新型镁钛系BCC结构储氢合金制备与性能研究
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摘要
金属氢化物中,氢原子主要占据在金属原子间的间隙位置上,与FCC结构或者HCP结构的储氢合金相比,具有BCC结构的储氢合金能存储氢原子的位置更多,因此受到了广大学者的青睐。镁、钛金属氢化物MgH2和TiH2的储氢量分别为7.6wt.%和4.0wt.%,这两种金属氢化物的储氢容量较高,是车载储氢燃料和镍氢电池的理想材料。目前,对于Mg-Ti BCC结构储氢合金的研究也受人们的广泛关注。本文首先探索Mg-Ti系BCC结构固溶体储氢合金的制备方法,然后添加不同的催化剂加以改善其储氢性能。
采用机械合金化制备Mg76Ti12Ni12-xCr(x=0,3,6,9)合金,经过30小时球磨后,Mg76Til2Ni12中的二元合金相为FCC结构的Ti2Ni和六方结构的Mg2Ni,Mg76Ti12Ni12-xCrx(x=3,6,9)合金中除了FCC结构的Ti2Ni和六方结构的Mg2Ni二元合金相外,合金中还出现具有六方结构的Cr1.75Ni0.25Ti。随着Cr含量的增加,合金的非晶化程度提高。其中,适量的Cr能降低合金的吸放氢滞后系数以及提高合金的吸氢速率。而当以Mg76Ti12Ni9Cr3为研究对象,通过改变合金中Ti/Mg的比例发现,Mg76-xTi12+xNi9Cr3(x=4,8,12,16)合金相结构主要由Mg2Ni相和Ti2Ni相组成,合金经过20h到80h球磨后,其储氢量分别从3.93wt.%、3.82wt.%、3.64wt.%和2.81wt.%下降到2.36.wt%、2.16.wt%、1.81.wt%和2.0.wt%；随着球磨时间的增加,合金的储氢量下降；经过40h球磨后Mg76-xTi12+Ni9Cr3(x=4,8,12,16)合金氢化物的释氢温度分别为550K、528K、518K和506K,释氢温度随着Ti/Mg比例的增加而降低。Mg76-xTi12+x Ni9Cr3(x=4,8,12,16)合金氢化物的分解焓分别为-80.2kJ/mol、-78.5kJ/mol.-73.5kJ/mol和-80.0kJ/mol。随着Ti含量的增加,合金氢化物分解焓先减小后增大,适当的Ti能有效的降低合金氢化物的稳定性。
通过研究Mn对镁基储氢性能的影响发现,在Mg76-xTi12Ni12Mnx(x=2,4,6,8)合金中,合金相主要为Mg2Ni和Ti2Ni相,在x=6和x=8的合金中,还出现TiMn2的二元合金相；Mg76-xTi12Ni12Mnx(x=2,4,6,8)合金最大储氢量分别为3.47wt.%、3.32wt.%、3.60wt.%和3.11wt.%,Mg76-xTi12Ni12Mnx(x=2,4,6,8)合金氢化物分解焓分别为：-79.2kJ/mol、-78.0kJ/mol、-73.7kJ/mol和-73.6kJ/mol; Mn能有效提高合金的储氢量,降低合金氢化物的稳定性,有利于改善合金的放氢热力学性能。
基于Mg70Ti12Ni12Mn6合金具有较好的储氢性能,我们以Mg70Ti12Ni12Mn6为研究对象,采用机械合金化制备Mg70-xTi12+xNi12Mn6(x=8,16,24,32)合金,在球磨50h阶段,合金主要由具有HCP.FCC结构的元素组成；当球磨时间为100h时,Mn固溶到Ti晶格内部中,其对应的衍射峰基本消失,Mg和Ni对应的衍射峰逐渐减弱,合金的粒度减小且非晶化程度提高；当球磨时间增加到200h时,一方面由于Mg2Ni的出现导致衍射峰强度增加,另一方面,Mg和Ni逐渐固溶到Ti的晶格内部中,导致Ti对应的衍射峰强度增加,与此同时,在Mg46Ti36Ni12Mn6和Mg38Ti44Ni12Mn6合金中,在20=43.1°、63.1°和70.7°位置出现具有BCC结构的衍射峰；具有BCC结构的Mg46Ti36Ni12Mn6合金在573K温度下吸氢量为1.36wt.%,其氢化物的脱氢温度明显低于Mg62Ti20Ni12Mn6、Mg54Ti28Ni12Mn6和Mg38Ti44Ni12Mn6氢化物的脱氢温度。当球磨时间增加到400h时,Mg46Ti36Ni12Mn6和Mg38Ti44Ni12Mn6合金中,Mg的衍射峰全部消失,部分Ni衍射峰也消失,合金中仅剩FCC和BCC结构,Mg和Ni进一步固溶到Ti的基体中,合金中FCC结构是部分没有被固溶的Ni元素。为进一步改善BBC结构Mg46Ti36Ni12Mn6合金的储氢性能,在Mg46Ti36Ni12Mn6合金中添加不同含量的TiF3,研究发现,Mg46Ti36Ni12Mn6+xwt.%TiF3(x=2,5,8,11)合金的吸氢量分别为1.65wt.%,2.33wt.%,1.95wt.%和1.87wt.%,当TiF3的质量分数为5%时,合金的储氢性能最佳。
为了比较相同含量不同添加剂的催化效果,在Mg46Ti36Ni12Mn6合金中添加质量分数为5%M(M=LiH, TiF3, Nb2O5, C)作为催化剂发现,添加C后合金主衍射峰所对应的FWHM最小,合金的晶格畸变越小,其次分别是TiF3、LiH和Nb205。在Mg46Ti36Ni12Mn6合金中添加5wt.%M,当M=C和LiH,能显著提高球磨效率,在相同的球磨时间内,合金的颗粒尺寸更小,但并不能提高合金的储氢性能；当M=TiF3和Nb205时,能有效的提高合金的储氢性能。Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3, C, Nb2O5, LiH)合金经过200h的球磨后,其储氢量分别为2.33wt.%、0.68wt.%、2.36wt.%和1.49wt.%。Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3, C, Nb2O5, LiH)合金氢化物的初始放氢温度温度分别为：568K、608K、535K和627K。
而当以5wt%M(M=MgH2,CaH2,LiAlH4,NaH)作为添加剂后,Mg46Ti36-Ni12Mn6合金的储氢性能有了较大改善,经过200h的球磨后,合金中都出现了BCC结构的相。与MgH2和LiAlH4相比,添加NaH和CaH2后,合金的颗粒更小,合金的固溶度以及非晶化程度更高,当添加NaH和CaH2后,以Mg-Ti为基体,其他元素更易于固溶到Mg-Ti基体中,形成较为稳定的Mg-Ti基BCC结构。在303K温度下,其吸氢量分别为2.78wt.%、2.16wt.%、0.71wt.%和0.85wt.%。当温度在573K时,除了以CaH2作为添加剂的合金外,其他合金均在较短的时间内吸氢达到平衡,合金的吸氢量分别为3.1wt.%、2.76wt.%、3.2wt.%和1.95wt.%,随着温度的增加,合金吸氢量略有上升。合金氢化物经过加热后第一个吸热峰分别为：534K、517K、521K和553K。当以CaH2、 LiAlH4、MgH2和NaH做为添加剂后,在一定程度上降低储氢合金的释氢温度。
以Co,Cr,Fe和V取代Mg46Ti36Ni12Mn6合金中的Mn,在Mg46Ti36Ni12Cr6、 Mg46Ti36Ni12Fe6和Mg46Ti36Ni12V6合金中BCC结构相出现在40.4°、58.6°和73.9°位置,合金中除了出现BCC结构外,还有FCC结构相和Diamond Cubic结构相；而在M946Ti36Ni12Co6合金中,BCC结构出现在42.9°和62.2°位置,合金中未出现FCC结构相和diamond Cubic结构相,但有Primitive Cubic结构相。Mg46Ti36Ni12M6(M=Co,Cr,Fe,V)合金BCC结构相晶格参数分别为：0.2982、0.3148、0.3140和0.3376nm,BCC结构的晶格参数随着替代元素原子半径的增大而增大。在303K时,Mg46Ti36Ni12M6(M=Co,Cr,Fe,V)合金的吸氢量分别为1.14wt.%、1.59wt.%、1.55wt.%和2.38wt.%；在573K时,其吸氢量分别为1.95wt.%、2.25wt.%、2.01wt.%和2.95wt.%,合金的吸氢量随着替代元素原子半径的增大而增大。Mg46Ti36Ni12M6(M=Co,Cr,Fe,V)合金氢化物初始放氢温度分别为460K、441K、441K和453K,在加热过程第一个吸热峰分别出现在624K、530K、514K和569K。
Hydrogen atoms mainly occupy the interstitial site among metal atoms in metal hydrides. In comparison with FCC and HCP structures, BCC structures have more interstitial site to hold much more hydrogen. Mg and Ti are more popular metallic elements which form stable hydrides because of their higher hydrogen capacities (theoretically up to7.6wt%) and lower costs (they form MgH2and TiH2hydrides including7.6mass%and4.0mass%hydrogen, respectively), so that MgH2and TiH2hydrides are excellent materials for vehicle fuel and nickel-metal hydride batteries. In the present work, we have explored the preparation method to synthesize Mg-Ti BCC alloys and tried to improve the hydrogen storage performance of these alloys by adding different kinds of additives.
Mg76Ti12Ni12-xCrx (x=0,3,6,9) alloys were prepared by mechanical alloying. For Mg76Ti12Ni12alloy, the binary alloy phase of Mg2Ni and Ti2Ni phase formed after milled30h. Besides Ti2Ni phase and Mg2Ni phase, Cr1.75Nio.25Ti phase also formed in the Mg76Tii2Ni12-xCrx (x=3,6,9) alloys. For Mg76Ti12Ni12-xCrx (x=0,3,6,9) alloys, the amorphous degree increased with the increase of Cr content. The hysteresis coefficient of hydrogen absorptiondes-orption decreased, as well as the hydrogen absorption rate could be improved by adding proper Cr content.
The Ti and Mg content were changed based on Mg76Ti,2Ni9Cr3alloy. Mg76-xTi12+xNi9Cr3(x=4,8,12,16) alloys were prepared by mechanical alloying. For Mg76-xTi12+xNi9Cr3(x=4,8,12,16) alloys, the main binary alloy phase was Mg2Ni and Ti2Ni after milled. And the hydrogen storage capacity was3.93wt.%,3.82wt.%,3.64wt.%and2.81wt.%after milled20h. However, it decreased to2.36wt.%,2.16wt.%,1.81wt.%,2.0wt.%when the milling time increased to80h. It was found that the hydrogen storage capacity decreased with the increase of the milling time and the ratio of Ti/Mg. It was also found from DTA results that the hydrogen desorption temperature of the Mg76-xTi12+xNi9Cr3(x=4,8,12,16) hydride were550K,528K,518K and506K, respectively. The hydrogen desorption temperature decreased with increasing the rate of Ti/Mg. The decomposition enthalpies of the Mg76-xTi12+xNi9Cr3(x=4,8,12,16) hydride were-80.2kJ/mol,-78.5kJ/mol,-73.5kJ/mol and-80.0kJ/mol, respectively. The decomposition enthalpy decreased with the increase of Ti content firstly, then increased with increasing Ti content. The stability of the hydride can be reduced with proper Ti content.
Mg76-xTi12Ni12Mnx (x=2,4,6,8) alloys were prepared by mechanical alloying and the effects of Mn content on the hydrogen storage properties were investig-ated systematically. For Mg76-xTi12Ni12Mnx (x=2,4,6,8) alloys, the main binary alloy phase consist of Mg2Ni and Ti2Ni too. It was found that TiMn2phase appeare when x=6and x=8. The hydrides decomposition enthalpies of Mg76-xTi12Ni12Mnx (x=2,4,6,8) alloys were-79.2kJ/mol,-78.0kJ/mol,-73.7kJ/mol and-73.6kJ/mol. The hydrogen storage capacity increased, as well as the stability of the hydride reduced with the addition of the Mn element. The thermodynamics performance was also improved with addition of the element Mn.
According to the good hydrogen storage properties of Mg70Ti12Ni12Mn6alloy mentioned above, Mg70-xTi12+xNi12Mn6(x=8,16,24,32) alloys were prepared by mechanical alloying. The alloys were mainly composed of HCP and FCC structures after ball-milling for50h. When the milling time increased to100h, it was shown that the diffraction peak of Mn element disappeared, as well as the diffraction peak of Mg and Ni weakened gradually. However, the peak intensities of Ti increase significantly. It was suggested that Mg, Ni and Mn dissolve into Ti lattice to form solid solution. When the milling time increased to200h, X-ray diffraction (XRD) testing showed that the diffraction peak of Mg2Ni occurs, and the diffraction peak of Mg and Ni decreased while the intensity of X-rays diffraction pattern of Ti was improved at2θ=35.3°,38.4°,40.2°nd43.1°. These results demonstrated that Mg and Ni further dissolve into Ti lattice. For Mg46Ti36Ni12Mn6and Mg38Ti44Ni12Mn6alloys, the peaks with the BCC structure appeared at20=43.1°,63.1°and70.7°. After ball-milling for400h, the diffraction peak of Mg disappeared, and part of the diffraction peak of Ni also disappeared, only FCC and BCC structure exist. These results were also due to that Mg and Ni further dissolved into Ti lattice. And, the FCC structure which corresponded to Ni was due to Ni element not yet diffusing into Ti lattice. The hydrogen storage capacity of Mg46Ti36Ni12Mn6alloy with BCC structure was1.36wt.%at573K, and the dehydriding temperature was lower than that of Mg62Ti2oNi12Mn6, Mg54Ti28Ni12Mn6and Mg38Ti44Ni12Mn6hydrides.
To improve the hydrogen storage performance of BCC solid solution Mg46Ti36Ni12Mn6alloy, we added xwt.%TiF3(x=2,5,8,11) to Mg46Ti36Ni12Mn6alloy. The hydrogen storage capacity of Mg46Ti36Ni12Mn6+xwt.%TiF3(x=2,5,8,11) was1.65wt.%,2.33wt.%,1.95wt.%and1.87wt.%, respectively. Among these alloys, the Mg46Ti36Ni12Mn6+5wt.%TiF3alloy presented the best hydrogen storage performance.
To study the effects of different kinds of catalyst on the hydrogen storage performance of the Mg46Ti36Ni12Mn6alloy with BCC structure,5wt.%M (M=LiH,TiF3,Nb205and C) was added. For Mg46Ti36Ni,2Mn6+5wt.%M (M=LiH,TiF3,Nb205and C) alloys, X-ray diffraction studies indicated that the full width at half maximum (FWHM) of main diffraction peaks corresponding to Mg46Ti36Ni12Mn6+5wt.%C was the smallest. The results revealed that the crystal lattice distortion of Mg46Ti36Ni12Mn6alloy was the least when adding C, the next was TiF3, LiH and Nb2O5. After ball-milling for200h, the hydrogen storage capacity of Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3,C,Nb205,LiH) alloys were2.33wt.%,0.68wt.%,2.36wt.%and1.49wt.%respectively. Among these alloys, the particle size of Mg46Ti36Ni12Mn6+5wt.%M(M=C,LiH) was smaller. The result implied that C and LiH could raise mechanical milling efficiency but did not improve the hydrogen storage performance. However, the hydrogen storage performance can be improved by adding TiF3and Nb2O5. It could be seen from the DTA results that the initial exothermic temperature for Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3,C,Nb205,LiH) hydride were568K,608K,535K and627K, respectively.
The effect of metal hydride on hydrogen storage properties of Mg46Ti36Ni12-Mn6alloy were investigated By adding5wt.%M (M=MgH2, CaH2, LiAlH4, NaH). It could be found that the BCC structure came into being after ball-milling for200h. SEM results showed that the particle size was smaller, the solubility was better and the efficiency of amorphousness was higher when NaH and CaH2other than MgH2and LiAlH4were used as additives. Furthermore, other elements were easier to dissolve into the Mg-Ti matrix and to form stable BCC structure when NaH and CaH2were used as additives. At303K, the hydrogen storage capacity of Mg46Ti36Ni12Mn6+5wt.%M(M=MgH2, CaH2, LiAlH4, NaH) alloys were2.78wt.%,2.16wt.%,0.71wt.%and0.85wt.%, respectively, and were3.1wt.%,2.76wt.%,3.2wt.%and1.95wt.%as the temperature increased to573K. That was to say, the hydrogen storage capacity increased with increasing the temperature. The differential thermal analysis (DTA) results showed that the first endothermic peaks of Mg46Ti36Ni]2Mn6+5wt.%M(M=MgH2, CaH2, LiAlH4, NaH)hydride were534K,517K,521K and553K, respectively. The hydrogen desorption temperature were deduced by adding MgH2, CaH2, LiAlH4and NaH additives.
The effect of substituting elements M (M=Co, Cr, Fe, V) for element Mn on hydrogen storage performance of Mg46Ti36Ni12M6alloy has been studied. For Mg46Ti36Ni12Cr6, Mg46Ti36Ni12Fe6and Mg46Ti36Ni12V6alloys, BCC structure, FCC structure as well as diamond cubic structure were observed, and the BCC structure appeared at29=40.4°,58.6°nd73.9°. For Mg46Ti36Ni12Co6alloy, they were only BCC structure and Primitive Cubic structure, not FCC structure and diamond Cubic structure, and the BCC structure appeared at2θ=42.9°and62.2°. The crystal lattice parameter of the BCC solid solution of Mg46Ti36Ni12M6(M=Co,Cr,Fe,V) alloys were2.9828,3.1475,3.1403and3.3764nm, respectively. The crystal lattice parameter increased with the increase of atomic radius of substitute elements.It was found that synthesized Mg46Ti36Ni12M6(M=Co, Cr, Fe, V) alloys were able to absorb hydrogen up to1.14wt.%,1.59wt.%,1.55wt.%and2.38wt.%at303K, respectively. And it increased to1.95wt.%,2.25wt.%,2.01wt.%and2.95wt.%when the temperature rised to573K. The hydrogen storage capacities of Mg46Ti36Ni12M6(M=Co, Cr, Fe, V) increased with the increasing of the substitution elements atomic radius. The initial hydrogen desorption temperature of Mg46Ti36Ni12M6(M=Co,Cr,Fe,V) hydride was460K,441K,441K and453K, and, the first endothermic peak appeared at624K,530K,514K and569K, respectively.
采用机械合金化制备Mg76Ti12Ni12-xCr(x=0,3,6,9)合金,经过30小时球磨后,Mg76Til2Ni12中的二元合金相为FCC结构的Ti2Ni和六方结构的Mg2Ni,Mg76Ti12Ni12-xCrx(x=3,6,9)合金中除了FCC结构的Ti2Ni和六方结构的Mg2Ni二元合金相外,合金中还出现具有六方结构的Cr1.75Ni0.25Ti。随着Cr含量的增加,合金的非晶化程度提高。其中,适量的Cr能降低合金的吸放氢滞后系数以及提高合金的吸氢速率。而当以Mg76Ti12Ni9Cr3为研究对象,通过改变合金中Ti/Mg的比例发现,Mg76-xTi12+xNi9Cr3(x=4,8,12,16)合金相结构主要由Mg2Ni相和Ti2Ni相组成,合金经过20h到80h球磨后,其储氢量分别从3.93wt.%、3.82wt.%、3.64wt.%和2.81wt.%下降到2.36.wt%、2.16.wt%、1.81.wt%和2.0.wt%；随着球磨时间的增加,合金的储氢量下降；经过40h球磨后Mg76-xTi12+Ni9Cr3(x=4,8,12,16)合金氢化物的释氢温度分别为550K、528K、518K和506K,释氢温度随着Ti/Mg比例的增加而降低。Mg76-xTi12+x Ni9Cr3(x=4,8,12,16)合金氢化物的分解焓分别为-80.2kJ/mol、-78.5kJ/mol.-73.5kJ/mol和-80.0kJ/mol。随着Ti含量的增加,合金氢化物分解焓先减小后增大,适当的Ti能有效的降低合金氢化物的稳定性。
通过研究Mn对镁基储氢性能的影响发现,在Mg76-xTi12Ni12Mnx(x=2,4,6,8)合金中,合金相主要为Mg2Ni和Ti2Ni相,在x=6和x=8的合金中,还出现TiMn2的二元合金相；Mg76-xTi12Ni12Mnx(x=2,4,6,8)合金最大储氢量分别为3.47wt.%、3.32wt.%、3.60wt.%和3.11wt.%,Mg76-xTi12Ni12Mnx(x=2,4,6,8)合金氢化物分解焓分别为：-79.2kJ/mol、-78.0kJ/mol、-73.7kJ/mol和-73.6kJ/mol; Mn能有效提高合金的储氢量,降低合金氢化物的稳定性,有利于改善合金的放氢热力学性能。
基于Mg70Ti12Ni12Mn6合金具有较好的储氢性能,我们以Mg70Ti12Ni12Mn6为研究对象,采用机械合金化制备Mg70-xTi12+xNi12Mn6(x=8,16,24,32)合金,在球磨50h阶段,合金主要由具有HCP.FCC结构的元素组成；当球磨时间为100h时,Mn固溶到Ti晶格内部中,其对应的衍射峰基本消失,Mg和Ni对应的衍射峰逐渐减弱,合金的粒度减小且非晶化程度提高；当球磨时间增加到200h时,一方面由于Mg2Ni的出现导致衍射峰强度增加,另一方面,Mg和Ni逐渐固溶到Ti的晶格内部中,导致Ti对应的衍射峰强度增加,与此同时,在Mg46Ti36Ni12Mn6和Mg38Ti44Ni12Mn6合金中,在20=43.1°、63.1°和70.7°位置出现具有BCC结构的衍射峰；具有BCC结构的Mg46Ti36Ni12Mn6合金在573K温度下吸氢量为1.36wt.%,其氢化物的脱氢温度明显低于Mg62Ti20Ni12Mn6、Mg54Ti28Ni12Mn6和Mg38Ti44Ni12Mn6氢化物的脱氢温度。当球磨时间增加到400h时,Mg46Ti36Ni12Mn6和Mg38Ti44Ni12Mn6合金中,Mg的衍射峰全部消失,部分Ni衍射峰也消失,合金中仅剩FCC和BCC结构,Mg和Ni进一步固溶到Ti的基体中,合金中FCC结构是部分没有被固溶的Ni元素。为进一步改善BBC结构Mg46Ti36Ni12Mn6合金的储氢性能,在Mg46Ti36Ni12Mn6合金中添加不同含量的TiF3,研究发现,Mg46Ti36Ni12Mn6+xwt.%TiF3(x=2,5,8,11)合金的吸氢量分别为1.65wt.%,2.33wt.%,1.95wt.%和1.87wt.%,当TiF3的质量分数为5%时,合金的储氢性能最佳。
为了比较相同含量不同添加剂的催化效果,在Mg46Ti36Ni12Mn6合金中添加质量分数为5%M(M=LiH, TiF3, Nb2O5, C)作为催化剂发现,添加C后合金主衍射峰所对应的FWHM最小,合金的晶格畸变越小,其次分别是TiF3、LiH和Nb205。在Mg46Ti36Ni12Mn6合金中添加5wt.%M,当M=C和LiH,能显著提高球磨效率,在相同的球磨时间内,合金的颗粒尺寸更小,但并不能提高合金的储氢性能；当M=TiF3和Nb205时,能有效的提高合金的储氢性能。Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3, C, Nb2O5, LiH)合金经过200h的球磨后,其储氢量分别为2.33wt.%、0.68wt.%、2.36wt.%和1.49wt.%。Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3, C, Nb2O5, LiH)合金氢化物的初始放氢温度温度分别为：568K、608K、535K和627K。
而当以5wt%M(M=MgH2,CaH2,LiAlH4,NaH)作为添加剂后,Mg46Ti36-Ni12Mn6合金的储氢性能有了较大改善,经过200h的球磨后,合金中都出现了BCC结构的相。与MgH2和LiAlH4相比,添加NaH和CaH2后,合金的颗粒更小,合金的固溶度以及非晶化程度更高,当添加NaH和CaH2后,以Mg-Ti为基体,其他元素更易于固溶到Mg-Ti基体中,形成较为稳定的Mg-Ti基BCC结构。在303K温度下,其吸氢量分别为2.78wt.%、2.16wt.%、0.71wt.%和0.85wt.%。当温度在573K时,除了以CaH2作为添加剂的合金外,其他合金均在较短的时间内吸氢达到平衡,合金的吸氢量分别为3.1wt.%、2.76wt.%、3.2wt.%和1.95wt.%,随着温度的增加,合金吸氢量略有上升。合金氢化物经过加热后第一个吸热峰分别为：534K、517K、521K和553K。当以CaH2、 LiAlH4、MgH2和NaH做为添加剂后,在一定程度上降低储氢合金的释氢温度。
以Co,Cr,Fe和V取代Mg46Ti36Ni12Mn6合金中的Mn,在Mg46Ti36Ni12Cr6、 Mg46Ti36Ni12Fe6和Mg46Ti36Ni12V6合金中BCC结构相出现在40.4°、58.6°和73.9°位置,合金中除了出现BCC结构外,还有FCC结构相和Diamond Cubic结构相；而在M946Ti36Ni12Co6合金中,BCC结构出现在42.9°和62.2°位置,合金中未出现FCC结构相和diamond Cubic结构相,但有Primitive Cubic结构相。Mg46Ti36Ni12M6(M=Co,Cr,Fe,V)合金BCC结构相晶格参数分别为：0.2982、0.3148、0.3140和0.3376nm,BCC结构的晶格参数随着替代元素原子半径的增大而增大。在303K时,Mg46Ti36Ni12M6(M=Co,Cr,Fe,V)合金的吸氢量分别为1.14wt.%、1.59wt.%、1.55wt.%和2.38wt.%；在573K时,其吸氢量分别为1.95wt.%、2.25wt.%、2.01wt.%和2.95wt.%,合金的吸氢量随着替代元素原子半径的增大而增大。Mg46Ti36Ni12M6(M=Co,Cr,Fe,V)合金氢化物初始放氢温度分别为460K、441K、441K和453K,在加热过程第一个吸热峰分别出现在624K、530K、514K和569K。
Hydrogen atoms mainly occupy the interstitial site among metal atoms in metal hydrides. In comparison with FCC and HCP structures, BCC structures have more interstitial site to hold much more hydrogen. Mg and Ti are more popular metallic elements which form stable hydrides because of their higher hydrogen capacities (theoretically up to7.6wt%) and lower costs (they form MgH2and TiH2hydrides including7.6mass%and4.0mass%hydrogen, respectively), so that MgH2and TiH2hydrides are excellent materials for vehicle fuel and nickel-metal hydride batteries. In the present work, we have explored the preparation method to synthesize Mg-Ti BCC alloys and tried to improve the hydrogen storage performance of these alloys by adding different kinds of additives.
Mg76Ti12Ni12-xCrx (x=0,3,6,9) alloys were prepared by mechanical alloying. For Mg76Ti12Ni12alloy, the binary alloy phase of Mg2Ni and Ti2Ni phase formed after milled30h. Besides Ti2Ni phase and Mg2Ni phase, Cr1.75Nio.25Ti phase also formed in the Mg76Tii2Ni12-xCrx (x=3,6,9) alloys. For Mg76Ti12Ni12-xCrx (x=0,3,6,9) alloys, the amorphous degree increased with the increase of Cr content. The hysteresis coefficient of hydrogen absorptiondes-orption decreased, as well as the hydrogen absorption rate could be improved by adding proper Cr content.
The Ti and Mg content were changed based on Mg76Ti,2Ni9Cr3alloy. Mg76-xTi12+xNi9Cr3(x=4,8,12,16) alloys were prepared by mechanical alloying. For Mg76-xTi12+xNi9Cr3(x=4,8,12,16) alloys, the main binary alloy phase was Mg2Ni and Ti2Ni after milled. And the hydrogen storage capacity was3.93wt.%,3.82wt.%,3.64wt.%and2.81wt.%after milled20h. However, it decreased to2.36wt.%,2.16wt.%,1.81wt.%,2.0wt.%when the milling time increased to80h. It was found that the hydrogen storage capacity decreased with the increase of the milling time and the ratio of Ti/Mg. It was also found from DTA results that the hydrogen desorption temperature of the Mg76-xTi12+xNi9Cr3(x=4,8,12,16) hydride were550K,528K,518K and506K, respectively. The hydrogen desorption temperature decreased with increasing the rate of Ti/Mg. The decomposition enthalpies of the Mg76-xTi12+xNi9Cr3(x=4,8,12,16) hydride were-80.2kJ/mol,-78.5kJ/mol,-73.5kJ/mol and-80.0kJ/mol, respectively. The decomposition enthalpy decreased with the increase of Ti content firstly, then increased with increasing Ti content. The stability of the hydride can be reduced with proper Ti content.
Mg76-xTi12Ni12Mnx (x=2,4,6,8) alloys were prepared by mechanical alloying and the effects of Mn content on the hydrogen storage properties were investig-ated systematically. For Mg76-xTi12Ni12Mnx (x=2,4,6,8) alloys, the main binary alloy phase consist of Mg2Ni and Ti2Ni too. It was found that TiMn2phase appeare when x=6and x=8. The hydrides decomposition enthalpies of Mg76-xTi12Ni12Mnx (x=2,4,6,8) alloys were-79.2kJ/mol,-78.0kJ/mol,-73.7kJ/mol and-73.6kJ/mol. The hydrogen storage capacity increased, as well as the stability of the hydride reduced with the addition of the Mn element. The thermodynamics performance was also improved with addition of the element Mn.
According to the good hydrogen storage properties of Mg70Ti12Ni12Mn6alloy mentioned above, Mg70-xTi12+xNi12Mn6(x=8,16,24,32) alloys were prepared by mechanical alloying. The alloys were mainly composed of HCP and FCC structures after ball-milling for50h. When the milling time increased to100h, it was shown that the diffraction peak of Mn element disappeared, as well as the diffraction peak of Mg and Ni weakened gradually. However, the peak intensities of Ti increase significantly. It was suggested that Mg, Ni and Mn dissolve into Ti lattice to form solid solution. When the milling time increased to200h, X-ray diffraction (XRD) testing showed that the diffraction peak of Mg2Ni occurs, and the diffraction peak of Mg and Ni decreased while the intensity of X-rays diffraction pattern of Ti was improved at2θ=35.3°,38.4°,40.2°nd43.1°. These results demonstrated that Mg and Ni further dissolve into Ti lattice. For Mg46Ti36Ni12Mn6and Mg38Ti44Ni12Mn6alloys, the peaks with the BCC structure appeared at20=43.1°,63.1°and70.7°. After ball-milling for400h, the diffraction peak of Mg disappeared, and part of the diffraction peak of Ni also disappeared, only FCC and BCC structure exist. These results were also due to that Mg and Ni further dissolved into Ti lattice. And, the FCC structure which corresponded to Ni was due to Ni element not yet diffusing into Ti lattice. The hydrogen storage capacity of Mg46Ti36Ni12Mn6alloy with BCC structure was1.36wt.%at573K, and the dehydriding temperature was lower than that of Mg62Ti2oNi12Mn6, Mg54Ti28Ni12Mn6and Mg38Ti44Ni12Mn6hydrides.
To improve the hydrogen storage performance of BCC solid solution Mg46Ti36Ni12Mn6alloy, we added xwt.%TiF3(x=2,5,8,11) to Mg46Ti36Ni12Mn6alloy. The hydrogen storage capacity of Mg46Ti36Ni12Mn6+xwt.%TiF3(x=2,5,8,11) was1.65wt.%,2.33wt.%,1.95wt.%and1.87wt.%, respectively. Among these alloys, the Mg46Ti36Ni12Mn6+5wt.%TiF3alloy presented the best hydrogen storage performance.
To study the effects of different kinds of catalyst on the hydrogen storage performance of the Mg46Ti36Ni12Mn6alloy with BCC structure,5wt.%M (M=LiH,TiF3,Nb205and C) was added. For Mg46Ti36Ni,2Mn6+5wt.%M (M=LiH,TiF3,Nb205and C) alloys, X-ray diffraction studies indicated that the full width at half maximum (FWHM) of main diffraction peaks corresponding to Mg46Ti36Ni12Mn6+5wt.%C was the smallest. The results revealed that the crystal lattice distortion of Mg46Ti36Ni12Mn6alloy was the least when adding C, the next was TiF3, LiH and Nb2O5. After ball-milling for200h, the hydrogen storage capacity of Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3,C,Nb205,LiH) alloys were2.33wt.%,0.68wt.%,2.36wt.%and1.49wt.%respectively. Among these alloys, the particle size of Mg46Ti36Ni12Mn6+5wt.%M(M=C,LiH) was smaller. The result implied that C and LiH could raise mechanical milling efficiency but did not improve the hydrogen storage performance. However, the hydrogen storage performance can be improved by adding TiF3and Nb2O5. It could be seen from the DTA results that the initial exothermic temperature for Mg46Ti36Ni12Mn6+5wt.%M(M=TiF3,C,Nb205,LiH) hydride were568K,608K,535K and627K, respectively.
The effect of metal hydride on hydrogen storage properties of Mg46Ti36Ni12-Mn6alloy were investigated By adding5wt.%M (M=MgH2, CaH2, LiAlH4, NaH). It could be found that the BCC structure came into being after ball-milling for200h. SEM results showed that the particle size was smaller, the solubility was better and the efficiency of amorphousness was higher when NaH and CaH2other than MgH2and LiAlH4were used as additives. Furthermore, other elements were easier to dissolve into the Mg-Ti matrix and to form stable BCC structure when NaH and CaH2were used as additives. At303K, the hydrogen storage capacity of Mg46Ti36Ni12Mn6+5wt.%M(M=MgH2, CaH2, LiAlH4, NaH) alloys were2.78wt.%,2.16wt.%,0.71wt.%and0.85wt.%, respectively, and were3.1wt.%,2.76wt.%,3.2wt.%and1.95wt.%as the temperature increased to573K. That was to say, the hydrogen storage capacity increased with increasing the temperature. The differential thermal analysis (DTA) results showed that the first endothermic peaks of Mg46Ti36Ni]2Mn6+5wt.%M(M=MgH2, CaH2, LiAlH4, NaH)hydride were534K,517K,521K and553K, respectively. The hydrogen desorption temperature were deduced by adding MgH2, CaH2, LiAlH4and NaH additives.
The effect of substituting elements M (M=Co, Cr, Fe, V) for element Mn on hydrogen storage performance of Mg46Ti36Ni12M6alloy has been studied. For Mg46Ti36Ni12Cr6, Mg46Ti36Ni12Fe6and Mg46Ti36Ni12V6alloys, BCC structure, FCC structure as well as diamond cubic structure were observed, and the BCC structure appeared at29=40.4°,58.6°nd73.9°. For Mg46Ti36Ni12Co6alloy, they were only BCC structure and Primitive Cubic structure, not FCC structure and diamond Cubic structure, and the BCC structure appeared at2θ=42.9°and62.2°. The crystal lattice parameter of the BCC solid solution of Mg46Ti36Ni12M6(M=Co,Cr,Fe,V) alloys were2.9828,3.1475,3.1403and3.3764nm, respectively. The crystal lattice parameter increased with the increase of atomic radius of substitute elements.It was found that synthesized Mg46Ti36Ni12M6(M=Co, Cr, Fe, V) alloys were able to absorb hydrogen up to1.14wt.%,1.59wt.%,1.55wt.%and2.38wt.%at303K, respectively. And it increased to1.95wt.%,2.25wt.%,2.01wt.%and2.95wt.%when the temperature rised to573K. The hydrogen storage capacities of Mg46Ti36Ni12M6(M=Co, Cr, Fe, V) increased with the increasing of the substitution elements atomic radius. The initial hydrogen desorption temperature of Mg46Ti36Ni12M6(M=Co,Cr,Fe,V) hydride was460K,441K,441K and453K, and, the first endothermic peak appeared at624K,530K,514K and569K, respectively.
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