CN102286684A - Magnesium-based hydrogen storage alloy - Google Patents
Magnesium-based hydrogen storage alloy Download PDFInfo
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- CN102286684A CN102286684A CN 201110226110 CN201110226110A CN102286684A CN 102286684 A CN102286684 A CN 102286684A CN 201110226110 CN201110226110 CN 201110226110 CN 201110226110 A CN201110226110 A CN 201110226110A CN 102286684 A CN102286684 A CN 102286684A
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- base hydrogen
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 364
- 239000001257 hydrogen Substances 0.000 title claims abstract description 315
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 239000000956 alloy Substances 0.000 title claims abstract description 171
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 171
- 239000011777 magnesium Substances 0.000 title claims abstract description 119
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000003860 storage Methods 0.000 title abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 239000001996 bearing alloy Substances 0.000 claims description 48
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 230000006698 induction Effects 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000005300 metallic glass Substances 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003795 desorption Methods 0.000 abstract description 30
- 238000010521 absorption reaction Methods 0.000 abstract description 29
- 150000002431 hydrogen Chemical class 0.000 description 41
- 238000009792 diffusion process Methods 0.000 description 16
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000007599 discharging Methods 0.000 description 13
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- 238000005275 alloying Methods 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000010949 copper Substances 0.000 description 5
- 230000003434 inspiratory effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910019083 Mg-Ni Inorganic materials 0.000 description 4
- 229910019403 Mg—Ni Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- 230000006872 improvement Effects 0.000 description 3
- 239000002707 nanocrystalline material Substances 0.000 description 3
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- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
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- 238000003723 Smelting Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a magnesium-based hydrogen which is composed of Mg, Ni and Mm three components, wherein Mg is magnesium element and accounts for 68-76% by mass; Ni is nickel element and accounts for 14-24% by mass; and Mm is rare earth element, accounts for 4-12% by mass and is composed of Ce and La. According to the magnesium-based hydrogen storage alloy provided by the invention, the cost is lowered and the hydrogen absorption and desorption performance is improved.
Description
Technical field
The present invention relates to a kind of hydrogen storage alloy, relate in particular to a kind of Mg base hydrogen bearing alloy.
Background technology
The energy is the basic substance of human existence and Sustainable development.Because of the not reusable edible of traditional energies such as oil, coal, Sweet natural gas, the alternative energy such as sun power, wind energy, Geothermal energy, Hydrogen Energy are much accounted of and constantly obtain exploitation already, and wherein to be known as be one of the most promising future source of energy to Hydrogen Energy.Alloy (being called alloy) with form of metal compound storage hydrogen is to generally acknowledge one of best hydrogen storage method at present.When needs were inhaled hydrogen, alloy and H-H reaction formed metal hydride, thereby with storing hydrogen; When needs are put hydrogen, make metal hydride discharge hydrogen by controlled temperature and/or pressure.Inhaling hydrogen and putting hydrogen is simple and easy to do reversing process.
In alloy, by alloying constituent and structure, metal hydrogen storage material can be divided into: (the AB of rare earth system
5Type), (AB of zirconium system
2Type), (A of ferrotitanium system (AB type) and magnesium system
2Type B) wherein A be meant can with the heat release shaped metal of hydrogen evolution stable hydride, based on IA, IIA, IIIB～VB family metal and Pd, Mm (Ti, Zr, Mg, Ca, V, RE etc., wherein, RE represents rare earth metal), B is meant difficult with hydrogen evolution hydride but the endothermic metal with catalytic activity mainly is VIB～VIII (except Pd, the Mm) transition metal (Fe, Co, Ni, Cr, Mn, Al, Cu etc.).
In the metal hydrogen storage material, MAGNESIUM METAL is owing to have high hydrogen storage, the density of 7.6wt.%H little (only being 1.74g/cm3), aboundresources, cheap characteristics such as safe in utilization, and being acknowledged as has one of hydrogen storage material of DEVELOPMENT PROSPECT most.The Mg base hydrogen bearing alloy system comprises that mainly Mg-Co, Mg-Cu, Mg-Ni, Mg-Fe, Mg-La, Mg-Al system reach ternary and the multicomponent alloy that develops on this basis.Wherein, Mg
2The reaction Enthalpies of Formation of Ni is 64.5KJ/mol, far below MgH
274.5J/mol, reduced the thermodynamic stability of magnesium alloy, Mg-Ni is that alloy just becomes important research and development object thus.
Although lot of domestic and foreign scholar is that alloy has carried out research extensively and profoundly to Mg-Ni, the Mg-Ni that still requires further improvement is an alloy, to reduce cost and to improve hydrogen storage property.
Summary of the invention
In view of the problem that exists in the background technology, the object of the present invention is to provide a kind of Mg base hydrogen bearing alloy, it can reduce cost.
A further object of the present invention is to provide a kind of Mg base hydrogen bearing alloy, and it can improve hydrogen storage property.
In order to achieve the above object, the invention provides a kind of Mg base hydrogen bearing alloy, form by Mg, Ni and three kinds of components of Mm, wherein: Mg, promptly magnesium elements accounts for 68～76 quality %; Ni, promptly nickel element accounts for 14～24 quality %; Mm, the expression rare earth account for 4～12 quality %, and Mm is made up of Ce and La.
In according to Mg base hydrogen bearing alloy of the present invention, La accounts for 36.98 quality % in Mm, and Ce accounts for 63.00 quality % in Mm.
In according to Mg base hydrogen bearing alloy of the present invention, described Mg base hydrogen bearing alloy is a cast alloy.
In according to Mg base hydrogen bearing alloy of the present invention, described Mg base hydrogen bearing alloy is a nanometer crystal alloy.
In according to Mg base hydrogen bearing alloy of the present invention, described Mg base hydrogen bearing alloy is a non-crystaline amorphous metal.
In according to Mg base hydrogen bearing alloy of the present invention, described Mg base hydrogen bearing alloy comprises Mg, Mg
2Ni and MmMg
12Three thing phases.
In according to Mg base hydrogen bearing alloy of the present invention, Mg is 72 quality %, and Ni is 20 quality %, and Mm is 8 quality %.
In according to Mg base hydrogen bearing alloy of the present invention, described Mg base hydrogen bearing alloy is a nanometer crystal alloy, and grain-size is no more than 20nm before the described nanometer crystal alloy suction hydrogen.
In according to Mg base hydrogen bearing alloy of the present invention, Ni in the described magnesium nickel rare earth-based alloy and the melting of Mm elder generation prepare prealloy, more than being the magnesium fusing point, Heating temperature carries out induction melting with Mg again after the prealloy fragmentation with preparation then, to obtain the ternary master alloy of Mg base hydrogen bearing alloy, ternary master alloy solidifies and obtains as cast condition Mg base hydrogen bearing alloy, nanocrystalline Mg base hydrogen bearing alloy or amorphous Mg base hydrogen bearing alloy.
In according to Mg base hydrogen bearing alloy of the present invention, the temperature of described induction melting is a magnesium fusing point to 670 ℃.
Technique effect of the present invention is as follows.
In Mg base hydrogen bearing alloy of the present invention, owing to adopt cheap mishmetal (La+Ce) preparation Mg base hydrogen bearing alloy, thus reduced cost.
In Mg base hydrogen bearing alloy of the present invention, because the configuration of Ni and Mm has improved hydrogen storage property.
Description of drawings
XRD composed before Fig. 1 illustrated as cast condition Mg-Ni-Mm absorption hydrogen;
Fig. 2 illustrates the PCT curve of 325 ℃ of as cast condition Mg-10Ni-xMm (x=1,2,3) alloys;
Fig. 3 illustrates as cast condition Mg-10Ni-xMm (x=1,2,3) alloy at 325 ℃, suction hydrogen curve during P=1.0MPa;
Fig. 4 illustrate as cast condition Mg-10Ni-xMm (x=1,2,3) alloy 325 ℃, put the hydrogen curve during P=1.0MPa;
Fig. 5 illustrates the PCT curve of 325 ℃ of as cast condition Mg-yNi-2Mm (y=8,10,12) alloys;
Suction hydrogen curve when Fig. 6 illustrates 325 ℃ of as cast condition Mg-yNi-2Mm (y=8,10,12) alloys, P=1.4MPa;
When illustrating 325 ℃ of as cast condition Mg-yNi-2Mm (y=8,10,12) alloys, P=1.4MPa, Fig. 7 puts the hydrogen curve;
XRD composed before Fig. 8 illustrated as cast condition Mg-10Ni-2Mm (B) absorption hydrogen;
Fig. 9 illustrates as cast condition Mg-10Ni-2Mm (B) alloy PCT curve at each temperature;
Figure 10 illustrates as cast condition Mg-10Ni-2Mm (B) alloy Mg and Mg
2Ni inhales Van ' the t Hoff curve of hydrogen;
Figure 11 illustrates under as cast condition Mg-10Ni-2Mm (B) the alloy 1.8MPa 275～375 ℃ suction hydrogen kinetic curve;
Hydrogen desorption kinetics curve when Figure 12 illustrates under as cast condition Mg-10Ni-2Mm (B) the alloy 1.8MPa 275～375 ℃;
Figure 13 illustrates the XRD spectra of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy;
Figure 14 illustrates the TEM photo before nanocrystalline M g-10Ni-2Mm (Cu1000) absorption hydrogen;
Figure 15 is illustrated in the TEM photo behind nanocrystalline M g-10Ni-2Mm (Cu1000) absorption hydrogen;
Figure 16 illustrates the PCT curve of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 275 ℃～350 ℃;
Figure 17 illustrates the suction hydrogen curve of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 1.0MPa, 275 ℃～350 ℃ conditions;
Figure 18 illustrates nanocrystalline M g-10Ni-2Mm (Cu1000) alloy and put the hydrogen curve under 1.0MPa, 275 ℃～350 ℃ condition;
The suction hydrogen curve that Figure 19 is nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 300 ℃, 0.65～1.0MPa condition;
Figure 20 is nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 300 ℃, 0.65～1.0MPa condition puts the hydrogen curve;
Figure 21 illustrates the optimum regime of nanocrystalline material hydrogen storage property at each temperature;
Figure 22 illustrates the XRD spectra of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy;
Figure 23 illustrates the TEM photo behind non-crystalline state Mg-10Ni-2Mm (Cu2000) absorption hydrogen;
Figure 24 illustrates the MmH behind non-crystalline state Mg-10Ni-2Mm (Cu2000) absorption hydrogen
3-xThe TEM photo of the high resolution phase of phase;
Figure 25 illustrates the PCT curve of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=275 ℃～350 ℃;
Figure 26 illustrates the suction hydrogen curve of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under P=1.8MPa, T=275～350 ℃;
Figure 27 illustrates non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy and put the hydrogen curve under P=1.8MPa, T=275～350 ℃;
The suction hydrogen curve that Figure 28 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=350 ℃, P=1.0～1.8MPa;
Figure 29 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=350 ℃, P=1.0～1.8MPa puts the hydrogen curve;
The suction hydrogen curve that Figure 30 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=275 ℃, P=0.2～1.8MPa;
Figure 31 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=275 ℃, P=0.2～1.8MPa puts the hydrogen curve;
Figure 32 illustrates Van ' the t Hoff curve of the alloy of various grain forms;
Figure 33 illustrates kinetic curve under T=325 ℃ of the Mg-10Ni-2Mm alloy, P=1.0MPa of different tissues state.
Embodiment
Below in conjunction with accompanying drawing each embodiment according to Mg-Ni-Mm alloy of the present invention is described.
Table 1 provides prescription and the alloy of each embodiment and represents formula.In each embodiment that table 1 is listed, the purity 99.90% of Mg, the purity of Ni are 99.95%, and the purity of Mm is 99.98%.In Mm, La accounts for 36.98%, and Ce accounts for 63.00%.Wt% representation quality per-cent.
For embodiment 1-5, its preparation process is: in the ratio that table 1 provides, Ni and the Mm with said ratio carries out the prealloy melting with electric arc furnace earlier; Mix with the prealloy fragmentation and with the magnesium grain, carry out vacuum induction melting; Mother alloy with induction melting obtains carries out naturally cooling, obtains the as cast condition Mg-Ni-Mm alloy of embodiment 1-5 correspondence.
The high vacuum magnetic control arc stove of Shenyang Scientific Instrument Research ﹠ Mfg. Center Co., Ltd., C.A.S is adopted in the prealloy melting.In the prealloy fusion process, build lid in the smelting pot with the Ni of said ratio and Mm, be evacuated to 6 * 10
-3Below the Pa, 30min is arranged approximately, charge into argon gas and stop to 0.05MPa; Starting rod slowly raises starting rod after the starting the arc in distance raw material 1-2mm place's striking then, progressively regulates the striking electric current, strengthen the intensity of electric arc, treat can strengthen the magnetic stir current after the raw material fusing, stir current is controlled at about 10A, and raw material is stirred fully.Each melting is intact once wait to solidify after, with mechanical manipulator it is overturn, carry out melting next time.This prealloy melting repeatedly three times promptly even substantially.
In vacuum induction melting, induction melting equipment is intermediate frequency vacuum induction furnace ZG-25, peak power 60KW, and standard capacity is 25kg, 1800 ℃ of maximum operating temperatures, final vacuum 1.0 * 10
-2Pa.Vacuum induction furnace is furnished with thermopair, accurately controlled temperature.In the vacuum induction melting process, adopt temperature on a little higher than Mg fusing point (651 ℃) (adopt 651 ℃ to 680 ℃ in the method, preferred 651 ℃ to 670 ℃, more preferably 651 ℃ to 660 ℃) insulation certain hour, be equipped with stirring to a certain degree; Feed argon gas during vacuum induction melting, can avoid the magnesium alloy oxidation and suppress the Mg volatilization.
For embodiment 6 and embodiment 7, its preparation process is: adopt the mother alloy of Mg-10Ni-2Mm (B) alloy of embodiment 2 preparations, adopting under argon shield and the molten state, spray the copper cooling wheel disc in rapid solidification equipment.When adopting the copper cooling wheel disc of 10.5m/s linear velocity, obtain the crystalline state nanometer Mg-10Ni-2Mm alloy of embodiment 6, and be denoted as Mg-10Ni-2Mm (Cu1000); When adopting the copper cooling wheel disc of 20.9m/s linear velocity, obtain non-crystalline state Mg-10Ni-2Mm alloy, and be denoted as Mg-10Ni-2Mm (Cu2000).The rapid solidification equipment of embodiment 6-7, commercially available from Shenyang Scientific Instrument Research ﹠ Mfg. Center Co., Ltd., C.A.S.It should be noted that copper cooling wheel disc can adopt stainless steel, graphite wheel disc to wait to substitute, and all is in the row of rapid solidification method.
The prescription of each embodiment of table 1, test value and alloy are represented formula
After to above-mentioned each embodiment preparation, carry out analyses such as composition analysis, material phase analysis, microstructure analysis, the test of alloy hydrogen storage property.Composition analysis adopt the analysis of German S4Pioneer type X-ray fluorescence spectra (X Ray Fluorescence, XRF).Material phase analysis adopts the D8Discover X-ray diffractometer.Microstructure analysis the Hitachi S-3400N/EDS of company scanning electronic microscope and energy spectrum analysis system, transmission electron microscope (TEM) is the JEM2010 type of NEC company.PCT tester (the model: PCT-1SPWIN) of the Japanese Suzuki of the hydrogen storage property test employing company of alloy.
The composition test sample of embodiment is the rectangular parallelepiped of surface size 2cm * 2cm.For fear of the error that oxidation or impurity bring, in glove box, sample surfaces has been carried out the turning processing.The alloying constituent detected result sees Table 1, the elemental composition deviation slightly of alloying constituent and design alloy, and the component segregation that forms in stirring inequality and the alloy process of cooling in this main and melting has much relations, and alloy has a spot of volatilization in addition.
Below each embodiment is carried out other analyses.
At first, the as cast condition Mg-Ni-Mm alloy of comparative example 1-5 acquisition.
XRD composed before Fig. 1 illustrated as cast condition Mg-Ni-Mm absorption hydrogen.
As shown in Figure 1, thing phase basically identical before the suction hydrogen of the cast alloy of each proportioning among the embodiment 1-5, and as cast condition Mg-Ni-Mm alloy comprises three thing phase: Mg, Mg
2Ni and MmMg
12Phase.Mg and Mg
2There is very high intensity at the corresponding peak of Ni, means that this biphase content is higher in the alloy, is main thing phase, and collection of illustrative plates shows that the Mg that also has a spot of rich Mm exists mutually mutually, demarcates to be MmMg
12Phase.
Secondly, comparative example 1, embodiment 2 and embodiment 3 and with reference to Fig. 1, Fig. 2, Fig. 3, Fig. 4 illustrate the influence of Mm content to the Mg-Ni-Mm alloy.
As shown in Figure 1, the add-on along with Mm increases (Mg-10Ni-1Mm (A)＜Mg-10Ni-2Mm (B)＜Mg-10Ni-3Mm (C)), MmMg
12The peak obviously change gradually, near the peak 2 θ=17 ° and 34 ° especially, the latter is near (002) corresponding peak of magnesium.Broadening to a certain degree appears in the Mg peak.In all cast alloy, the figure spectral curve of Mg-10Ni-3Mm (C) back of the body end, is the most mixed and disorderly, no matter is Mg or Mg
2Tangible broadening phenomenon all appears in the peak of Ni phase.Therefore too much Mm helps the refinement of alloying pellet, and the crystal state of alloying pellet is improved active effect.
Fig. 2 illustrates the PCT curve of 325 ℃ of as cast condition Mg-10Ni-xMm (x=1,2,3) alloys.As shown in Figure 2, the PCT curve is seen the not variation of pressure platform from integral body, and plateau pressure overlaps substantially, so the thermodynamics of alloys performance is not obviously improved.The width of height two platforms all changes, and with the increase of Mm content, platform broadens, and particularly in the alloy of x=3, low platform extends to 4.337wt.%H, and the potentiality that pure magnesium is inhaled hydrogen have obtained further excavation.As seen,, promote that the hydrogenation effect is remarkable,, have only dynamic performance to be improved for the diffusion condition that facilitates though the increase of Mm amount is few.
Fig. 3 illustrates as cast condition Mg-10Ni-xMm (x=1,2,3) alloy at 325 ℃, suction hydrogen curve during P=1.0MPa.As shown in Figure 3, the initial hydrogen-absorption speed basically identical of as cast condition Mg-10Ni-xMm alloy, total but hydrogen increase with Mm amount and improve.When Mg-10Ni-1Mm (A) alloy hydride speed reduced significantly, the inspiratory capacity minimum only was about 2.65wt.%H, and final inspiratory capacity also is lower than 3.5wt.%H.Mg-10Ni-2Mm (B) alloy kept stable after inspiratory capacity reaches 4.4wt.%H.Mg-10Ni-3Mm (C) alloy is when the suction hydrogen amount of reaching is neighbouring to 3.3wt.%H, and hydrogen-absorption speed slightly slows down, and the speed-raising phenomenon is arranged again subsequently, and inspiratory capacity has greatly improved after this point, finally reaches maximum hydrogen 5.165wt.%H.This phenomenon has been confirmed the relative Mg of rich Mm once more and has been inhaled the katalysis of hydrogen and the promoter action that hydrogen is spread mutually.
Fig. 4 illustrate as cast condition Mg-10Ni-xMm (x=1,2,3) alloy 325 ℃, put the hydrogen curve during P=1.0MPa.As shown in Figure 4, this system alloy all has hydrogen desorption kinetics performance preferably, the fastest 5min on the whole.The slowest 10min is dehydrogenation fully just, and the difference of hydrogen desorption capacity comes from the difference of hydrogen.
To sum up, in Mg-10Ni-xMm (x=1,2,3), the comprehensive hydrogen storage property of as cast condition Mg-10Ni-3Mm (C) alloy is best.For as cast condition Mg-10Ni-3Mm (C), best suction is put hydrogen condition and is: 325 ℃, and 1.0MPa, maximal inspiratory capacity is 5.16wt.%H, 6.2min can finish to put hydrogen, hydrogen-releasing rate 95.6%.
Then, comparative example 2, embodiment 4 and embodiment 5 and with reference to Fig. 1, Fig. 5, Fig. 6 and Fig. 7 illustrate the influence of the quantitative changeization of Ni to the Mg base hydrogen bearing alloy hydrogen storage property.
As shown in Figure 1, in the cast alloy (Mg-8Ni-2Mm (D)＜Mg-10Ni-2Mm (B)＜Mg-12Ni-2Mm (E)) that Ni content increases, Mg is comparatively clearly arranged all
2Ni, but that intensity is just distinguished is not obvious.2 θ=17 ° the MmMg that locates among the MG-8NI-2MM (D)
12The peak is all obvious than other alloys; Mg among the Mg-10Ni-3Mm (C)
2The peak of Ni is the strongest in all cast alloy unexpectedly, simultaneously with comparatively tangible MmMg
12The peak.Therefore deducibility, increasing of Ni may suppress MmMg
12Formation, but when the add-on of Ni and Mm reaches certain proportion, Mg
2Ni and MmMg
12Clear sharp-pointed peak appears in Xiang Douhui, to the alloy hydrogen storage property good promoter action should be arranged.Thus, the ratio of Ni and Mm (being that qualitative ratio is 5: 3) is preferred in the preferred embodiment 3.
Fig. 5 illustrates the PCT curve of 325 ℃ of as cast condition Mg-yNi-2Mm (y=8,10,12) alloys.As shown in Figure 5, the suction hydrogen curve of Mg-12Ni-2Mm (E), the pressure platform of Mg-12Ni-2Mm (E) has slightly rising than the pressure platform of other two composition samples, no matter be low pressure platform or high pressure platform, all depicted by two points, as seen when pressure exceeded the phase transformation equilibrium pressure slightly, alloy just can be inhaled hydrogen fast in a large number, finish transformation mutually, total hydrogen-storage amount of Mg-12Ni-2Mm (E) alloy descends to some extent than Mg-10Ni-2Mm (B); Mg-8Ni-2Mm (D) low pressure platform is also more smooth, and phase transition rate is also very fast, and high voltage platform is obviously shorter, and the hydrogen-storage amount Mg-10Ni-2Mm (B) mutually more with containing Ni still has gap.
Suction hydrogen curve when Fig. 6 illustrates 325 ℃ of as cast condition Mg-yNi-2Mm (y=8,10,12) alloys, P=1.4MPa.As shown in Figure 6, the hydrogen-absorption speed of Mg-10Ni-2Mm (B) is the fastest, and Mg-12Ni-2Mm (E) takes second place, and Mg-8Ni-2Mm (D) speed is the slowest.Rate curve shows that under the pressure of alloy at 1.4MPa of other two kinds of compositions, when hydrogen began slowly to rise, Mg-12Ni-2Mm (E) had still kept hydrogenation speed faster, and hydrogen is much larger than the alloy of other two compositions.Yet the final hydrogen of contrast PCT curve M g-12Ni-2Mm (E) is not maximum, that is to say that hydrogen has a process that descends.
When illustrating 325 ℃ of as cast condition Mg-yNi-2Mm (y=8,10,12) alloys, P=1.4MPa, Fig. 7 puts the hydrogen curve.As shown in Figure 7, Mg-8Ni-2Mm (D) initial stage hydrogen discharging speed is the slowest, but hydrogen desorption capacity can be caught up with and surpassed Mg-12Ni-2Mm (E) behind the 15min, and after this hydrogen desorption capacity still has rising tendency.Mg-10Ni-2Mm (B) hydrogen discharging speed is the fastest, and hydrogen desorption capacity keeps 4.2wt.%H constant substantially behind the 15min.Contain the maximum Mg-12Ni-2Mm of Ni (E) and tend to be steady soon, hydrogen desorption capacity is constant substantially behind the 7min.But the hydrogen desorption capacity of Mg-12Ni-2Mm (E) is minimum, and hydrogen discharging rate is between Mg-8Ni-2Mm (D), Mg-10Ni-2Mm (B).
To sum up, in Mg-yNi-2Mm, it is best that Ni adds the comprehensive hydrogen storage property of moderate Mg-10Ni-2Mm (B), and 325 ℃ of hydrogen-storage amount 5.309wt.%H inhale hydrogen 10min and finish 90% suction hydrogen (3.9wt.%H), put in the hydrogen 15min to reach stable.
Based on the explanation of Fig. 2-4 and Fig. 5-7, alloy all is beneficial to the hydrogenation forming core mutually and the short-range diffusion of hydrogen because of the adding of Ni and Mm, and by contrast, the better effects if of Mm is a little.
Next, contrast identical component but different embodiment 2, embodiment 6, the embodiment 7 of structural state are described.
The thing phase character of embodiment 2 is described with reference to Fig. 8.XRD composed before Fig. 8 illustrated as cast condition Mg-10Ni-2Mm (B) absorption hydrogen.As shown in Figure 8, as cast condition Mg-10Ni-2Mm (B) alloy is being inhaled Mg phase peak, the inferior strong Mg that hydrogen moves ahead very strong
2Ni phase peak, there is a spot of MmMg that peak shape is comparatively narrow and intensity is very high simultaneously
12Phase.
Fig. 9 illustrates as cast condition Mg-10Ni-2Mm (B) alloy PCT curve at each temperature.Mg-10Ni-2Mm (B) alloy promptly reaches stable through inhaling hydrogen after the activation of inhaling hydrogen 5 times repeatedly under 325 ℃, 1.8MPa test condition, begin immediately to test.Measuring temperature is 275～375 ℃, measuring stress scope 0～2.5MPa.
In Fig. 9, hydrogen is 4.929wt.%H during 275 ℃ of as cast condition Mg-10Ni-2Mm (B) alloys, and hydrogen is 5.37wt.%H in the time of 300 ℃, and hydrogen is 5.309wt.%H in the time of 325 ℃, 350 ℃ of hydrogen 5.531wt.%H, hydrogen is 5.26wt.%H in the time of 375 ℃.
As shown in Figure 9, the hydrogen curve is put in suction all two pressure platforms, i.e. the corresponding Mg → MgH of low pressure platform
2Generate platform, the corresponding Mg of high pressure platform
2Ni → Mg
2NiH
4Generate platform.Utilize the force value of pressure platform intermediate point and the relation of temperature can make Van ' t Hoff curve.
Table 2 illustrates 275～350 ℃ of Mg-10Ni-2Mm (B) alloys pressure platform at each temperature.
275～350 ℃ of pressure platforms at each temperature of table 2 as cast condition Mg-10Ni-2Mm (B)
Figure 10 illustrates as cast condition Mg-10Ni-2Mm (B) alloy Mg and Mg
2Ni inhales Van ' the t Hoff of hydrogen by line, the T representation temperature in the X-coordinate, the P representative pressure in the ordinate zou.
From Van ' t Hoff curve, can obtain MgH in as cast condition Mg-10Ni-2Mm (B) alloy
2And Mg
2NiH
4Hydrogen enthalpy entropy is put in suction, and is as shown in table 3.
MgH in table 3 as cast condition Mg-10Ni-2Mm (B) alloy
2And Mg
2NiH
4Hydrogen enthalpy entropy is put in suction
| ΔH f((kJ/mol)) | Theoretical value | ΔS f(J/mol·K) | Theoretical value | |
| MgH 2-suction hydrogen | -74.2 | -74.5 | -133.1 | -135 |
| MgH 2-put hydrogen | -74.3 | -74.5 | -132.2 | -135 |
| Mg 2NiH 4-suction hydrogen | -56.9 | -64.5 | -110.7 | -122 |
| Mg 2NiH 4-put hydrogen | -67.5 | -64.5 | -124.4 | -122 |
As can be seen from Table 3, MgH
2Δ H consistent with Δ S value with theoretical value; Mg
2NiH
4Δ H and Δ S be respectively-56.9kJ/mol H when inhaling hydrogen
2With-110.7J/mol, far below theoretical value-64.5kJ/mol H
2With-122J/mol, find out that thus the thermomechanical property of absorption hydrogen makes moderate progress.
With reference to Figure 11 and Figure 12, as cast condition Mg-10Ni-2Mm (B) alloy hydrogen absorption and desorption dynamic performance is described.
Figure 11 illustrates under as cast condition Mg-10Ni-2Mm (B) the alloy 1.8MPa 275～375 ℃ suction hydrogen kinetic curve.As shown in figure 11, finish 80% suction hydrogen process required time for 275 ℃, 300 ℃, 325 ℃, 350 ℃, 375 ℃ and be respectively 0.5min (2.9wt.%H), 0.8min (3.8wt.%H), 1.8min (4.0wt.%H), 5.5min (4.3wt.%H), 10min (3.9wt.%H).Absorption hydrogen speed comes from the existence that two kinds of catalysis phases are arranged in the alloy soon, and the dynamic performance of alloy monolithic improves a lot.275 ℃, 300 ℃, 325 ℃, 350 ℃, 375 ℃ maximum hydrogen is respectively 4.14,4.75,5.03,5.23,4.70wt.%H.Hydrogen obviously increases with the rising of temperature.The increase of total hydrogen comes from Ni, Mm and Mg forms cenotype, promotes MgH
2Forming core grow up, and respectively inhale hydrogen and have bigger thermodynamic driving force effect mutually under the high temperature, finish the hydrogenation process more fully.
Hydrogen desorption kinetics curve when Figure 12 illustrates under as cast condition Mg-10Ni-2Mm (B) the alloy 1.8MPa 275～375 ℃.As shown in figure 12, putting hydrogen for 275 ℃, 300 ℃, 325 ℃, 350 ℃, 375 ℃ finishes substantially in 35.8min (0.213wt.%H), 31.30min (1.30wt.%), 26.23min (3.64wt.%), 7.5min (4.78wt.%), 3.3min (4.399wt.%H).After 165 minutes, total hydrogen desorption capacity of 275 ℃, 300 ℃, 325 ℃, 350 ℃, 375 ℃ is respectively 0.39wt.%H, 1.65wt.%H, 4.05wt.%H, 4.88wt.%H, 4.45wt.%H.Under the uniform pressure, from inhaling hydrogen releasing efficient 350 ℃ best, hydrogen is near 5.2wt.%H, and puts substantially in 10 minutes, though 275 ℃ and 300 ℃ of suction hydrogen are fast, can only emit a spot of hydrogen, hydrogen discharging rate is low.Alloy has very high hydrogen discharging rate in the time of 375 ℃, and hydrogen is lower than 350 ℃, and corresponding hydrogen desorption capacity is also just low.
To sum up, the best down suction hydrogen discharging temperature of as cast condition Mg-10Ni-2Mm (B) alloy 1.8MPa is 350 ℃.
Next illustrates embodiment 6.
Figure 13 illustrates the XRD spectra of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy.As shown in figure 13, there is tangible broadening at the XRD peak of Mg-10Ni-2Mm (Cu1000) alloy, and the back of the body end is strengthened, and illustrates that the alloy grain size significantly reduces.Intensity raises and illustrates that appearance is decrystallized in the alloy privately.The peak of (010) crystal face of corresponding Mg disappears substantially, and the corresponding peak value of (002) crystal face also descends Mg to some extent
2Ni and MmMg
12Most of peak disappear.In conjunction with the displaing microstructure observing of Figure 14, alloying pellet has reached Nano grade.This alloy should contain a large amount of nanocrystalline and a small amount of amorphous.Explanation thus, Mg-10Ni-2Mm (Cu1000) alloy belongs to the crystalline state nanometer alloy.
Figure 14 illustrates the TEM photo before nanocrystalline M g-10Ni-2Mm (Cu1000) absorption hydrogen.As shown in figure 14, dark glomerate particle is MmH
3-x, brighter part is MgH
2, brightness between bright and dark is Mg
2NiH
4Phase mostly is strip.The crystal grain maximum is no more than 20nm before inhaling hydrogen.The nanometer crystal alloy crystal grain of preparation is much smaller than the limit of diffusion of hydrogen in hydride layer, Mg
2The rectangular form of Ni provides long crystal boundary, should avoid this diffusion drawback.As seen from the figure, the interphase density of crystal grain is big, then effectively just increase greatly of interface in the alloy.Inhale hydrogen and always begin to carry out on crystal boundary, hydrogen at first arrives the position forming core suction then hydrogen that arrives easily on the crystal boundary.Therefore, this alloy should have higher hydrogenation initial rate.
Figure 15 illustrates the TEM photo behind nanocrystalline M g-10Ni-2Mm (Cu1000) absorption hydrogen.As shown in figure 15, the particle size of hydride is about 35nm; The grain boundary of hydride is clear, thus explanation hydrogen diffusion carry out along crystal boundary, the hydrogenation of whole crystal grain is finished in diffusion; MgH
2Particle become hexagon more, and occur that several crystal grain are shared crystal boundary and the phenomenon that flocks together, this mode can effectively reduce interfacial energy.
Figure 16 illustrates the PCT curve of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 275 ℃～350 ℃.As shown in figure 16, be that high pressure platform or low pressure all exist inclination to a certain degree, there be not the smooth of cast alloy, this has also embodied the advantage that nanometer crystal alloy is inhaled hydrogen.In addition, as shown in figure 16,275 ℃, 300 ℃, 325 ℃, 350 ℃ hydrogen-storage amounts are respectively 4.877wt.%H, 5.07wt.%H, 5.094wt.%H, 4.981wt.%H, promptly along with the rising of temperature, hydrogen increases, but the final hydrogen difference of each temperature is little.
Figure 17 and Figure 18 illustrate the suction hydrogen desorption kinetics performance under nanocrystalline M g-10Ni-2Mm (Cu1000) the alloy uniform pressure.
Figure 17 illustrates the suction hydrogen curve of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 1.0MPa, 275 ℃～350 ℃ conditions.As shown in figure 17, curve is followed the slow characteristics of high temperature hydrogen-absorption speed substantially, yet nanocrystal is tiny, have advantages such as the forming core of being beneficial to diffusion, make 275 ℃～325 ℃ initial hydrogen-absorption speed differ and be not very big, slowly inhaling the transformation that the hydrogen curve can obviously be found out hydrogen-absorption speed by 325 ℃, was that hydrogen-absorption speed is bigger before flex point, was that hydrogen-absorption speed slows down after the flex point.
Figure 18 illustrates nanocrystalline M g-10Ni-2Mm (Cu1000) alloy and put the hydrogen curve under 1.0MPa, 275 ℃～350 ℃ condition.As shown in figure 18, high more to put hydrogen fast more for temperature.350 ℃ put the hydrogen curve and can reach stationary value in 2～3 minutes put hydrogen substantially fully, but hydrogen desorption capacity is subjected to the influence of hydrogen, and is unsatisfactory in several temperature.And 275 ℃ put the hydrogen curve and can in 30 minutes, slowly reach stationary value, hydrogen desorption capacity is but very low.Generally speaking, high more to put hydrogen fast more for temperature.
The explanation of comprehensive Figure 17 and Figure 18, under the pressure condition of 1.0MPa, 325 ℃ of hydrogen storage properties are ideal.
Figure 19 and Figure 20 illustrate the suction hydrogen desorption kinetics performance under Mg-10Ni-2Mm (Cu1000) the nanometer crystal alloy uniform temp.Based on the PCT curve of Figure 16, in the time of 300 ℃, Mg
2Ni hydrogenation platform finishes when the pressure of 0.6MPa, therefore selects this pressure range very approaching more than pressure platform to test its dynamic performance.
The suction hydrogen curve that Figure 19 is nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 300 ℃, 0.65～1.0MPa condition.As shown in figure 19, during 300 ℃ of same temperature, the rising of certain limit internal pressure makes hydrogen that a small amount of raising be arranged, very near the 0.65MPa of plateau pressure, approaching substantially under the initial suction hydrogen rate of hydrogenation process and other pressure conditions, but be diffusion master control stage after forming core is finished substantially after flex point, hydrogen-absorption speed slows down, behind the 30min with other pressure conditions under the speed basically identical, final hydrogen is also very approaching.This shows the superiority of nano-crystalline granule suction hydrogen.
Figure 20 is nanocrystalline M g-10Ni-2Mm (Cu1000) alloy under 300 ℃, 0.65～1.0MPa condition puts the hydrogen curve.As shown in figure 20, the raising of hydrogen desorption capacity then is more prone to the low pressure condition.Pressure drops to a certain degree, and the small variations of pressure promptly varies to 0.65MPa from 0.7MPa, and is very little to inhaling the hydrogen influence, and put the variation that hydrogen has 0.6wt.%H.The hydrogen process of putting of alloy does not have tangible phased manifestation yet, unlike inhaling the flex point that the hydrogen curve has obvious speed to slow down, but a kind of trend of decay gradually.This trend has shown that two main hydrogenations have the well collaborative hydrogen effect of putting mutually in the alloy.This working in coordination with put hydrogen mainly by diffusion control.Suitably reduction suction hydrogen pressure can increase hydrogen desorption capacity under the prerequisite that does not influence hydrogen, and promptly specified temp exists best pressure condition to make that suction hydrogen is bigger, puts Hydrogen Energy and carries out enough more fully.
The above-mentioned explanation of comprehensive Figure 19 and Figure 20,0.7MPa optimum hydrogenation conditions under the temperature for this reason in the time of 300 ℃, hydrogen-releasing rate can reach 86.1%.
Figure 21 illustrates the optimum regime of nanocrystalline material hydrogen storage property at each temperature.325 ℃ of hydrogen releasing efficients have been up to 95.6%, have possessed the high hydrogen storage of 5.069wt.%H simultaneously and inhaled faster to take speed.Therefore the best storage of nanocrystalline material hydrogen state is 325 ℃, 1.0MPa.
The 3rd explanation embodiment 7.
Figure 22 illustrates the XRD spectra of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy.As shown in figure 22, in the XRD peak in Mg-10Ni-2Mm (Cu2000) alloy, most peak all disappears, residue discrete peak intensity is also very weak, two tangible diffuse scattering peaks appear in whole spectral line, illustrate to have occurred a large amount of decrystallized phenomenons in this alloy, but still have a small amount of nanocrystalline existence.Explanation successfully prepares non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy thus.
Figure 23 illustrates the TEM photo behind non-crystalline state Mg-10Ni-2Mm (Cu2000) absorption hydrogen, and Figure 24 illustrates the MmH behind non-crystalline state Mg-10Ni-2Mm (Cu2000) absorption hydrogen
3-xThe TEM photo of the high resolution phase of phase.As Figure 23 and shown in Figure 24, MgH
2Mostly be to wrap dark MmH mutually
3-xOccur mutually, have katalysis, thereby can be used as nucleating center, drive MgH thereby explanation Mm, Ni inhale hydrogen to magnesium alloy
2Forming core.As shown in figure 24, MmH
3-xGui Ze atom is arranged more to reflect and has been demonstrate,proved non-crystaline amorphous metal suction hydrogen mutually, is the process of amorphous particle crystallization.There is a large amount of lattice defects in the amorphous, helps forming core, be greatly improved than the hydrogen storage property of cast alloy.
Figure 25 illustrates the PCT curve of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=275 ℃～350 ℃.As shown in figure 25, the hydrogen curve is put in suction all two platforms, along with the rising of temperature, inhales the pressure hysteresis of putting the hydrogen curve and increases gradually, and the pressure difference of high platform and low pressure platform is apart from also increase thereupon; Also increase with the rising hydrogen of temperature, 325 ℃ have the highest hydrogen 5.023wt.%H thereupon, and the highest hydrogen of other temperature is consistent to be 4.958wt.%H, think that best suction puts the hydrogen characteristic and should appear at 325 ℃.
Figure 26 and Figure 27 illustrate the suction hydrogen desorption kinetics performance of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under uniform pressure.For guaranteeing non-crystaline amorphous metal hydrogenation fully at each temperature, select the suction hydrogen discharging rate of beta alloy under the 1.8MPa.
Figure 26 illustrates the suction hydrogen curve of non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under P=1.8MPa, T=275～350 ℃.As shown in figure 26, the highest hydrogen can reach 5.746wt.%H in the time of 325 ℃, hydrogen desorption capacity 4.848wt.%H, and the hydrogen under other temperature is roughly approaching, presents the high characteristics of the high hydrogen of temperature; Particularly outstanding is, the low more suction hydrogen of temperature speed is fast more, and 275 ℃～350 ℃ suction hydrogen can reach the hydrogen of 4.204wt.%H, 4.263wt.%H, 3.56wt.%H, 2.181wt.%H respectively in the time of 1 minute, and the preceding 275 ℃ hydrogen-absorption speed of 0.9min takes the lead always, after this, temperature is to Mg
2The influence of Ni hydrogen is greater than the influence to suction hydrogen nucleation rate, hydrogen when showing as 300 ℃ rises, exceeded 275 ℃ hydrogen-absorption speed curve, final this two temperatures hydrogen not too big difference then is because the resistance of hydrogen diffusion is little in the non-crystaline amorphous metal, hydride particle size behind the forming core is also little, and what the hydrogenation phase-change energy was very fast finishes.And the hydrogen of following 325 ℃ and 350 ℃ of identical time still is lower than 3.7wt.%H.Temperature raises, and hydrogen-absorption speed has slightly and reached saturated hydrogen again rapidly after slowing down.Alloy finally also meets the big characteristics of the high hydrogen of temperature in the time of 350 ℃.
Figure 27 illustrates non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy and put the hydrogen curve under P=1.8MPa, T=275～350 ℃.As shown in figure 27, in the time of 350 ℃, 5.8min is put hydrogen substantially and is finished, and hydrogen desorption capacity is 4.54wt.%H; In the time of 325 ℃, 8.8min is put hydrogen substantially and is finished, and hydrogen desorption capacity is 4.809wt.%H, and these two temperature have showed hydrogen storage property preferably.Because the influence of crystal grain state, alloy also keeps higher hydrogen-storage amount in the test duration when 350 ℃ of high temperature, so hydrogen desorption capacity is also very big.275 ℃ temperature is minimum, and the hydrogen diffusion is the most weak under the several temperature, and again to exceed under a lot of pressure condition of its high pressure platform 0.4MPa storage hydrogen, it is little to put the hydrogen motivating force, and it is undesirable to put the hydrogen effect.
Figure 28, Figure 29, Figure 30, Figure 31 illustrate the suction hydrogen desorption kinetics curve under the non-crystaline amorphous metal uniform temp different pressures.
The suction hydrogen curve that Figure 28 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=350 ℃, P=1.0～1.8MPa.As shown in figure 28, occurred a peculiar phenomenon in the curve, promptly same temperature has in the influence process of different pressures to hydrogen that hydrogen keeps a steady state value in the pressure range, and pressure exceeds this scope, and inhaling hydrogen has slow growth again, inhales hydrogen and two stages occur.This pressure range probably is 0.8～1.3MPa, the pressure range of height between two platforms just, supposition should with alloy in contain two kinds of main suction hydrogen certain relation arranged mutually.The rate test pressure 1.0MPa that is further noted that this moment is between the height pressure platform of PCT curve, can infer thus, and the phase transformation of high pressure platform need to take place certain pressure just can finish transformation mutually.Same phenomenon also appears among rate curve Figure 30 of 275 ℃ of low temperature, and this pressure range probably is 0.1～0.3MPa, the low and characteristics that are more or less the same of height platform corresponding to pressure platform in the PCT curve.
Figure 29 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=350 ℃, P=1.0～1.8MPa puts the hydrogen curve.As shown in figure 29, though the hydrogenation pressure difference, the initial stage that puts hydrogen initial rate curve partially overlaps.The hydrogenation that occurs in cast alloy and the nanometer crystal alloy is pressed and is changed slightly, and hydrogen desorption capacity just has the situation of significant difference not exist, and this should put hydrogen with alloy is relevant by diffusion control, and non-crystaline amorphous metal possesses the superiority condition of hydrogen diffusion.It is the greatest differences that comes from the absorption hydrogen amount that difference is arranged on the hydrogen desorption capacity.All overlap 1.0MPa put the hydrogen curve with the 1.2MPa suction, therefore infer, hydrogen desorption capacity is stressed to influence also a pressure range.
The suction hydrogen curve that Figure 30 is non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy under T=275 ℃, P=0.2～1.8MPa, Figure 31 are non-crystalline state Mg-10Ni-2Mm (Cu2000) alloys under T=275 ℃, P=0.2～1.8MPa puts the hydrogen curve.As Figure 30 and shown in Figure 31,0.2MPa, 0.3MPa obviously are between the height pressure platform on the PCT curve, and the hydrogen sucting discharging hydrogen amount is all very consistent, and initial rate speed difference occurs because of the phase driving force difference that pressure causes when having only the hydrogen of suction.0.4MPa pressure spot has just been finished in phase transformation under the temperature, hydrogen occurred inhaling and slow down phenomenon near platform when same hydrogen-storage amount, but inhaled the very fast quickening of hydrogen speed for this reason, hydrogen is improved largely again.0.6MPa it is little to the hydrogen influence below to present the variation of pressure again, and hydrogen desorption capacity is influenced tangible characteristics.
The 4th, comparative example 2, embodiment 6 and embodiment 7 and in conjunction with Figure 32 illustrate the influence of different tissues state to the thermomechanical property of alloy.
Therefore find that from the alloy test process alloy of each composition, crystalline state is all brought into play and stored up the hydrogen over-all properties preferably in the time of 325 ℃, select that each crystal alloy compares the dynamic performance analysis under this temperature.
Figure 32 illustrates Van ' the t Hoff curve of the alloy of various grain forms, obtains Δ H, the Δ S value of the various grain form alloys of table 4 by Figure 32.In Figure 32 and table 4, the B in the bracket, Cu1000, Cu2000 refer to corresponding Mg-10Ni-2Mm (B), Mg-10Ni-2Mm (Cu1000), Mg-10Ni-2Mm (Cu2000) respectively.
The Δ H of the various grain form alloys of table 4, Δ S value
Shown in figure 32, from as cast condition to nanocrystalline again to amorphous, for Mg
2NiH
4, find out that from Van ' t Hoff curve along with grain-size diminishes to decrystallized, the absolute value of rate of curve is reducing, the absolute value of the Δ H value that correspondence calculates also just reduces thereupon.The absolute value of the occurrence that calculates in the contrast table 4 is all little than theoretical value, and amorphous entropy enthalpy is all a lot of less than theoretical value, visible Mg
2NiH
4Generation thermodynamics very big improvement has been arranged, especially for amorphous alloy.
Shown in figure 32, from as cast condition to nanocrystalline again to amorphous, for MgH
2Phase, as cast condition and nanometer product Van ' t Hoff curve approximation, very approaching with theoretical value, and Van ' the t Hoff rate of curve absolute value of non-crystalline state diminishes, and the absolute value of the enthalpy entropy that correspondence calculates also reduces to some extent, and therefore non-product attitude alloy is for MgH
2The generation thermodynamics of phase also makes moderate progress, and other two crystalline state improvement effects are little, this may with MgH under the situation about adding at Ni and Mm
2The fast grain growth of forming core is relevant.
In a word, reducing of grain-size inhales hydrogen phase reaction thermodynamics for two kinds and all makes moderate progress, for Mg thereupon
2NiH
4The effect of phase is especially obvious, and the refinement alloying pellet improves inhales hydrogen phase reaction thermodynamics.
The 5th, comparative example 2, embodiment 6 and embodiment 7 and in conjunction with Figure 33 illustrate the influence of different tissues state to the dynamic performance of alloy.
Therefore find that from the alloy test process alloy of each composition, crystalline state is all brought into play and stored up the hydrogen over-all properties preferably in the time of 325 ℃, select that each crystal alloy compares the dynamic performance analysis under this temperature.
Figure 33 illustrates kinetic curve under T=325 ℃ of the Mg-10Ni-2Mm alloy, P=1.0MPa of different tissues state.
As shown in figure 33, nanocrystalline M g-10Ni-2Mm (Cu1000) alloy has showed and has inhaled hydrogen and hydrogen discharging rate preferably under the same terms, and hydrogen also is maximum in the test duration.The initial hydrogen discharging rate of crystalline state nanometer is the fastest, and crystal boundary face in this and the nanometer crystal alloy, phase interface are many, and the childlike again characteristics of the second phase hydride poor stability are relevant, Mg when putting hydrogen
2NiH
4Preferentially put hydrogen, and because the Hydrogen Energy short-range diffusion is promptly finished and put hydrogen, therefore, alloy there is hydrogen discharging speed preferably.
As shown in figure 33, as cast condition Mg-10Ni-2Mm (B) alloy is because alloying pellet is excessive, diffusion accounts for the leading stage and has just shown tangible deficiency with regard to hydrogen sucking function behind a large amount of forming cores, but hydrogen discharging rate and amorphous hydrogen discharging rate curve are very approaching, has confirmed once more to put hydrogen and be the leading supposition of diffusion.
As shown in figure 33, non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy has improved the thermomechanical property of alloy, and plateau pressure increases, so therefore the test pressure condition is subjected to Mg just for hydrogenation high pressure platform finishes force value
2NiH
4Form influence slowly, the amorphous hydrogen is not as nanocrystalline in the test duration.
Comprehensive above explanation, non-crystalline state Mg-10Ni-2Mm (Cu2000) alloy improves the most obvious to thermomechanical property, the thermodynamics and kinetics performance of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy all is greatly improved than as cast condition Mg-10Ni-2Mm (B) alloy, has best comprehensive hydrogen storage property.The best storage hydrogen condition of nanocrystalline M g-10Ni-2Mm (Cu1000) alloy is: T=325 ℃, and P=1.0MPa, hydrogen storage capability 5.094wt.%H, hydrogen desorption capacity 4.86wt.%H, hydrogen-releasing rate 95.6%.
Claims (10)
1. a Mg base hydrogen bearing alloy is characterized in that, form by Mg, Ni and three kinds of components of Mm, wherein:
Mg, promptly magnesium elements accounts for 68～76 quality %;
Ni, promptly nickel element accounts for 14～24 quality %;
Mm, the expression rare earth account for 4～12 quality %, and Mm is made up of Ce and La.
2. Mg base hydrogen bearing alloy according to claim 1 is characterized in that, La accounts for 36.98 quality % in Mm, and Ce accounts for 63.00 quality % in Mm.
3. Mg base hydrogen bearing alloy according to claim 1 is characterized in that, described Mg base hydrogen bearing alloy is a cast alloy.
4. Mg base hydrogen bearing alloy according to claim 1 is characterized in that, described Mg base hydrogen bearing alloy is a nanometer crystal alloy.
5. Mg base hydrogen bearing alloy according to claim 1 is characterized in that, described Mg base hydrogen bearing alloy is a non-crystaline amorphous metal.
6. according to each described Mg base hydrogen bearing alloy among the claim 3-5, it is characterized in that described Mg base hydrogen bearing alloy comprises Mg, Mg
2Ni and MmMg
12Three thing phases.
7. Mg base hydrogen bearing alloy according to claim 3 is characterized in that, Mg is 72 quality %, and Ni is 20 quality %, and Mm is 8 quality %.
8. Mg base hydrogen bearing alloy according to claim 7 is characterized in that, described Mg base hydrogen bearing alloy is a nanometer crystal alloy, and grain-size is no more than 20nm before the described nanometer crystal alloy suction hydrogen.
9. Mg base hydrogen bearing alloy according to claim 1, it is characterized in that, Ni in the described Mg base hydrogen bearing alloy and the melting of Mm elder generation prepare prealloy, more than being the magnesium fusing point, Heating temperature carries out induction melting with Mg again after the prealloy fragmentation with preparation then, to obtain the ternary master alloy of Mg base hydrogen bearing alloy, ternary master alloy solidifies and obtains as cast condition Mg base hydrogen bearing alloy, nanocrystalline Mg base hydrogen bearing alloy or amorphous Mg base hydrogen bearing alloy.
10. Mg base hydrogen bearing alloy according to claim 9 is characterized in that, the temperature of described induction melting is a magnesium fusing point to 670 ℃.
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|---|---|---|---|---|
| WO2015032158A1 (en) * | 2013-09-05 | 2015-03-12 | 华南理工大学 | Magnesium-based hydrogen storage material and preparation method therefor |
| CN105063447A (en) * | 2015-08-17 | 2015-11-18 | 安泰科技股份有限公司 | High-capacity Mg-Ni-Cu-La hydrogen storage alloy and preparing method thereof |
| CN107299268A (en) * | 2017-05-10 | 2017-10-27 | 燕山大学 | A kind of Mg base hydrogen bearing alloy with ultra-fine long period ordered structure and preparation method thereof |
| CN112930018A (en) * | 2021-01-26 | 2021-06-08 | 中科超睿(青岛)技术有限公司 | Magnesium-containing neutron target based on multi-principal-element design and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130845A (en) * | 2007-10-15 | 2008-02-27 | 鞍山鑫普新材料有限公司 | Rare earth hydrogen storage alloy containing Mg and preparing method thereof |
| CN101713055A (en) * | 2009-11-03 | 2010-05-26 | 清华大学 | Mg-Ni-Gd-Ag serial block amorphous alloy and preparation method thereof |
-
2011
- 2011-08-09 CN CN 201110226110 patent/CN102286684B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130845A (en) * | 2007-10-15 | 2008-02-27 | 鞍山鑫普新材料有限公司 | Rare earth hydrogen storage alloy containing Mg and preparing method thereof |
| CN101713055A (en) * | 2009-11-03 | 2010-05-26 | 清华大学 | Mg-Ni-Gd-Ag serial block amorphous alloy and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of Alloys and compounds》 20070106 Ying Wu et al. The effect of solidification rate on microstructural evolution of a melt-spun Mg-20Ni-8Mm hydrogen storage alloy 1-8 第446-447卷, * |
| 《Journal of Alloys and compounds》 20070106 Ying Wu et al. The effect of solidification rate on microstructural evolution of a melt-spun Mg-20Ni-8Mm hydrogen storage alloy 9-10 第446-447卷, * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015032158A1 (en) * | 2013-09-05 | 2015-03-12 | 华南理工大学 | Magnesium-based hydrogen storage material and preparation method therefor |
| US9764951B2 (en) | 2013-09-05 | 2017-09-19 | South China University Of Technology | Magnesium-based hydrogen storage material and method for preparing the same |
| CN105063447A (en) * | 2015-08-17 | 2015-11-18 | 安泰科技股份有限公司 | High-capacity Mg-Ni-Cu-La hydrogen storage alloy and preparing method thereof |
| CN105063447B (en) * | 2015-08-17 | 2017-04-19 | 安泰科技股份有限公司 | High-capacity Mg-Ni-Cu-La hydrogen storage alloy and preparing method thereof |
| CN107299268A (en) * | 2017-05-10 | 2017-10-27 | 燕山大学 | A kind of Mg base hydrogen bearing alloy with ultra-fine long period ordered structure and preparation method thereof |
| CN112930018A (en) * | 2021-01-26 | 2021-06-08 | 中科超睿(青岛)技术有限公司 | Magnesium-containing neutron target based on multi-principal-element design and preparation method thereof |
| CN112930018B (en) * | 2021-01-26 | 2022-12-06 | 中科超睿(青岛)技术有限公司 | Magnesium-containing neutron target based on multi-principal element design and preparation method thereof |
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