Please wait a minute...
 
材料工程  2015, Vol. 43 Issue (3): 48-53    DOI: 10.11868/j.issn.1001-4381.2015.03.009
  材料与工艺 本期目录 | 过刊浏览 | 高级检索 |
碳助磨制备纳米镁铝储氢合金的结构及储氢性能研究
张同环1, 周仕学1, 牛海丽1, 肖成柱2, 王乃飞1
1. 山东科技大学 化学与环境工程学院, 山东 青岛 266590;
2. 日照钢铁控股集团有限公司, 山东 日照 276806
Microstructure and Hydrogen Storage Properties of Nanostructured Mg-Al Alloy from Reactive Milling with Carbon as Milling Aid
ZHANG Tong-huan1, ZHOU Shi-xue1, NIU Hai-li1, XIAO Cheng-zhu2, WANG Nai-fei1
1. College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, Shandong, China;
2. Rizhao Steel Holding Group Co., LTD., Rizhao 276806, Shandong, China
全文: PDF(1825 KB)  
输出: BibTeX | EndNote (RIS)      
摘要 以改性无烟煤为助磨剂,在氢气气氛下球磨制备了具有纳米结构的镁铝合金储氢材料,通过SEM,XRD,TPD等手段对比研究了球磨吸氢材料及静态再吸氢材料的晶相结构及放氢动力学性能。结果表明:改性无烟煤具有良好的助磨作用,经5.5h球磨,材料平均粒度可达74nm;镁铝合金经反应球磨后,其中的Mg转化成了β-MgH2和γ-MgH2,放氢峰温低于300℃;静态再吸氢后,MgH2全部以β-MgH2存在,且晶体粒度增长60%,Mg17Al12分解为单质Mg和Al,其中单质Al使储氢材料放氢活化能降低,用Kissinger方程计算出球磨储氢和再吸氢材料的放氢一级表观活化能分别为107.3kJ/mol和67.1kJ/mol。
服务
把本文推荐给朋友
加入引用管理器
E-mail Alert
RSS
作者相关文章
张同环
周仕学
牛海丽
肖成柱
王乃飞
关键词 镁铝储氢合金Kissinger方程碳助磨剂动力学性能活化能    
Abstract:Nanostructured Mg-Al alloy hydrogen storage material was prepared with modified anthracite as milling aid by ball milling under hydrogen atmosphere. The crystal phase structure and dehydrogenation kinetics properties of the ball milled hydrogen absorbing materials and static re-hydrogenated materials were analyzed by SEM, XRD and TPD. The results show that the modified anthracite plays a good milling aid role, after 5.5 h of milling, the average particle size of Mg-Al alloy reaches to 74 nm; The Mg in the Mg-Al alloy transforms into β-MgH2 and γ-MgH2 after reaction ball milling, whose peak dehydrogenation temperature is lower than 300 ℃. Yet, after static re-hydrogenation, the MgH2 all exists in β-MgH2 which shows a 60% increase in crystal size, and the Mg17Al12 decomposes into elementary Mg and Al. The elementary Al decreases the dehydrogenation activation energy of hydrogen storage materials, where the hydrogen level of apparent activation energy of the ball milled hydrogen storage material and re-hydrogenated material is 107.3kJ/mol and 67.1kJ/mol, respectively, calculated according to the Kissinger equation.
Key wordsmagnesium based hydrogen storage alloy    Kissinger equation    carbon milling aid    kinetics    activation energy
收稿日期: 2013-07-26     
1:  TG139  
基金资助:国家自然科学基金资助项目(21176145,51408347)
通讯作者: 周仕学(1966-),男,博士,教授,博士生导师,主要从事功能材料方面的研究工作,联系地址:山东省青岛经济技术开发区前湾港路579号山东科技大学化工学院(266590),zhoushixue66@163.com     E-mail: zhoushixue66@163.com
引用本文:   
张同环, 周仕学, 牛海丽, 肖成柱, 王乃飞. 碳助磨制备纳米镁铝储氢合金的结构及储氢性能研究[J]. 材料工程, 2015, 43(3): 48-53.
ZHANG Tong-huan, ZHOU Shi-xue, NIU Hai-li, XIAO Cheng-zhu, WANG Nai-fei. Microstructure and Hydrogen Storage Properties of Nanostructured Mg-Al Alloy from Reactive Milling with Carbon as Milling Aid. Journal of Materials Engineering, 2015, 43(3): 48-53.
链接本文:  
http://jme.biam.ac.cn/jme/CN/10.11868/j.issn.1001-4381.2015.03.009      或      http://jme.biam.ac.cn/jme/CN/Y2015/V43/I3/48
[1] IMAMURA H, MASANARI K, KUSUHARA M, et al. High hydrogen storage capacity of nanosized magnesium synthesized by high energy ball-milling [J]. Journal of Alloys and Compounds, 2005, 386(1-2): 211-216.
[2] NARAYANAN D L, LUEKING A D. Mechanically milled coal and magnesium composites for hydrogen storage [J]. Carbon, 2007, 45(4): 805-820.
[3] 胡秀颖, 周仕学, 王振华, 等. 球磨时间对镁碳复合储氢材料结构和性能的影响[J]. 功能材料, 2008, 39 (3): 424-429.HU X Y, ZHOU S X, WANG Z H, et al. Effect of ball milling time on the structure and properties of Mg-C composites for hydrogen storage [J]. Journal of Functional Materials, 2008, 39 (3):424-429.
[4] 卢国俭, 周仕学, 马怀营, 等. 反应球磨法制备镁/碳纳米复合储氢材料[J]. 功能材料, 2007, 38(7): 1128-1131. LU G J, ZHOU S X, MA H Y, et al. Preparation of magnesium/carbon nanocomposites for hydrogen storage by reaction milling[J]. Journal of Functional Materials, 2007, 38(7): 1128-1131.
[5] CRIVELLO J C, NOBUKI T, KUJI T. Improvement of Mg-Al alloys for hydrogen storage applications [J]. International Journal of Hydrogen Energy, 2009, 34: 1937-1943.
[6] JIANG J J, WEI J, LENG H Y. Effect of Al on the hydrogen storage properties of Mg(BH4)2 [J]. International Journal of Hydrogen Energy, ISSN:03603199; DOI:10.1016/j.ijhydene.2013.01. 093
[7] 肖学章, 陈立新, 刘广成, 等. 球磨Mg17Al12纳米晶/非晶合金的微结构和储氢性能[J]. 西安交通大学学报, 2007, 41(11): 1368-1372. XIAO X Z, CHEN L X, LIU G C, et al. Microstructures and hydrogen storage characteristics of nanocrystal/amorphous Mg17Al12 alloy prepared by ball milling[J]. Journal of Xi'an Jiaotong University, 2007, 41(11): 1368-1372.
[8] HUANG L W, ELKEDIM O, NOWAK M, et al. Synergistic effects of multiwalled carbon nanotubes and Al on the electrochemical hydrogen storage properties of Mg2Ni-type alloy prepared by mechanical alloying[J]. International Journal of Hydrogen Energy, 2012, 37(2): 1538-1545.
[9] BOUOUDINA M, GUO Z X. Comparative study of mechanical alloying of (Mg+Al) and (Mg+Al+Ni) mixtures for hydrogen storage [J]. Journal of Alloys and Compounds, 2002, 336(1-2): 222-231.
[10] PALMA A S, ITURBE G, JOSE L, et al. MgAl alloy synthesis, characterization and its use in hydrogen storage[J]. International Journal of Hydrogen Energy, 2010, 35(21): 12120-12124.
[11] 谢昭明, 付安庆, 陈玉安, 等. Al的添加对Mg2Ni储氢合金结构和氢扩散能力的影响研究 [J]. 功能材料, 2006, 37(4): 601-603. XIE Z M, FU A Q, CHEN Y A, et al. Effect of Al addition on microstructure and hydrogen diffusion capability of Mg2Ni alloy[J]. Journal of Functional Materials, 2006, 37(4): 601-603.
[12] 王美涵, 张连中, 孙立贤, 等. Mg1.75Al0.25Ni1-xCrx(0≤x≤0.2)合金的制备及其性能[J]. 高等学校化学学报, 2005, 26(10):1877- 1880. WANG M H, ZHANG L Z, SUN L X, et al. Preparation and properties of Mg1.75Al0.25Ni1-xCrx(0≤x≤0.2) alloys[J]. Chemical Journal of Chinese Universities, 2005, 26(10): 1877-1880.
[13] 罗翔, 郑坊平, 王春涛, 等. 添加Ti0.9Zr0.1Mn1.5复合球磨对Ti9.6V86.4Fe4合金储氢性能的影响[J]. 西安交通大学学报, 2007, 41(12):1491-1494. LUO X, ZHENG F P, WANG C T, et al. Influence of composite ball milling with Ti0.9Zr0.1Mn1.5 on hydrogen storage properties of Ti9.6V86.4Fe4 alloy [J]. Journal of Xi'an Jiaotong University, 2007, 41(12): 1491-1494.
[14] BORTZ M, BERTHEVILLE B, BOTTGER G. Structure of the high pressure phase λ-MgH2 by neutron powder diffraction [J]. Journal of Alloys and Compounds, 1999, 287: L4-L6.
[15] ZHOU S X, CHEN H P, DING C, et al. Effectiveness of crystallitic carbon from coal as milling aid and for hydrogen storage during milling with magnesium [J]. Fuel, 2012, 109: 68-75.
[16] 许娟, 李鹏飞, 郭锋. 热处理对 AZ91D 镁合金相结构的影响[J]. 材料热处理学报, 2011, 32(4): 30-33. XU J, LI P F, GUO F. Effect of heat treatment on microstructure of AZ91D alloy [J]. Transactions of Materials and Heat Treatment, 2011, 32(4): 30-33.
[17] 李武会, 田保红, 马坪, 等. ScMn2 合金贮氢(氘)性能[J]. 金属学报, 2012, 48(7): 822-829. LI W H, TIAN B H, MA P, et al. Hydrogen storage properties of ScMn2 alloy [J]. Acta Metallurgica Sinica, 2012, 48(7): 822-829.
[18] 余学斌, 陈金舟, 吴铸, 等. Cr含量对TiMn1.2-xCrxV0.25Fe0.05 合金吸/放氢性能的影响[J]. 金属学报, 2004, 40(5): 527-530. YU X B, CHEN J Z, WU Z, et al. Effect of Cr content on the sorption performance of TiMn1.2-xCrxV0.25Fe0.05 alloys [J]. Acta Metallurgica Sinica, 2004, 40(5): 527-530.
[1] 杨中正, 姚亚刚, WONG C P, 陆跃军. 微沸法合成纳米莫来石及活化能的研究[J]. 材料工程, 2015, 43(6): 26-30.
[2] 宋仔标, 刘代志, 王红霞. 碳纳米材料空气动力学性能的实验研究[J]. 材料工程, 2009, 0(8): 53-56,62.
[3] 庄园园, 司小娟, 陈建军, 程丹丹, Jeong Cheol Kim, 王依民. UHMWPP/UHMWPE合金纤维结晶能力与结晶活化能研究[J]. 材料工程, 2008, 0(10): 239-242.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
版权所有 © 2015《材料工程》编辑部
地址:北京81信箱44分箱 邮政编码: 100095
电话:010-62496276 E-mail:matereng@biam.ac.cn
本系统由北京玛格泰克科技发展有限公司设计开发 技术支持:support@magtech.com.cn