a pressure-composition-temperature (P-C-T)apparatus.It is shown that the phase structure of the materials remains almost unchanged even after 2,4,and 7h of ball milling,respectively and only a small amount of Mg Ni forms.However,a sharp deprecia- tion in the average particle size of the alloy was observed with the ball milling time prolonging.Furthermore,there are Ni and NiO par- ticles in the Mg matrix.In company with the changes above,the activation performance and absorption performance of the materials are gradually improved.The materials ball-milled for 7 h can reach the maximal desorption rate after one activation,the onset desorption temperature is 60C,the compounds exhibit a hydrogen storage capacity of 6.4%(mass fraction)at 200C under the hydrogen pres- sure of 4.0 MPa,and they can absorb 80%of their full hydrogen capacity in 60s and 90%in 10 min.As the ball milling time is pro- longed to 4h,the performance of the materials is stable,the onset desorption temperature is 310 C under 0.I MPa,and the materials are able to desorb about 80%of their full hydrogen capacity in 500s at 350 C under the hydrogen pressure of 0.I MPa. KEY WORDS hydrogen storage materials;magnesium:cryomilling:hydrogen storage property 收稿日期：2010-10-09 基金项目：国家高技术研究发展计划资助项目(No.2006AA05Z132):教有部长江学者和创新团队发展计划资助项目(No.2P407)第 33 卷 第 7 期 2011 年 7 月 北京科技大学学报 Journal of University of Science and Technology Beijing Vol． 33 No． 7 Jul． 2011 低温球磨制备 Mg--4%Ni--1%NiO 储氢材料及其性能 李 平1)  王 腾1) 范丽珍1) DIN Rafi-ud1，2) 曲选辉1) 1) 北京科技大学材料科学与工程学院，北京 100083 2) 巴基斯坦核科学与技术研究所化学部，伊斯兰堡，巴基斯坦  通信作者，E-mail: liping@ ustb． edu． cn 摘 要 采用低温球磨技术制备了 Mg--4% Ni--1% NiO 储氢材料，主要研究低温球磨时间对材料形貌结构以及储氢性能的影 响． 采用扫描电子显微镜( SEM) 和 X 射线衍射( XRD) 分析材料的形貌和相组成，采用压力--组成--温度( P--C--T) 设备研究材 料的储氢性能． 结果表明: 分别经过 2、4 和 7 h 球磨后，材料的相组成没有发生明显改变，只有极少量的 Mg2Ni 合金相生成． 随着球磨时间的延长，材料的平均粒度逐渐下降，作为催化剂的 Ni、NiO 相逐渐揉进基体内部． 伴随着上述变化，材料的活化 性能、吸氢性能逐渐提高，球磨到 7 h 后材料仅需活化 1 次即可达到最大吸放氢速率，初始吸氢温度降为 60 ℃，在 4. 0 MPa 初 始氢压和 200 ℃下吸氢量为 6. 4% ( 质量分数) ，60 s 即可完成饱和吸氢量的 80% ，10 min 内完成饱和吸氢量的 90% ; 材料的放 氢性能则在球磨 4 h 后已经基本保持不变，0. 1 MPa 下初始放氢温度为 310 ℃，在 350 ℃、0. 1 MPa 下材料可在 500 s 内释放饱和 储氢量的 80% ． 关键词 储氢材料; 镁; 低温球磨; 储氢性能 分类号 TG139 + . 7; TG146. 2 + 2 Preparation and performance of Mg-4%Ni-1%NiO hydrogen storage materials by cryomilling LI Ping1)  ，WANG Teng1) ，FAN Li-zhen1) ，DIN Rafi-ud1，2) ，QU Xuan-hui 1) 1) School of Materials Science and Engineering，University of Science and Technology Beijing，Beijing 100083，China 2) Chemistry Division，Pakistan Institute of Nuclear Science and Technology，Nilore Islamabad，Pakistan  Corresponding author，E-mail: liping@ ustb． edu． cn ABSTRACT A novel material Mg-4% Ni-1% NiO for hydrogen storage applications was fabricated by mechanical milling at cryogenic temperature ( cryomilling) ． The effects of ball milling time on the structure morphology and the hydrogen storage performance of the newly developed materials were investigated at cryogenic temperature． The phase structure and surface morphology were analyzed by X-ray diffraction ( XRD) and scanning electron microscopy ( SEM) ． The hydrogenation and dehydrogenation characteristics were stud￾ied by a pressure-composition-temperature ( P-C-T) apparatus． It is shown that the phase structure of the materials remains almost unchanged even after 2，4，and 7 h of ball milling，respectively and only a small amount of Mg2Ni forms． However，a sharp deprecia￾tion in the average particle size of the alloy was observed with the ball milling time prolonging． Furthermore，there are Ni and NiO par￾ticles in the Mg matrix． In company with the changes above，the activation performance and absorption performance of the materials are gradually improved． The materials ball-milled for 7 h can reach the maximal desorption rate after one activation，the onset desorption temperature is 60℃，the compounds exhibit a hydrogen storage capacity of 6. 4% ( mass fraction) at 200 ℃ under the hydrogen pres￾sure of 4. 0 MPa，and they can absorb 80% of their full hydrogen capacity in 60 s and 90% in 10 min． As the ball milling time is pro￾longed to 4 h，the performance of the materials is stable，the onset desorption temperature is 310 ℃ under 0. 1 MPa，and the materials are able to desorb about 80% of their full hydrogen capacity in 500 s at 350 ℃ under the hydrogen pressure of 0. 1 MPa． KEY WORDS hydrogen storage materials; magnesium; cryomilling; hydrogen storage property 收稿日期: 2010--10--09 基金项目: 国家高技术研究发展计划资助项目( No． 2006AA05Z132) ; 教育部长江学者和创新团队发展计划资助项目( No． I2P407) DOI:10.13374/j.issn1001-053x.2011.07.012