采用基于密度泛函理论(DFT)的平面波赝势(PW-PP)方法,计算并分析了Mg2Ni1-xMx(M=Mn,Fe,Co,Ni,Cu,x=0.25)合金及其氢化物Mg2Ni1-xMxH4的电子结构和热力学稳定性.计算结果表明:Mg2NiH4和Mg2Ni1-xMx 的晶胞参数与实验值吻合较好.对Mg2Ni1-xMxH4的电子结构分析发现:氢化物中的Ni-H和M-H键为共价键、Mg-H键为离子键,且Ni-H与M-H键的相互作用强于Mg-H键的.Mn、Fe和Co的部分替代对Ni-H键的相互作用影响较小,而Cu的替代则减弱了Ni-H键的相互作用,这可能是Cu替代后氢化物结构稳定性降低的一个原因.计算了Mg2Ni0.75M0.25H4 (M=Mn,Fe,Co,Ni,Cu)的生成焓,分别为-57.7、-61.5、-61.4、63.4和41.6kJ/mol,与实验值吻合较好.
参考文献
| [1] | Wojciech Grochala;Peter P.Edwards .Thermal Decomposition of the Non-Interstitial Hydrides for the Storage and Production of Hydrogen[J].Chemical Reviews,2004(3):1283-1315. |
| [2] | SCHLAPBACH L;ZUTTEL A .Hydrogen-storage materials for mobile applications[J].Nature,2001,414:353-358. |
| [3] | YANG Hua-bin;YUAN Hua-tang;JI Jing-tao;SUN Hua,ZHOU Zuo-xiang,ZHANG Yun-shi .Characteristics of Mg2Ni0.75M0.25 (M=Ti,Cr,Mn,Fe,Co,Ni,Cu and Zn) alloys after surface treatnent[J].Journal of Alloys and Compounds,2002,330:640-644. |
| [4] | 吕光烈,陈林深,胡秀荣,王连邦,袁华堂.Mg3MNi2（M=Ti,Al）的晶体结构[J].金属学报,2001(05):459-462. |
| [5] | TAKAHASHI Y;YUKAWA H;MORINAGA M .Alloying effects on the electronic structure of Mg2Ni intermetallic hydride[J].Journal of Alloys and Compounds,1996,242(1/2):98-107. |
| [6] | van Setten MJ;de Wijs GA;Brocks G .Ab initio study of the effects of transition metal doping of Mg2NiH4[J].Physical review, B. Condensed matter and materials physics,2007(7):5125-1-5125-8-0. |
| [7] | Paula V. Jasen;Estela A. Gonzalez;Graciela Brizuela;Oscar A. Nagel;Gustavo A. Gonzalez;Alfredo Juan .A theoretical study of the electronic structure and bonding of the monoclinic phase of Mg_2NiH_4[J].International journal of hydrogen energy,2007(18):4943-4948. |
| [8] | 罗湖斌,胡青苗,杨锐.合金化对β钛合金热膨胀系数的影响：第一性原理研究[J].中国有色金属学报,2010(z1):399-403. |
| [9] | 刘奕新,梁初,蒋龙,黎光旭,韦文楼,郭进.Li-Al-N-H系络合物贮氢反应的第一性原理研究[J].中国有色金属学报,2009(01):108-113. |
| [10] | MARLO M;MILMAN V .Density-functional study of bulk and surface properties of titanium nitride using different exchange-correlation functionals[J].Physical Review B,2000,62(04):2899-2907. |
| [11] | VANDERBILT D .Soft self-consistent pseudopotentials in a generalized eigenvalue formalism[J].Physical Review B,1990,41(11):7892-7895. |
| [12] | Segall MD.;Lindan PJD.;Probert MJ.;Pickard CJ.;Hasnip PJ.;Clark SJ. Payne MC. .First-principles simulation: ideas, illustrations and the CASTEP code[J].Journal of Physics. Condensed Matter,2002(11):2717-2744. |
| [13] | MONKHORST H J;PACK J D .Special points for Brillouin-zone integrations[J].Physical Review B,1976,13(12):5188-5192. |
| [14] | DARRIET B;SOUBEYROUX J L;PEZAT M .Structural and hydrogen diffusion study in the Mg2Ni-H2 system[J].Journal of the Less-Common Metals,1984,103(01):153-162. |
| [15] | NOREUS D;WEKNER P .Structural studies of hexagonal Mg2NiHx[J].Acta Chemica Scandinavica Series A:Physical and Inorganic Chemistry,1982,36(10):874-851. |
| [16] | ZOLLIKER P;YVON K;JORGENSEN J;ROTELLA F J .Structural studies of the hydrogen storage material magnesium nickel hydride (Mg2NiH4):2.Monoclinic low-temperature structure[J].Inorganic Chemistry,1986,25(20):3590-3593. |
| [17] | Broedersz CP;Gremaud R;Dam B;Griessen R;Lovvik OM .Highly destabilized Mg-Ti-Ni-H system investigated by density functional theory and hydrogenography[J].Physical review, B. Condensed matter and materials physics,2008(2):024204-1-024204-10-0. |
| [18] | R.J. Zhang;Y.M. Wang;D.M. Chen .First-principles calculations of LaNi_4Al-H solid solution and hydrides[J].Acta materialia,2006(2):465-472. |
| [19] | S.L. Li;P. Wang;W. Chen .Hydrogen storage properties of LaNi_(3.8)Al_(1.0)M_(0.2)(M = Ni, Cu, Fe, Al, Cr, Mn) alloys[J].Journal of Alloys and Compounds: An Interdisciplinary Journal of Materials Science and Solid-state Chemistry and Physics,2009(1/2):867-871. |
| [20] | REILLY J J;WISWALL R H .The reaction of hydrogen with alloys of magnesium and Nickel and the formation of Mg2NiH4[J].Inorganic Chemistry,1968,7(11):2254-2256. |
| [21] | Yanli Zeng;Ke Fan;Xiaoyan Li;Baoen Xu;Xiaozhen Gao;Lingpeng Meng .First-principles studies of the structures and properties of Al- and Ag-substituted Mg_2Ni alloys and their hydrides[J].International journal of hydrogen energy,2010(19):10349-10358. |
| [22] | SELVAM P;VISWANATHAN B;SWAMY C S;SRINIVASAN V .Studies on the thermal characteristics of hydrides of Mg,Mg2Ni,Mg2Cu and Mg2Ni1-xMx (M=Fe,Co,Cu or Zn;0《x《1)alloys[J].International Journal of Hydrogen Energy,1988,13(02):87-94. |
| [23] | Li S;Jena P;Ahuja R .Dehydrogenation mechanism in catalyst-activated MgH2[J].Physical review, B. Condensed matter and materials physics,2006(13):2106-1-2106-4-0. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%