CN105132741A - Rear earth-ferrotitanium hydrogen storage alloy for wind power storage and preparation method thereof - Google Patents
Rear earth-ferrotitanium hydrogen storage alloy for wind power storage and preparation method thereof Download PDFInfo
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- CN105132741A CN105132741A CN201510623781.4A CN201510623781A CN105132741A CN 105132741 A CN105132741 A CN 105132741A CN 201510623781 A CN201510623781 A CN 201510623781A CN 105132741 A CN105132741 A CN 105132741A
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Abstract
The invention belongs to the technical field of hydrogen storage alloys, and relates to a rear earth-ferrotitanium hydrogen storage alloy for wind power storage and a preparation method thereof. The rear earth-ferrotitanium hydrogen storage alloy consists of Ti, Fe, Mn, multi-component rear earth and few LaNi5 alloy, and has a chemical formula as follows: Ti1.1-xFe0.8Mn0.2Mx+yLaNi5, wherein x is an atomic ratio greater than 0 and less than or equal to 0.09, y is mass percent greater than or equal to 2% and less than or equal to 8%, and M is multi-component rear earth which further contains at least one of Ce, Y, Nd, Pr and Gd in addition to La with the atomic ratio of 0.5-0.7. The alloy is prepared by the following steps: proportioning, carrying out vacuum smelting, carrying out rapid quenching, carrying out mechanical crushing and carrying out ball-milling. The rear earth-ferrotitanium hydrogen storage alloy mainly adopts Ti and Fe elements which are rich in the natural world and cheap, so that large-scale popularization and application are facilitated. Compared with a smelting and annealing process, the alloy with high-density nanocrystalline grains is prepared through the rapid quenching process; and by virtue of mechanical ball-milling, the alloy forms high-density crystal defects. The rapid quenching process and the ball-milling process are simple and easy to grasp, so that the preparation method is suitable for large-scale production.
Description
Technical field
The invention belongs to hydrogen storage alloy technical field, relate to a kind of wind-powered electricity generation energy storage rare earth-ferrotianium hydrogen storage alloy and preparation method thereof.
Background technology
Wind energy, as a kind of clean renewable energy source, has become generating approach with the fastest developing speed in the world, forward is extensive, Large Copacity, industrialization future development.At present, there are three aspects deficiencies in wind-power electricity generation.The first, wind-powered electricity generation has violent fluctuation in voltage, frequency and phase place, and in order to maintain the stable of electrical network, the online amount of Utilities Electric Co.'s restriction wind-powered electricity generation can not exceed 10% of net capacity.The second, China's wind-power electricity generation area distance load center is comparatively far away, needs extensive long-distance transmission line.3rd, wind-powered electricity generation has anti-peak-shaving capability, and when namely night, power load was at a low ebb, wind-power electricity generation amount is comparatively large, and when wind-powered electricity generation electricity is much larger than valley power consumption load, in order to the safety and stability of keeping system, also there will be rations the power supply abandons the phenomenon of wind.According to the data that National Energy Board announces, in 2013, wind capacity integrated into grid was 7.716 × 10
7kW ﹒ h, but ration the power supply that to abandon air quantity be 1.62 × 10
10kW ﹒ h.
In order to solve the restriction of wind capacity integrated into grid, transmission of electric energy high cost and problems such as abandoning wind of rationing the power supply, various energy storage technology obtains extensive research.Such as, water-storage technology, this technology is ripe and investment is lower, but due to China's wind-power electricity generation area, as Gansu, Inner Mongol etc. ten million multikilowatt wind power base be all in water-deficient area, and physical features is comparatively smooth, cannot build extensive pumped storage station; Batteries to store energy technology, this technological controllability is better, but expensive; Other energy storage mode, if compressed-air energy storage, flywheel energy storage, chemical energy storage etc. are all because efficiency is too low, capacity is too little, expense is too high and can not use on a large scale.
Hydrogen is considered to the optimum capacity carrier of renewable energy source, and it is easily changed mutually with electricity, can realize balancing between generating and electrical network supply.When electrical network power load is lower, wind-powered electricity generation is directly made hydrogen storage, when electrical network is in peak of power consumption, be that electric energy feedback is to electrical network by the hydrogen of storage by fuel cells convert again, this is a kind of new way solving wind-powered electricity generation storage, and it has the advantages such as the storage time is long, the reaction times is fast, pollution-free.
Wind-powered electricity generation direct hydrogen production and fuel cell generation relate to the technology such as water electrolysis hydrogen production, Chu Qing, fuel cell, inversion and wind-powered electricity generation energy hole, the technology such as water electrolysis hydrogen production, fuel cell, inversion and wind-powered electricity generation energy hole are all comparatively ripe, and extensive, efficient, safe hydrogen storage technology is the key of Hydrogen Energy energy storage sizable application.
Hydride hydrogen-storing, namely utilizes hydride hydrogen-storing alloy to store and release hydrogen.This inhales hydrogen with metal hydride form after utilizing some metal or alloy and H-H reaction, discharges hydrogen after the metal hydride heating of generation.Hydride hydrogen-storing density can reach 1000 times of hydrogen under standard state, identically with liquid hydrogen even exceedes liquid hydrogen.Hydride hydrogen-storing mode has following characteristics: storage hydrogen weight density ratio is large, volume ratio is large, and security is good, and hydrogen purity is high, reversible cycle etc.
For the application of hydride hydrogen-storing technology in large-scale wind power energy storage, maximum obstacle is high cost.Current hydrogen storage material mainly adopts LaNi
5be alloy, but the price of rare earth and nickel higher be a major reason of its high cost.Ferro-titanium is the Typical Representative of AB type hydrogen storage alloy, and it has the following advantages: first, and the hydrogen-storage amount of ferro-titanium is large, theoretical value is 1.86wt%, and it is little that hydrogen platform slope rate is put in the suction of alloy, and the decomposition pressure of hydride is only several normal atmosphere, dynamic performance is good, is very applicable to industrial application.In addition, Fe, Ti two kinds of elements are at occurring in nature rich reserves, and low price, is conducive to large-scale promotion application.But the subject matter of ferro-titanium is reactivation process complexity and activation condition is harsh, and not activated alloy at room temperature cannot complete reversible hydrogen adsorption and desorption.In addition, when Ti is containing quantity not sufficient in ferro-titanium, as lower than 45.7% time, TiFe phase and Fe in alloy
2ti coexists, Fe
2ti does not inhale hydrogen phase, and hydrogen－sucking amount can be caused to reduce.If Ti content will be solidly soluted in TiFe more than 48%, Ti, the Ti of solid solution will generate very stable TiH when inhaling hydrogen
2, cause reversible capacity to decline.
Researchist add from element and substitute, suction hydrogen activation performance that crystalline structure and viscous deformation angularly improve ferro-titanium.Research finds to add the elements such as Al, Cr, Mn, Cu, Zr, Mg, S, V, Ni, and the activation number of times of alloy reduces greatly, only needs 1-3 time, but activation condition is still harsher, needs the high temperature of 300 DEG C.In addition, researchist adopts the methods such as mechanical alloying, rolling and torsion to make alloy generation severe plastic deformation, alloy inside is made to form high-density lattice defect (as plane defect, L&S line defect, point defect), the activation performance of this alloy, so active influence is created to the improvement of the suction hydrogen desorption kinetics characteristic of alloy after activation.
Summary of the invention
The object of the present invention is to provide a kind of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy and preparation method thereof, the activation performance of ferrotianium hydrogen storage alloy is improved greatly.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy, this alloy is by Ti, Fe, Mn, multicomponent rare earth and a small amount of LaNi
5alloy is formed, and its chemical formula consists of: Ti
1.1-xfe
0.8mn
0.2m
x+ yLaNi
5, wherein, x is atomic ratio, 0 < x≤0.09, and y is mass percent, 2%≤y≤8%, and M represents multicomponent rare earth, except containing atomic ratio being the La of 0.5-0.7, also containing at least one in Ce, Y, Nd, Pr, Gd;
This alloy is prepared as follows: proportioning → vacuum melting → fast quenching → mechanical disintegration → ball milling.
Prepared the alloy with the nanocrystalline crystal grain of high-density by rapid quenching technique, then through mechanical ball milling, form the alloy of high-density lattice defect.
A small amount of LaNi is added during vacuum melting
5alloy.
The maximum hydrogen－sucking amount of alloy reaches 1.73wt%, and close to TiFe alloy theory hydrogen－sucking amount 1.86wt%, 1-3 suction is put hydrogen and namely activated completely.
A preparation method for wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy, the method comprises the steps:
A, proportioning: by chemical formula composition Ti
1.1-xfe
0.8mn
0.2m
x+ yLaNi
5carry out weighing and proportioning, wherein, x is atomic ratio, 0 < x≤0.09, y is mass percent, 2%≤y≤8%, M represents multicomponent rare earth, except containing atomic ratio being the La of 0.5-0.7, also containing at least one in Ce, Pr, Y, Nd, Gd;
B, vacuum melting: the raw material prepared is placed in zirconium white crucible, vacuumizes, be then filled with inert protective gas, adopt induction heating to carry out melting to the raw material prepared, obtain the liquid mother alloy of melting;
C, fast quenching: after each raw material mixes, directly inject tundish by liquid mother alloy, drops on the surface of water-cooled copper roller of rotation by the nozzle continuous spraying of tundish bottom, obtains quenched alloy thin slice;
D, mechanical disintegration: quenched alloy thin slice is obtained rare earth-ferro-titanium powder by airflow milling mechanical disintegration;
E, ball milling: the stainless steel jar mill that the rare earth after mechanical disintegration-ferro-titanium powder puts into high-purity argon gas is carried out ball milling, after ball milling terminates, ball grinder is placed in and is full of high-purity argon gas vacuum glove box, take out powder, sieve and weigh, seal with Vacuum Packaging Machine.
In steps A, metal purity >=99.5% of Ti, Fe, Mn;
Rare earth in described chemical formula composition increases the scaling loss amount of 5-10wt% when proportioning.
In step B, the raw material prepared is placed in zirconium white crucible, the decoration form of each raw material in crucible is: iron staff is along sidewall of crucible vertical display, and titanium sponge on crucible bottom uniform spreading, block manganese is placed in above titanium sponge, rare earth and LaNi
5alloy is placed on topmost.
In step B, be evacuated to 1 × 10
-3more than Pa, be then filled with 0.04MPa inert protective gas.
In step B, described inert protective gas is helium or argon gas and helium mix gas, and described argon gas and helium mix gas volume are than being 1:1.
In step B, smelting temperature is 1680-1720 DEG C.
In step C, the linear resonance surface velocity of copper roller is 5-30m/s.
In step C, the thickness of this quenched alloy thin slice is 100-500 μm, has the nanocrystalline crystalline-granular texture of high-density.
In step D, powder size meets D
10=7-11 μm, D
50=38-46 μm, D
90=80-100 μm.
In step e, ball milling condition is as follows: ratio of grinding media to material is 20:1-60:1, and rotational speed of ball-mill is 200-450r/min, and each Ball-milling Time is 1-5h, and each time of having a rest is 10min, and total Ball-milling Time is at 3-21h.
Beneficial effect of the present invention is:
(1) the present invention mainly adopts Ti, Fe element, and these two kinds of elements are at occurring in nature rich reserves, and low price, is conducive to large-scale promotion application.In addition, add a small amount of rare earth element, rare earth element easily and hydrogen evolution MH
3hydride, MH
3become the catalytic active center of ferro-titanium.Further, fusion process adds a small amount of LaNi
5alloy, contributes to ferro-titanium Composition Control.The theoretical hydrogen－sucking amount of ferro-titanium reaches 1.86wt%, comparatively LaNi
5alloy promotes 30%, and material cost reduces by more than 50%.Adopt multicomponent rare earth to combine alternative, play the comprehensive action of rare earth element.
(2) helium or helium and argon gas mixed gas is adopted to be inert protective gas; greatly reduce the volatilization loss of rare earth element during induction melting; simultaneously; the rare earth element into 5-10wt% is added during batching; to make up scaling loss amount, ensure that the alloying constituent of preparation meets design component mol ratio.
(3) compare with traditional founding annealing process, the present invention prepares the alloy with the nanocrystalline crystal grain of high-density by rapid quenching technique, then through mechanical ball milling, makes alloy form high-density lattice defect.Highdensity nanocrystalline and defect is that the diffusion of hydrogen atom provides passage, reduces hydrogen atom transport resistance in the alloy or energy barrier.Fundamentally solve the technical barrier of ferro-titanium difficulty activation.
(4) fast quenching, ball-milling technology simple, be easy to grasp, be applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the alloy adopting the chemical formula of the embodiment of the present invention 2 composition and preparation method to prepare;
Fig. 2 is the TEM photo of the alloy adopting the chemical formula of the embodiment of the present invention 5 composition and preparation method to prepare;
Fig. 3 is the TEM photo of the alloy adopting the chemical formula of the embodiment of the present invention 6 composition and preparation method to prepare;
Fig. 4 is the TEM photo of the alloy adopting the chemical formula of the embodiment of the present invention 7 composition and preparation method to prepare;
Fig. 5 is the TEM photo of the alloy adopting the chemical formula of the embodiment of the present invention 8 composition and preparation method to prepare;
Fig. 6 is the TEM photo of the alloy adopting the chemical formula of the embodiment of the present invention 9 composition and preparation method to prepare.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.
Mentality of designing of the present invention is as follows:
Composition Design aspect, first, adds multicomponent rare earth in ferro-titanium, and rare earth element easily and hydrogen evolution MH
3compound, MH
3become the catalytic active center of ferro-titanium; Secondly, a small amount of LaNi is added during melting
5alloy, contributes to ferro-titanium control composition, and reason is in fusion process, and unnecessary Ti enters LaNi
5the La position of alloy, unnecessary Fe enters LaNi
5the Ni position of alloy, and LaNi
5alloy also has hydrogen storage property, LaNi when wider non-stoichiometric
5alloy add the activation performance effectively improving ferro-titanium.
Preparation method aspect, the present invention adopts the technique of vacuum melting → fast quenching → mechanical disintegration → ball milling to prepare rare earth-ferrotianium hydrogen storage alloy, this alloy obtains highdensity nanocrystalline structure through vacuum quick quenching method, then through mechanical disintegration and ball milling, makes alloy form high-density lattice defect.Highdensity nanocrystalline and lattice defect is that the diffusion of hydrogen atom provides passage, reduces the transport resistance of hydrogen atom in tin oxide layers or energy barrier.
Wind-powered electricity generation energy storage rare earth-ferrotianium hydrogen storage alloy of the present invention is primarily of Ti, Fe, Mn, multicomponent rare earth and a small amount of LaNi
5alloy is formed, and its chemical formula consists of: Ti
1.1-xfe
0.8mn
0.2m
x+ yLaNi
5, wherein, x is atomic ratio, 0 < x≤0.09, and y is mass percent, 2%≤y≤8%, and M represents multicomponent rare earth, except containing atomic ratio being the La of 0.5-0.7, also containing at least one in Ce, Y, Nd, Pr, Gd.
The preparation method of wind-powered electricity generation energy storage rare earth-ferrotianium hydrogen storage alloy of the present invention, comprises the following steps:
A, proportioning: by chemical formula composition Ti
1.1-xfe
0.8mn
0.2m
x+ yLaNi
5carry out weighing and proportioning, wherein, x is atomic ratio, 0 < x≤0.09, y is mass percent, 2%≤y≤8%, M represents multicomponent rare earth, except containing atomic ratio being the La of 0.5-0.7, also containing at least one in Ce, Pr, Y, Nd, Gd; Metal purity>=99.5% of Ti, Fe, Mn, because Ti, Fe, Mn fusing point is higher, be respectively 1675,1535,1244 DEG C, and the most fusing point of rare earth element is lower, La, Ce, Y, Nd, Pr, Gd fusing point is respectively 921,799,931,1021,1522,1313 DEG C, the rare earth element added in fusion process is volatile, and therefore, the rare earth in described chemical formula composition increases the scaling loss amount of 5-10wt% when proportioning;
B, vacuum melting: the raw material prepared is placed in zirconium white crucible, the decoration form of each raw material in crucible be iron staff along sidewall of crucible vertical display, titanium sponge on crucible bottom uniform spreading, block manganese is placed in above titanium sponge, rare earth and LaNi
5alloy is placed on topmost, is evacuated to 1 × 10
-3pa, then 0.04MPa inert protective gas is filled with, induction heating is adopted to carry out melting to the raw material prepared, described inert protective gas is helium or argon gas and helium mix gas, described argon gas and helium mix gas volume are than being 1:1, smelting temperature is 1680-1720 DEG C, obtains the liquid mother alloy of melting;
C, fast quenching: after each raw material mixes, liquid mother alloy is injected tundish, drop on the smooth surface of water-cooled copper roller of rotation by the nozzle continuous spraying of tundish bottom, the linear resonance surface velocity of copper roller is 5-30m/s, obtain quenched alloy thin slice, the thickness of this quenched alloy thin slice is 100-500 μm, has the nanocrystalline crystalline-granular texture of high-density;
D, mechanical disintegration: quenched alloy thin slice is obtained rare earth-ferro-titanium powder by airflow milling mechanical disintegration, and powder size meets D
10=7-11 μm, D
50=38-46 μm, D
90=80-100 μm;
E, ball milling: the rare earth after mechanical disintegration-ferro-titanium powder is put into the stainless steel jar mill being filled with high-purity argon gas and carries out ball milling, ball milling condition is as follows: ratio of grinding media to material is 20:1-60:1, rotational speed of ball-mill is 200-450r/min, and each Ball-milling Time is 1-5h, and each time of having a rest is 10min, total Ball-milling Time is at 3-21h, after ball milling terminates, ball grinder is placed in and is full of high-purity argon gas vacuum glove box, take out powder materials, sieve and weigh, seal with Vacuum Packaging Machine.
Below in conjunction with embodiment, the present invention is described in detail.
The chemical formula of embodiment of the present invention 1-31 is composed as follows:
Comparative example 1Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 1Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 2Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 3Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 4Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 5Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 6Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 7Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 8Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 9Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 10Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 11Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 12Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 13Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 5%LaNi
5
Embodiment 14Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 2%LaNi
5
Embodiment 15Ti
1.055fe
0.8mn
0.2la
0.03ce
0.015+ 8%LaNi
5
Embodiment 16Ti
1.01fe
0.8mn
0.2la
0.06ce
0.03+ 5%LaNi
5
Embodiment 17Ti
1.01fe
0.8mn
0.2la
0.06pr
0.03+ 5%LaNi
5
Embodiment 18Ti
1.01fe
0.8mn
0.2la
0.06nd
0.03+ 5%LaNi
5
Embodiment 19Ti
1.01fe
0.8mn
0.2la
0.06y
0.03+ 5%LaNi
5
Embodiment 20Ti
1.01fe
0.8mn
0.2la
0.06gd
0.003+ 5%LaNi
5
Embodiment 21Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02pr
0.01+ 5%LaNi
5
Embodiment 22Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02nd
0.01+ 5%LaNi
5
Embodiment 23Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02y
0.01+ 5%LaNi
5
Embodiment 24Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02gd
0.01+ 5%LaNi
5
Embodiment 25Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02pr
0.005nd
0.005+ 5%LaNi
5
Embodiment 26Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02pr
0.005y
0.005+ 5%LaNi
5
Embodiment 27Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02pr
0.005gd
0.005+ 5%LaNi
5
Embodiment 28Ti
1.01fe
0.8mn
0.2la
0.06pr
0.02nd
0.005y
0.005+ 5%LaNi
5
Embodiment 29Ti
1.01fe
0.8mn
0.2la
0.06pr
0.02nd
0.005gd
0.005+ 5%LaNi
5
Embodiment 30Ti
1.01fe
0.8mn
0.2la
0.06nd
0.02y
0.005gd
0.005+ 5%LaNi
5
Embodiment 31Ti
1.01fe
0.8mn
0.2la
0.06ce
0.02pr
0.0025nd
0.0025y
0.0025gd
0.0025+ 5%LaNi
5
Concrete technology step is as follows:
A, proportioning: carry out weighing and proportioning by the chemical formula composition of above-described embodiment 1-31, wherein, rare earth increases the scaling loss amount of 5-10wt% when proportioning;
B, vacuum melting: the raw material prepared is placed in zirconium white crucible, is evacuated to 1 × 10
-3pa, then 0.04MPa inert protective gas is filled with, induction heating is adopted to carry out melting, described inert protective gas is helium or argon gas and helium mix gas, described argon gas and helium mix gas volume are than being 1:1, smelting temperature is 1680-1720 DEG C, and obtain the liquid mother alloy of melting, embodiment processing parameter refers to table 1;
C, fast quenching: after each raw material mixes, liquid mother alloy is injected tundish, drop on the smooth surface of water-cooled copper roller of rotation by the nozzle continuous spraying of tundish bottom, the linear resonance surface velocity of copper roller is 5-30m/s, obtain thickness quenched alloy thin slice between 100-500 μm, the processing parameter of embodiment 1-31 refers to table 1;
D, mechanical disintegration: quenched alloy thin slice mechanical disintegration in airflow milling is obtained rare earth-ferro-titanium powder;
E, ball milling: the rare earth after mechanical disintegration-ferro-titanium powder is put into the stainless steel jar mill being filled with high-purity argon gas and carries out ball milling, ball milling condition embodiment processing parameter refers to table 1.After ball milling terminates, ball grinder is placed in the vacuum glove box being filled with high-purity argon gas, takes out powder materials, sieve and weigh, seal with Vacuum Packaging Machine.
The concrete technology parameter of different embodiment 1-31 and comparative example 1 is see table 1.
The technical data of table 1 embodiment 1-31 and comparative example
Structural characterization and performance test are carried out to the alloy of above-mentioned preparation, adopts the microtexture of transmission electron microscope (TEM) beta alloy.
Fig. 1-6 is the TEM photo of the embodiment of the present invention 2,5,6,7,8,9.There is nanocrystalline, defect in a large number in rare earth-ferrotianium hydrogen storage alloy that the display of TEM photo adopts chemical formula of the present invention composition and preparation method to prepare.
Adopt the suction of Seviet tester beta alloy to put suction hydrogen dynamic performance that hydrogen capacity and PCT platform (as shown in table 2) adopt the isothermal Analytical system beta alloy of semi-automatic Sievelts device, test condition is 3MPa, 30 DEG C.
The result that hydrogen dynamic performance inhaled after tested by alloy prepared by above-described embodiment 1-31 is as shown in table 2.
The chemical property of table 2 embodiment alloy
Test result shows, the activation performance of alloy of the present invention improves greatly, 30 DEG C, can activate under the activation condition of 3MPa, and the activation condition of comparative example is 300 DEG C, 10MPa; The activation number of times of alloy of the present invention is 1-3 time, well below the activation number of times of comparative example alloy; The hydrogen－sucking amount of alloy of the present invention reaches 1.730wt%, comparatively LaNi
5alloy theory hydrogen－sucking amount promotes 23%, LaNi in prior art
5the theoretical hydrogen－sucking amount of alloy is 1.40wt%; Meanwhile, the material cost of alloy of the present invention reduces by more than 50%.
Claims (14)
1. wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy, is characterized in that:
This alloy is by Ti, Fe, Mn, multicomponent rare earth and a small amount of LaNi
5alloy is formed, and its chemical formula consists of: Ti
1.1-xfe
0.8mn
0.2m
x+ yLaNi
5, wherein, x is atomic ratio, 0 < x≤0.09, and y is mass percent, 2%≤y≤8%, and M represents multicomponent rare earth, except containing atomic ratio being the La of 0.5-0.7, also containing at least one in Ce, Y, Nd, Pr, Gd;
This alloy is prepared as follows: proportioning → vacuum melting → fast quenching → mechanical disintegration → ball milling.
2. rare earth according to claim 1-ferrotianium hydrogen storage alloy, is characterized in that:
Prepared the alloy with the nanocrystalline crystal grain of high-density by rapid quenching technique, then through mechanical ball milling, form the alloy of high-density lattice defect.
3. rare earth according to claim 1-ferrotianium hydrogen storage alloy, is characterized in that:
A small amount of LaNi is added during vacuum melting
5alloy.
4. rare earth according to claim 1-ferrotianium hydrogen storage alloy, is characterized in that:
The maximum hydrogen－sucking amount of alloy reaches 1.73wt%, and close to TiFe alloy theory hydrogen－sucking amount 1.86wt%, 1-3 suction is put hydrogen and namely activated completely.
5. a preparation method for wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy, is characterized in that:
The method comprises the steps:
A, proportioning: by chemical formula composition Ti
1.1-xfe
0.8mn
0.2m
x+ yLaNi
5carry out weighing and proportioning, wherein, x is atomic ratio, 0 < x≤0.09, y is mass percent, 2%≤y≤8%, M represents multicomponent rare earth, except containing atomic ratio being the La of 0.5-0.7, also containing at least one in Ce, Pr, Y, Nd, Gd;
B, vacuum melting: the raw material prepared is placed in zirconium white crucible, vacuumizes, be then filled with inert protective gas, adopt induction heating to carry out melting to the raw material prepared, obtain the liquid mother alloy of melting;
C, fast quenching: after each raw material mixes, directly inject tundish by liquid mother alloy, drops on the surface of water-cooled copper roller of rotation by the nozzle continuous spraying of tundish bottom, obtains quenched alloy thin slice;
D, mechanical disintegration: quenched alloy thin slice is obtained rare earth-ferro-titanium powder by airflow milling mechanical disintegration;
E, ball milling: the stainless steel jar mill that the rare earth after mechanical disintegration-ferro-titanium powder puts into high-purity argon gas is carried out ball milling, after ball milling terminates, ball grinder is placed in and is full of high-purity argon gas vacuum glove box, take out powder, sieve and weigh, seal with Vacuum Packaging Machine.
6. the preparation method of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy as claimed in claim 5, is characterized in that:
In steps A, metal purity >=99.5% of Ti, Fe, Mn;
Rare earth in described chemical formula composition increases the scaling loss amount of 5-10wt% when proportioning.
7. the preparation method of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy as claimed in claim 5, is characterized in that:
In step B, the raw material prepared is placed in zirconium white crucible, the decoration form of each raw material in crucible is: iron staff is along sidewall of crucible vertical display, and titanium sponge on crucible bottom uniform spreading, block manganese is placed in above titanium sponge, rare earth and LaNi
5alloy is placed on topmost.
8. the preparation method of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy as claimed in claim 5, is characterized in that:
In step B, be evacuated to 1 × 10
-3more than Pa, be then filled with 0.04MPa inert protective gas.
9. the preparation method of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy as claimed in claim 5, is characterized in that:
In step B, described inert protective gas is helium or argon gas and helium mix gas, and described argon gas and helium mix gas volume are than being 1:1.
10. the preparation method of wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloy as claimed in claim 5, is characterized in that:
In step B, smelting temperature is 1680-1720 DEG C.
The preparation method of 11. wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloys as claimed in claim 5, is characterized in that:
In step C, the linear resonance surface velocity of copper roller is 5-30m/s.
The preparation method of 12. wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloys as claimed in claim 5, is characterized in that:
In step C, the thickness of this quenched alloy thin slice is 100-500 μm, has the nanocrystalline crystalline-granular texture of high-density.
The preparation method of 13. wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloys as claimed in claim 5, is characterized in that:
In step D, powder size meets D
10=7-11 μm, D
50=38-46 μm, D
90=80-100 μm.
The preparation method of 14. wind-powered electricity generation energy storage device rare earth-ferrotianium hydrogen storage alloys as claimed in claim 5, is characterized in that:
In step e, ball milling condition is as follows: ratio of grinding media to material is 20:1-60:1, and rotational speed of ball-mill is 200-450r/min, and each Ball-milling Time is 1-5h, and each time of having a rest is 10min, and total Ball-milling Time is at 3-21h.
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| CN112387976B (en) * | 2020-11-27 | 2022-11-22 | 中稀(山东)稀土开发有限公司 | Easily-activated RE-Ti-Fe alloy for fuel cell and preparation method thereof |
| CN115141943A (en) * | 2022-05-17 | 2022-10-04 | 中稀(微山)稀土新材料有限公司 | RE catalyzed easy-to-activate Ti-Fe-Ni-Mn based hydrogen storage alloy for fuel cell and preparation method thereof |
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