CN105671405A - Low-temperature high-capacity Mg-RE-Ni-based A2B-type hydrogen storage alloy and preparation method thereof - Google Patents
Low-temperature high-capacity Mg-RE-Ni-based A2B-type hydrogen storage alloy and preparation method thereof Download PDFInfo
- Publication number
- CN105671405A CN105671405A CN201610037285.5A CN201610037285A CN105671405A CN 105671405 A CN105671405 A CN 105671405A CN 201610037285 A CN201610037285 A CN 201610037285A CN 105671405 A CN105671405 A CN 105671405A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- alloy
- storage alloy
- base
- temperature high
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Fuel Cell (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the technical field of hydrogen storage alloy materials, and particularly relates to a high-capacity Mg-RE-Ni-based A2B-type hydrogen storage alloy used for fuel cells and the preparation technology of the alloy. According to the hydrogen storage alloy, the amount of added A-side elements is increased for 25at.%; Mg is partly replaced by rare earth elements; Ni is partly replaced by Ti and Al; the chemical formula of the alloy is Mg25-xRExNi10-y-zTiyAlz, wherein the x, y, z in the formula are atomic ratios; x is greater than 1 and smaller than 5; y is greater than 1 and smaller than 3; z is larger than 0.2 and smaller than 1; and RE is one or more of the rare earth elements of lanthanum, cerium, praseodymium, neodymium, samarium and yttrium. The hydrogen storage alloy has high hydrogen storage capacity and fast hydrogen absorption and desorption dynamics; the hydrogen desorption temperature for a hydride is obviously lowered, and reversible hydrogen absorption and desorption can be performed at 200 DEG C; and the circulation stability for hydrogen absorption and desorption is remarkably improved.
Description
Technical field
The invention belongs to storage alloy material for hydrogen technical field, particularly to a kind of fuel cell high capacity Mg-RE-Ni base A2Type B hydrogen-storage alloy and technology of preparing thereof.
Background technology
In recent years, the automobile that fuel cell (fuelcell) drives receives both domestic and external showing great attention to, but, due on the low side as the capacity of the hydrogen storage material of hydrogen fuel carrier, hydride hydrogen discharging temperature is higher and slowly inhale hydrogen desorption kinetics and make its practical application be greatly limited. Magnesium base alloy, due to features such as storage hydrogen density are high and resource is extremely abundant, is acknowledged as the hydrogen storage material of most potentiality. Particularly A2Type B Mg base hydrogen-storing alloy has that hydrogen discharging temperature is low, hydrogen storage capacity is relatively big and is studied widely, such as Mg2NiH4For 3.6wt.%, Mg2CoH5For 4.5wt.%, Mg2FeH6For 5.4wt.%. These hydride poles are expected as the hydrogen storage material of fuel cell, the Mg-Ni base A that especially hydrogen discharging temperature is on the low side2Type B hydrogen-storage alloy.
But, polycrystalline Mg prepared by traditional handicraft2Ni type alloy is at room temperature almost without the ability of reversible hydrogen adsorption and desorption, and therefore, the heat stability reducing alloy hydride the dynamic performance improving alloy hydrogen absorption and desorption become the severe challenge that researcher faces. Research shows, in A side, the suction protiums that add are conducive to keeping the high power capacity of magnesium base alloy not change types of alloys more in right amount; Alloying element and element substitution can substantially reduce the heat stability of magnesium base alloy hydride and increase substantially the suction hydrogen desorption kinetics of alloy; The microstructure inhaling hydrogen desorption kinetics alloy of alloy is very sensitive. Various non-equilibrium treatment technologies, particularly mechanical alloying (MA) and fast melt-quenching (RQ), it is believed that be the very effective method obtaining nanocrystalline/non crystalline structure. Especially high-energy ball milling, it is verified that the suction hydrogen desorption kinetics of Mg base alloy can be significantly increased. But, it is very poor that hydrogen cyclical stability is put in the suction of milled Mg base alloy, and this has become the bottleneck that its practical application is difficult to overcome.
Summary of the invention
It is an object of the invention to provide a kind of fuel cell (fuelcell) and use low temperature high capacity Mg-RE-Ni base A2B type hydrogen-storage alloy.
It is a further object to provide the preparation method that a kind of fuel cell (fuelcell) uses low temperature high capacity Mg-RE-Ni base A2B type hydrogen-storage alloy
To achieve these goals, the technical scheme is that
The present invention provides a kind of low temperature high capacity Mg-RE-Ni base A2Type B hydrogen-storage alloy, this hydrogen-storage alloy is by many for A side element addition 25at.%, and is substituted Mg by rare earth element part, Ti and Al part replace Ni;The chemical formula of this alloy consists of: Mg25-xRExNi10-y-zTiyAlz, in formula, x, y, z is atomic ratio, and 1 < x < 5,1 < y < 3,0.2 < z < 1, RE is one or more in rare earth element La and Ce, Pr, Nd, Sm, Y.
Preferably, x=3, y=2, z=0.6.
Described hydrogen-storage alloy has the alloy thin band of nanocrystalline and amorphous structure by melting, preparation, prepared by broken, ball-milling technology.
Described hydrogen-storage alloy is the alloy powder with nanocrystalline and amorphous structure.
Described hydrogen-storage alloy carries out reversible suction at 200 DEG C of temperature and puts hydrogen.
The cyclical stability S of described hydrogen-storage alloy100It is 98.3%～98.8%; S100=C100/Cmax× 100%, wherein, CmaxIt is the saturated hydrogen-sucking amount of alloy, C100Hydrogen-sucking amount after 100th circulation.
The present invention provides a kind of low temperature high capacity Mg-RE-Ni base A2The preparation method of Type B hydrogen-storage alloy, comprises the steps:
(1) raw material prepares: by chemical formula Mg25-xRExNi10-y-zTiyAlzCarrying out dispensing, in formula, RE is at least one in rare earth element La and Ce, Pr, Nd, Sm, Y; X, y, z is atomic ratio, 1 < x < 5,1 < y < 3,0.2 < z < 1;
(2) melting: under protection gas, carries out the raw material that step (1) weighs up melting and obtains as cast condition mother alloy ingot;
(3) band is got rid of: the method for ingot casting fast melt-quenching above-mentioned steps (2) prepared prepares into melt spun alloy strip;
(4) broken ball milling: melt spun alloy strip step (3) prepared crushes, and after broken, sieve takes the powder size alloy less than 75 μm; It is then placed in ball mill ball milling, it is thus achieved that Mg-RE-Ni base A2Type B hydrogen-storage alloy.
Described step (1) when proportioning raw materials, the addition excessive 5%～10% of Mg and rare earth.
Described step (2) adopts vaccum sensitive stove to carry out melting, is first evacuated to 1 × 10-2～5 × 10-5Pa, then passes to the noble gas of 0.01-0.1MPa as protective gas, and protective gas is pure helium or helium adds argon oxygen mixture, the volume ratio of described mixing gas is about 1:1, heating-up temperature 1500-1700 DEG C, it is thus achieved that melted liquid foundry alloy, after keeping about 5 minutes; It is directly injected in copper mold, it is thus achieved that as cast condition mother alloy ingot.
As cast condition mother alloy ingot is placed in bottom by described step (3) and has in the quartz ampoule of slit; it is made to be completely melt with induction coil heating; the pressure utilizing protective gas makes it be injected in the smooth surface of the copper roller with the rotation of 10～40m/s linear velocity continuously from quartz ampoule slit, it is thus achieved that melt spun alloy strip.
Described step is filled with high-purity argon gas in (4) after ball mill evacuation, then ball milling 2-5 hour, wherein, ratio of grinding media to material 40:1, rotating speed: 350 revs/min.
Compared with prior art, the beneficial effects of the present invention is:
The present invention adds the suction protium of 25at.% to keep high power capacity more on composition designs, adopt rare earth element part to substitute magnesium, titanium and aluminum portions and replace nickel, improve nanocrystalline, the amorphous formation ability of alloy, and reduce the heat stability of alloy hydride simultaneously, improve the suction hydrogen desorption kinetics performance of alloy. Melt spun alloy, after ball milling, makes the surface activity of alloying pellet be improved, and reduce further the hydrogen decomposition temperature of alloy; And material can be reduced and inhale the activation energy (Ea) putting hydrogen, make the suction hydrogen desorption kinetics performance of alloy be further enhanced. Hydrogen-storage alloy of the present invention can carry out reversible suction at 200 DEG C of temperature and put hydrogen; Suction is put hydrogen cyclical stability and is significantly improved.
Accompanying drawing explanation
Fig. 1 is the photo in kind of the embodiment of the present invention 1 quenched alloy strip;
Fig. 2 is the embodiment of the present invention 1 quenched alloy microstructure morphology under high-resolution-ration transmission electric-lens (HRTEM) and electronic diffraction ring;
Fig. 3 is HRTEM microstructure and the electronic diffraction ring of alloying pellet after the embodiment of the present invention 1 fast quenching+ball milling;
Fig. 4 is that various embodiments of the present invention pass through the XRD diffraction spectra schematic diagram of alloy after fast quenching+ball milling.
Detailed description of the invention
The Mg base alloy with nanocrystalline or nanocrystalline/non crystalline structure has good suction hydrogen desorption kinetics, because this structure can provide substantial amounts of vantage point for hydrogen atom. The Mg of ultra-fine microstructure (at below 100nm)2Ni alloy just can be inhaled at 200 DEG C and put hydrogen, hydrogen discharging temperature reduces about 100 DEG C, this is because the alloy of nanocrystalline structure has the contact position that more forming core is grown up, and also increase with the specific surface area of hydrogen reaction, the alloy contracts of the hyperfine structure transmission range of hydrogen atom, increases hydrogen diffusion rate. In the process preparing superfine alloy, creating a lot of crystal defect such as dislocation, twin, this can also be obviously improved its hydrogen storage performance. Additionally, fast melt-quenching is the effective ways obtaining nanocrystalline/non crystalline structure, and it is very suitable for mass and prepares nanocrystalline and amorphous magnesium base alloy.
The present invention on composition designs by many for A side element addition 25at.%, and adopt rare earth fraction to substitute magnesium, titanium and aluminum portions replace nickel, first prepare the alloy with nanocrystalline and amorphous structure with rapid solidification. Quenched alloy is carried out ball milling, improves microstructure and the surface characteristic of alloying pellet further, under the premise keeping high hydrogen storage capacity, significantly reduce the hydrogen discharging temperature of alloy and improve the suction hydrogen desorption kinetics of alloy.
The present invention provides a kind of fuel cell (fuelcell) to use low temperature high capacity Mg-RE-Ni base A2Type B hydrogen-storage alloy, this alloy is by many for A side element addition 25at.%, and is substituted magnesium, titanium and aluminum portions replacement nickel by rare earth element part; Its chemical formula consists of: Mg25-xRExNi10-y-zTiyAlz, in formula, x, y, z is atomic ratio, and 1 < x < 5,1 < y < 3,0.2 < z < 1, RE is one or more in rare-earth elements of lanthanum, cerium, praseodymium, neodymium, samarium, yttrium.
Preferably, chemical formula composed atom ratio is: x=3, y=2, z=0.6.
The present invention provides a kind of fuel cell (fuelcell) to use low temperature high capacity Mg-RE-Ni base A2The preparation method of Type B hydrogen-storage alloy, comprises the steps:
(1) raw material prepares: by chemical formula Mg25-xRExNi10-y-zTiyAlzCarrying out dispensing, in formula, RE is at least one in rare-earth elements of lanthanum, cerium, praseodymium, neodymium, samarium, yttrium; X, y, z is atomic ratio, 1<x<5,1<y<3,0.2<z<1, it is preferred that x=3, y=2, z=0.6; Magnesium in described chemical formula composition, rare earth increase the scaling loss amount of 5%-10% ratio, raw-material metal purity>=99.5% when proportioning.
(2) melting: raw material step (1) weighed up adopts vaccum sensitive stove to carry out melting, is first evacuated to 1 × 10-2-5×10-5Pa, then passes to the noble gas of 0.01-0.1MPa as protective gas, and protective gas is pure helium or helium+argon oxygen mixture, the volume ratio of described mixing gas is about 1:1, heating-up temperature 1500-1700 DEG C, it is thus achieved that melted liquid foundry alloy, after keeping about 5 minutes; It is directly injected in copper mold, it is thus achieved that as cast condition mother alloy ingot.
(3) band is got rid of: ingot casting prepared by above-mentioned steps (2) is placed in bottom to be had in the quartz ampoule of slit; it is made to be completely melt with induction coil heating; the pressure utilizing protective gas makes it be injected in the smooth surface of the copper roller with the rotation of 10～40m/s linear velocity continuously from quartz ampoule slit; obtaining melt spun alloy strip, the alloy thin band obtained has nanocrystalline and amorphous structure.
(4) broken ball milling: by fast quenching Mg25-xRExNi10-y-zTiyAlzCross 200 mesh sieves after alloy mechanical is broken, reinstall stainless steel jar mill, after evacuation, be filled with high-purity argon gas, ball milling 2-5 hour (removing downtime), ratio of grinding media to material 40:1 in comprehensive planetary high-energy ball mill; Rotating speed: 350 revs/min. In mechanical milling process, every ball milling is shut down 1 hour for 3 hours, to prevent ball grinder temperature too high.
Test the structure of ball-milled powder with XRD, observe pattern and the microstructure of alloying pellet after ball milling with high-resolution-ration transmission electric-lens (HRTEM), and determine the crystalline state of ball milling alloy with SEAD (SEAD).
With the gaseous state hydrogen storage capacity of full-automatic Sieverts equipment beta alloy powder and suction hydrogen desorption kinetics. Inhaling hydrogen discharging temperature is 200 DEG C, and inhaling the initial hydrogen pressure of hydrogen is 2MPa, puts hydrogen 1 × 10-4Carry out under MPa pressure.
Below in conjunction with embodiment, the present invention is further described.
The chemical composition of the specific embodiment of the invention and ratio select as follows:
Embodiment 1:Mg22Y3Ni7.4Ti2Al0.6
Embodiment 2:Mg24La1Ni8.8Ti1Al0.2
Embodiment 3:Mg20Ce5Ni6.4Ti3Al0.6
Embodiment 4:Mg22Pr2NdNi7Ti2Al1
Embodiment 5:Mg22Nd3Ni7Ti2.6Al0.4
Embodiment 6:Mg21Sm3Ce0.5Y0.5Ni7.4Ti2Al0.6
Embodiment 7:Mg23La2Ni7.9Ti1.5Al0.6
Embodiment 8:Mg22Ce3Ni7.4Ti1.8Al0.8
Below, concrete technology parameter and process with regard to 8 embodiments describe.
Embodiment 1
By chemical formula Mg22Y3Ni7.4Ti2Al0.6Choose bulk metal magnesium, metallic yttrium, metallic nickel, Titanium and metallic aluminium, these metal purity >=99.5%, weigh by chemical dosage ratio. Weigh magnesium metal 872.9g, metallic yttrium 415.6g, metallic nickel 644.6g, Titanium 142.1g and metallic aluminium 24.0g.
Being joined in no particular order in magnesia crucible by all material beyond demagging, magnesium metal is placed in the top of crucible, then builds bell, is evacuated to vacuum 5 × 10-3More than Pa, is re-filled with-0.04MPa pressure helium as protective atmosphere. Regulate induction furnace power to control temperature, at 650 DEG C, to make metal Mg melt. Then increase power, make temperature rise to about 1700 DEG C, make all metal moltens. After keeping 5 minutes, liquid alloy is directly poured into Copper casting mould, come out of the stove after cooling down 30 minutes under helium protective atmosphere, it is thus achieved that diameter is the cylindric alloy cast ingot of φ 30mm.
Cast alloy bar is about 100g, and to put into diameter be that 30mm, bottom have in the quartz ampoule of slit, and slit is of a size of 0.05mm × 20mm (slit length can increase as required or reduce); Making alloy melt completely with radio frequency heating, molten alloy is directly injected on the water-cooled copper roller surface that linear resonance surface velocity is 10m/s under 1.05atm helium pressure effect by nozzle, it is thus achieved that quenched alloy strip, as shown in Figure 1; The microscopic appearance of quenched alloy is observed, as shown in Figure 2 with high-resolution-ration transmission electric-lens (HRTEM).
By fast quenching Mg17.5Y2Ti0.5Ni8Mn2Alloy sheet Mechanical Crushing also crosses 200 mesh sieves, claims the alloy powder 100 grams after sieving to load in stainless steel jar mill, and ratio of grinding media to material is 40:1, and evacuation also seals after being filled with high-purity argon gas. Ball milling 2 hours in comprehensive planetary high-energy ball mill, drum's speed of rotation is 300 revs/min.
Observe the pattern of ball milling alloying pellet with HRTEM, and analyze the crystalline state of ball-milled powder with electronic diffraction (SAD), it has been found that ball milling alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 3. The structure of ball milling alloy by XRD analysis, it has been found that it has nanocrystalline and amorphous structure, and result is shown in Fig. 4. Test gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy with full-automatic Sieverts, result is table 1 such as.
Embodiment 2
Alloying component is: Mg24La1Ni8.8Ti1Al0.2, weigh magnesium metal 993.3g, lanthanoid metal 225.8g, metallic nickel 799.5g, Titanium 74.1g and metallic aluminium 8.4g. According to example 1 method smelt as cast condition foundry alloy, then carry out fast quenching and ball-milling treatment, institute the difference is that employing Ball-milling Time be 5 hours. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is table 1 such as.
Embodiment 3
Alloying component is: Mg20Ce5Ni6.4Ti3Al0.6, weigh magnesium metal 621.0g, metallic cerium 854.3g, metallic nickel 436.3g, Titanium 166.8g and metallic aluminium 18.8g. Smelting as cast condition foundry alloy according to the method for example 1, then carry out fast quenching and ball-milling treatment, institute is 3 hours the difference is that Ball-milling Time. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is in Table 1.
Embodiment 4
Alloying component is: Mg22Pr2NdNi7Ti2Al1, weigh magnesium metal 787.2g, metal praseodymium 396.0g, neodymium metal 202.7g, metallic nickel 549.9g, Titanium 128.1g and metallic aluminium 36.1g. Smelting as cast condition foundry alloy according to the method for example 1, then carry out fast quenching and ball-milling treatment, institute is 4 hours the difference is that Ball-milling Time. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is in Table 1.
Embodiment 5
Alloying component is: Mg22Nd3Ni7Ti2.6Al0.4, weigh magnesium metal 777.2g, neodymium metal 600.4g, metallic nickel 542.9g, Titanium 164.5g and metallic aluminium 14.3g. Smelting as cast condition foundry alloy according to the method for example 1, then carry out fast quenching and ball-milling treatment, institute is the difference is that speed of quenching is for 40m/s. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is in Table 1.
Embodiment 6
Alloying component is: Mg21Sm3Ce0.5Y0.5Ni7.4Ti2Al0.6, weigh magnesium metal 692.2g, samarium metal 583.9g, metallic cerium 90.7g, metallic yttrium 57.5g, metallic nickel 535.5g, Titanium 118.0g and metallic aluminium 20.0g. Smelting as cast condition foundry alloy according to the method for example 1, then carry out fast quenching and ball-milling treatment, institute is the difference is that speed of quenching is for 20m/s. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is in Table 1.
Embodiment 7
Alloying component is: Mg23La2Ni7.9Ti1.5Al0.6, weigh magnesium metal 885.7g, lanthanoid metal 420.2g, metallic nickel 667.9g, Titanium 103.4g and metallic aluminium 23.3g. Smelting as cast condition foundry alloy according to the method for example 1, then carry out fast quenching and ball-milling treatment, institute is the difference is that speed of quenching is for 30m/s. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is in Table 1.
Embodiment 8
Alloying component is: Mg22Ce3Ni7.4Ti1.8Al0.8, weigh magnesium metal 785.7g, metallic cerium 589.6g, metallic nickel 580.2g, Titanium 115.1g and metallic aluminium 28.8g. Smelting as cast condition foundry alloy according to the method for example 1, then carry out fast quenching and ball-milling treatment, institute is the difference is that speed of quenching is for 10m/s. XRD test result shows that alloy has nanocrystalline and amorphous structure, and result is shown in Fig. 4; Testing gaseous state hydrogen sucting discharging hydrogen capacity and the kinetics of alloy, result is in Table 1.
The hydrogen storage capacity of the hydrogen-storage alloy of table 1 heterogeneity alloy powder and cyclical stability
It is at 2MPa and 150 DEG C at initial hydrogen pressure, 5 minutes interior hydrogen-sucking amounts (wt.%);It is 1 × 10 at initial pressure-4At MPa and 200 DEG C, 30 minutes interior hydrogen desorption capacities (wt.%). S100=C100/Cmax× 100%, wherein, CmaxIt is the saturated hydrogen-sucking amount of alloy, C100Hydrogen-sucking amount after 100th circulation.
Test result shows, after fast quenching, ball milling alloy powder has high suction at a lower temperature and puts hydrogen capacity and excellent dynamic performance. Comparing with domestic and international similar alloy, the performance of alloy of the present invention particularly low temperature is inhaled hydrogen desorption kinetics and is significantly improved.
Although its preferred embodiment is described by the present invention; those skilled in the art can take other embodiment obviously; such as change the technical parameters such as component content, heating-up temperature, FFR'S fuel assembly, Ball-milling Time and ratio of grinding media to material; in the scope without departing from design philosophy of the present invention; can carrying out various changes and modifications, these changes belong to protection scope of the present invention.
Claims (11)
1. a low temperature high capacity Mg-RE-Ni base A2Type B hydrogen-storage alloy, it is characterised in that: this hydrogen-storage alloy is by many for A side element addition 25at.%, and is substituted Mg by rare earth element part, Ti and Al part replace Ni; The chemical formula of this alloy consists of: Mg25-xRExNi10-y-zTiyAlz, in formula, x, y, z is atomic ratio, and 1 < x < 5,1 < y < 3,0.2 < z < 1, RE is one or more in rare earth element La and Ce, Pr, Nd, Sm, Y.
2. low temperature high capacity Mg-RE-Ni base A according to claim 12Type B hydrogen-storage alloy, it is characterised in that: x=3, y=2, z=0.6.
3. low temperature high capacity Mg-RE-Ni base A according to claim 12Type B hydrogen-storage alloy, it is characterised in that: described hydrogen-storage alloy has the alloy thin band of nanocrystalline and amorphous structure by melting, preparation, prepared by broken, ball-milling technology.
4. low temperature high capacity Mg-RE-Ni base A according to claim 12Type B hydrogen-storage alloy, it is characterised in that: described hydrogen-storage alloy is the alloy powder with nanocrystalline and amorphous structure.
5. low temperature high capacity Mg-RE-Ni base A according to claim 12Type B hydrogen-storage alloy, it is characterised in that: described hydrogen-storage alloy carries out reversible suction at 200 DEG C of temperature and puts hydrogen.
6. low temperature high capacity Mg-RE-Ni base A according to claim 12Type B hydrogen-storage alloy, it is characterised in that: the cyclical stability S of described hydrogen-storage alloy100It is 98.3%～98.8%; S100=C100/Cmax× 100%, wherein, CmaxIt is the saturated hydrogen-sucking amount of alloy, C100Hydrogen-sucking amount after 100th circulation.
7. a low temperature high capacity Mg-RE-Ni base A according to claim 12The preparation method of Type B hydrogen-storage alloy, it is characterised in that: the method comprises the steps:
(1) raw material prepares: by chemical formula Mg25-xRExNi10-y-zTiyAlzCarrying out dispensing, in formula, RE is at least one in rare earth element La and Ce, Pr, Nd, Sm, Y; X, y, z is atomic ratio, 1 < x < 5,1 < y < 3,0.2 < z < 1;
(2) melting: under protection gas, carries out the raw material that step (1) weighs up melting and obtains as cast condition mother alloy ingot;
(3) band is got rid of: the method for ingot casting fast melt-quenching above-mentioned steps (2) prepared prepares into melt spun alloy strip;
(4) broken ball milling: melt spun alloy strip step (3) prepared crushes, and after broken, sieve takes the powder size alloy less than 75 μm; It is then placed in ball mill ball milling, it is thus achieved that Mg-RE-Ni base A2Type B hydrogen-storage alloy.
8. low temperature high capacity Mg-RE-Ni base A according to claim 72The preparation method of Type B hydrogen-storage alloy, it is characterised in that: described step (1) when proportioning raw materials, the addition excessive 5%～10% of Mg and rare earth.
9. low temperature high capacity Mg-RE-Ni base A according to claim 72The preparation method of Type B hydrogen-storage alloy, it is characterised in that: described step (2) adopts vaccum sensitive stove to carry out melting, is first evacuated to 1 × 10-2～5 × 10-5Pa, then passes to the noble gas of 0.01-0.1MPa as protective gas, and protective gas is pure helium or helium adds argon oxygen mixture, the volume ratio of described mixing gas is about 1:1, heating-up temperature 1500-1700 DEG C, it is thus achieved that melted liquid foundry alloy, after keeping about 5 minutes; It is directly injected in copper mold, it is thus achieved that as cast condition mother alloy ingot.
10. low temperature high capacity Mg-RE-Ni base A according to claim 72The preparation method of Type B hydrogen-storage alloy; it is characterized in that: as cast condition mother alloy ingot is placed in described step (3) bottom to be had in the quartz ampoule of slit; it is made to be completely melt with induction coil heating; the pressure utilizing protective gas makes it be injected in the smooth surface of the copper roller with the rotation of 10～40m/s linear velocity continuously from quartz ampoule slit, it is thus achieved that melt spun alloy strip.
11. low temperature high capacity Mg-RE-Ni base A according to claim 72The preparation method of Type B hydrogen-storage alloy, it is characterised in that: described step is filled with high-purity argon gas in (4) after ball mill evacuation, then ball milling 2-5 hour, wherein, and ratio of grinding media to material 40:1, rotating speed: 350 revs/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610037285.5A CN105671405B (en) | 2016-01-20 | 2016-01-20 | A kind of low temperature high capacity Mg RE Ni bases A2Type B hydrogen-storage alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610037285.5A CN105671405B (en) | 2016-01-20 | 2016-01-20 | A kind of low temperature high capacity Mg RE Ni bases A2Type B hydrogen-storage alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105671405A true CN105671405A (en) | 2016-06-15 |
| CN105671405B CN105671405B (en) | 2017-09-29 |
Family
ID=56301720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610037285.5A Active CN105671405B (en) | 2016-01-20 | 2016-01-20 | A kind of low temperature high capacity Mg RE Ni bases A2Type B hydrogen-storage alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105671405B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099724A (en) * | 2017-04-28 | 2017-08-29 | 内蒙古科技大学 | Nanometer titanium trifluoride catalysis Mg RE Ni Al Ti Co base hydrogen-storing alloys and preparation method |
| CN110373562A (en) * | 2019-07-12 | 2019-10-25 | 广东工业大学 | A kind of magnesium-air cell AP65 magnesium-alloy anode material and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147472A (en) * | 2001-11-02 | 2003-05-21 | Toyota Central Res & Dev Lab Inc | Hydrogen storage magnesium alloy |
| CN1644737A (en) * | 2005-01-20 | 2005-07-27 | 南开大学 | Magnesium based hydrogen storing alloy composite material and production thereof |
| CN101985710A (en) * | 2010-09-03 | 2011-03-16 | 燕山大学 | Multiphase Mg-RE-Ni hydrogen storage alloy |
| CN104593651A (en) * | 2015-01-27 | 2015-05-06 | 内蒙古科技大学 | Mg-Ti-RE-Ni-based hydrogen-storage alloy and preparation method thereof |
-
2016
- 2016-01-20 CN CN201610037285.5A patent/CN105671405B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147472A (en) * | 2001-11-02 | 2003-05-21 | Toyota Central Res & Dev Lab Inc | Hydrogen storage magnesium alloy |
| CN1644737A (en) * | 2005-01-20 | 2005-07-27 | 南开大学 | Magnesium based hydrogen storing alloy composite material and production thereof |
| CN101985710A (en) * | 2010-09-03 | 2011-03-16 | 燕山大学 | Multiphase Mg-RE-Ni hydrogen storage alloy |
| CN104593651A (en) * | 2015-01-27 | 2015-05-06 | 内蒙古科技大学 | Mg-Ti-RE-Ni-based hydrogen-storage alloy and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099724A (en) * | 2017-04-28 | 2017-08-29 | 内蒙古科技大学 | Nanometer titanium trifluoride catalysis Mg RE Ni Al Ti Co base hydrogen-storing alloys and preparation method |
| CN110373562A (en) * | 2019-07-12 | 2019-10-25 | 广东工业大学 | A kind of magnesium-air cell AP65 magnesium-alloy anode material and its preparation method and application |
| CN110373562B (en) * | 2019-07-12 | 2020-10-09 | 广东工业大学 | AP65 magnesium alloy anode material for magnesium-air battery and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105671405B (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104593651B (en) | A kind of Mg-Ti-RE-Ni base hydrogen-storing alloy and preparation method thereof | |
| CN105063457B (en) | Nano-graphite compounded high-capacity RE-Mg-Ni-based hydrogen storage material and preparation method thereof | |
| CN103165873B (en) | A kind of power battery hydrogen storage electrode alloy and preparation method thereof | |
| CN103667837A (en) | Nanometer TiF3 catalyzed high-volume hydrogen-storing alloy and preparation method thereof | |
| CN103695753A (en) | High-capacity RE-Mg-Ni-Co based hydrogen storage alloy and preparation method thereof | |
| CN110656272B (en) | Magnesium-based hydrogen storage material based on high entropy effect and preparation method thereof | |
| CN110629091B (en) | High-capacity multi-phase hydrogen storage alloy for fuel cell and preparation method thereof | |
| CN103633339B (en) | A kind of nano Ce O 2high power capacity RE-Mg-Ni base hydrogen-storing alloy of catalysis and preparation method thereof | |
| CN107099724B (en) | The preparation method of nanometer titanium trifluoride catalysis Mg-RE-Ni-Al-Ti-Co base hydrogen-storing alloy | |
| CN103667836B (en) | MoS 2high capacity hydrogen storage alloy of catalysis and preparation method thereof | |
| CN108588521A (en) | A kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys and preparation method thereof | |
| CN108097947B (en) | High-capacity Mg-Zn-Ni ternary hydrogen storage alloy and preparation method thereof | |
| CN103741004B (en) | CoS 2high capacity hydrogen storage alloy of catalysis and preparation method thereof | |
| CN105671405B (en) | A kind of low temperature high capacity Mg RE Ni bases A2Type B hydrogen-storage alloy and preparation method thereof | |
| CN107338381B (en) | The hydrogen-storage alloy and preparation method thereof that fuel cell graphene is catalyzed | |
| CN103498089B (en) | A kind of fuel cell high capacity hydrogen storage alloy and preparation method thereof | |
| CN103938052B (en) | High capacity hydrogen storage electrode metal and preparation method thereof | |
| CN107385300B (en) | LaCl3The preparation method of the high capacity hydrogen storage alloy powder of catalysis | |
| CN106756355B (en) | Fuel cell stores hydrogen intermediate alloy, hydrogen storage material and preparation method with Mg-Sn-Ni ternary | |
| CN106967914B (en) | The preparation method of nanometer five neodymium fluorides catalysis RE-Mg-Ti-V-Ni-Al-Co base hydrogen-storing alloy | |
| CN103682285B (en) | Ni-MH battery high capacity hydrogen storage electrode metal and preparation method thereof | |
| CN107338380B (en) | The preparation method of fuel cell high capacity hydrogen storage alloy | |
| CN113881880A (en) | High-capacity Gd-Mg-Ni-based composite hydrogen storage material doped with fluoride and preparation method thereof | |
| CN107400814B (en) | The preparation method of fuel cell high capacity hydrogen storage alloy | |
| CN103682288A (en) | Hydrogen storage electrode alloy for Ni-MH battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |