CN105755302B - A kind of high-performance hydrogen bearing alloy and preparation method thereof - Google Patents
A kind of high-performance hydrogen bearing alloy and preparation method thereof Download PDFInfo
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- CN105755302B CN105755302B CN201410788219.2A CN201410788219A CN105755302B CN 105755302 B CN105755302 B CN 105755302B CN 201410788219 A CN201410788219 A CN 201410788219A CN 105755302 B CN105755302 B CN 105755302B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 98
- 239000001996 bearing alloy Substances 0.000 title claims abstract description 50
- 125000004435 hydrogen atom Chemical group [H]* 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 46
- 238000005275 alloying Methods 0.000 claims abstract description 20
- 239000008188 pellet Substances 0.000 claims abstract description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 238000004544 sputter deposition Methods 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 31
- 239000002245 particle Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 150000002431 hydrogen Chemical class 0.000 abstract description 15
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000011232 storage material Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000007771 core particle Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000013461 design Methods 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000003795 desorption Methods 0.000 description 11
- 238000005253 cladding Methods 0.000 description 10
- 230000006698 induction Effects 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910012375 magnesium hydride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000878 H alloy Inorganic materials 0.000 description 1
- -1 Hydride Chemical compound 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
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- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The invention discloses a kind of high-performance hydrogen bearing alloys and preparation method thereof.Hydrogen bearing alloy Pd@Mg Y are to coat Mg by Pd100‑xYxWhat (x=20~25) alloying pellet was formed, alloying pellet granularity is 50~150 microns, and Pd film thicknesses are 5~30nm.Preparation method is：Mg is prepared using vacuum melting method100‑xYx(x=20~25) master alloy ingot, then handled through Mechanical Crushing and granularity is made as 50~150 microns of hydrogen bearing alloy inner core particles, then use magnetron sputtering technology in Mg100‑xYxThe uniform coating Pd films in (x=20~25) inner core particles surface.The experimental results showed that：The Pd Mg prepared to top method77Y23The suction hydrogen discharging rate of hydrogen bearing alloy is significantly faster than that Mg77Y23Particle and faster in the suction hydrogen discharging rate of the pure Mg of same scale.Thus big granularity Pd@Mg are obtained77Y23Hydrogen bearing alloy has a good application prospect in terms of the hydrogen storage material and in terms of simplifying preparation process.
Description
Technical field
The present invention relates to a kind of material and preparation method thereof, in particular to a kind of hydrogen bearing alloy and preparation method thereof.
Background technology
As the hydrogen of green energy resource, due to its cleaning, and have the characteristics that convenient for storage with it is resourceful, so in future
It is occupied an important position in sustainable energy.So far, it is the storage of hydrogen to hinder the key factor of " hydrogen economy " development, therefore right
The research and development of hydrogen storage material become hydrogen utilization and move towards practical and scale one of key link.As largest application areas
Nickel-hydrogen battery negative pole material, it is desirable that the cycle life of discharge performance, length that hydrogen bearing alloy has had, suitable hydrogen decomposition pressure etc..
Magnesium-base hydrogen storage material becomes most potential since light weight, rich reserves, cheap and hydrogen storage capability are big (2200mAh/g)
One of hydrogen storage material, attracted the sight of countries in the world scientists.
But the hydrogen storage property of Mg base hydrogenous alloys is largely determined by the influence of granularity, and particle is smaller, inhales hydrogen desorption kinetics
Performance is more excellent.Because：Mg has high reaction activity to the oxygen in air, when inhaling hydrogen, can form densification in particle surface
MgH2Hydride coatings, and MgH2Stability is high, in 0.1MPa H2Decomposition temperature under pressure is up to 300 DEG C, and hydrogen discharge reaction speed
Rate is slow, so hindering the further diffusion of hydrogen, hydrogen desorption kinetics degradation.According to the literature, when hydride thickness
When degree is more than 30~50 μm, hydrogen cannot continue to spread, and absorptivity is close to 0.Therefore current studied Mg-base hydrogen-bearing closes
The granularity of gold is usually less than 60 μm.And the large scale of alloy is more suitable for industrialized production.Therefore, improve the storage of bulky grain granularity
The performance of hydrogen alloy directly affects the industrial applications of Mg base hydrogen bearing alloy.
For the improvement problem of bulky grain hydrogen bearing alloy dynamic performance, it is one of more effective method that surface, which is modified,.
Alloy surface covers one layer of catalyst, can promote the dissociation and absorption of hydrogen, and then improve and inhale hydrogen desorption kinetics performance, simultaneously
Mg can also be protected from oxidation.The technological approaches shows fabulous improvement in Mg base films.And big
Cladding seldom report is realized on particle hydrogen bearing alloy.So needing to provide a kind of Mg base hydrogen storages conjunction of which kind of element of selection and ingredient
Gold is simultaneously obtained by the technical solution of which kind of cladding with good dynamic performance.
Invention content：
The purpose of the present invention is to provide a kind of high-performance hydrogen bearing alloy Pd@Mg-Y.
It is a further object of the present invention to provide a kind of methods preparing Pd@Mg-Y hydrogen bearing alloys.
The purpose of the present invention is what is realized with following technical scheme：
High-performance hydrogen bearing alloy Pd@Mg-Y provided by the invention, the alloy core ingredient are Mg100-xYxAlloying pellet, x are
20~25, outer surface is coated with the Pd films of uniform thickness.
In first optimal technical scheme of the alloy provided by the invention, the granularity of kernel Mg-Y is 50~150 microns.
In second optimal technical scheme of the alloy provided by the invention, Pd film thicknesses are 5~30nm.
The preparation method of hydrogen bearing alloy Pd@Mg-Y provided by the present invention includes the following steps：
A, dispensing：Metal Mg and metal Y is 3 according to molar ratio:1~4:1 ratio dispensing；
B, master alloy is prepared：Raw material is placed in the graphite crucible of smelting furnace, is vacuumized, with argon gas to furnace chamber purging 3~5
Secondary, then heating obtains uniformly mixed Mg and y alloy molten liquid, and the melting charge is poured into copper cold-crucible and is condensed,
Obtain as cast condition Mg-Y master alloy ingots；
C, Mg-Y master alloy ingots made of step b are crushed, crosses the screening of 100~300 mesh, it is 50~150 micro- that granularity, which is made,
The alloying pellet of rice；
D, using Pd targets as the cathode of magnetron sputtering coater, by alloying pellet made from step c in magnetron sputtering coater
Sample vibration ware in, be coated with Pd films, obtain hydrogen bearing alloy Pd@Mg-Y.
In first optimal technical scheme of the alloy preparation method, the purity of metal Mg and metal Y 99.5% with
On.
In second optimal technical scheme of the alloy preparation method, the vacuum degree of the b step is higher than 5 × 10-4Pa；It blows
Purity of argon >=99.999% of prepurging chamber；After preheating 20~30 seconds, electric current is adjusted to 120~160A, keeps alloy block molten
Electric current is risen into 200~350A again after change, is heated 2~3 minutes.
In the third optimal technical scheme of the alloy preparation method, step c is completed in vacuum glove box.
In 4th optimal technical scheme of the alloy preparation method, cathode Pd target diameters described in step d be 60~
80mm, purity >=99.9%；Background vacuum 1 × 10-3~2 × 10-3Pa, with the sputtering argon of purity >=99.99%, in
Argon flow amount is 40~80sccm, and pressure is under 0.5~0.8Pa, and sputtering power is to be sputtered 120~300 seconds under 120~200W；
It is 5~20Hz that sample, which vibrates ware vibration frequency,.
With immediate prior art ratio, technical solution provided by the invention has following excellent effect:
1) the Pd@Mg-Y hydrogen bearing alloys for using the method for the present invention to prepare have system compared with sample prepared by conventional method
Product performance indicator regulates and controls the advantages that big degree of freedom, quality controllable, superior performance；
2) Pd@Mg-Y hydrogen bearing alloys prepared by the method for the present invention have kernel composition, particle diameter and clad Pd films
The features such as thickness is flexibly controllable, preparation process energy conservation and environmental protection is pollution-free, therefore extremely suitable industrial applications.
3) Pd@Mg-Y hydrogen bearing alloys provided by the invention are in activation process, Pd@Mg77Y23The hydrogen-absorbing ability of particle is better than
Mg77Y23Particle, hydrogen-absorption speed are significantly faster than that Mg77Y23Particle.And during subsequent hydrogen release, hydrogen discharging rate is also significantly fast
In Mg77Y23Particle.Show the Mg with sputter coating layer Pd77Y23The dynamic performance of particle is greatly improved.
Description of the drawings
Fig. 1 is vibrating device schematic diagram provided by the invention.
Fig. 2 is Pd@Mg prepared by the embodiment of the present invention 177Y23The SEM patterns (a) and Surface scan EDS (b) and Pd of particle
(c), the power spectrum mapping of Mg (d), Y (e).
Fig. 3 is Pd@Mg prepared by the embodiment of the present invention 177Y23Particle and Mg77Y23The suction Hydrogen desorption isotherms of particle compare.
Specific implementation mode
Embodiment 1
Prepare 60~80 μm of grain graininess, cladding Pd film thicknesses 5nm, composition Pd@Mg77Y23Hydrogen bearing alloy
1) dispensing
With purity design ingredient Mg is pressed in 99.5% or more metal Mg and metal Y77Y23Dispensing is carried out, and considers one
Fixed scaling loss (scaling loss of Y is set as 5wt%, Mg scaling loss 15wt%)；
2) alloy melting
Mg-Y master alloys are prepared using high vacuum high-frequency induction smelting furnace.The raw material that step 1) prepares is placed in high vacuum height
In the graphite crucible of frequency induction melting furnace, it is evacuated to background vacuum and is higher than 5 × 10-4Pa, then through with purity >=99.999%
Argon gas carries out 3 prepurgings to furnace chamber, then begins to warm up：Power supply preheated crucible is first opened after 20 seconds, adjustment electric current makes to 120A
Alloy block is completely melt；Then melting electric current is improved to 240A, is kept for 2 minutes, is waited for that Mg and y alloy molten liquid are mixed at high temperature
After closing uniformly, melt is poured into copper cold-crucible and is condensed, certain ingredients as cast condition mother's Mg-Y ingot is obtained.
3) break process
Mechanical Crushing will be carried out through Mg-Y master alloy ingots made of step 2) into fritter, then be put and be ground into the agate mortar
Fine powder is screened by 200 mesh, and the alloying pellet that granularity is 60~80 microns is made.To avoid particle from aoxidizing in air, it is crushed
Processing procedure is completed in vacuum glove box.
4) magnetron sputtering Pd films
Choose cathode of the Pd targets of diameter 60mm, purity >=99.9% as magnetron sputtering coater.It will be made through step 3)
At kernel alloying pellet be placed on the sample in magnetron sputtering coater vibration ware in.Sample vibrates ware schematic diagram such as Fig. 1 institutes
Show.
Sputter coating parameter, which is arranged, is：Background vacuum 1 × 10-3Pa, using the argon gas of purity >=99.99% as sputtering gas
Body, argon flow amount 50sccm, operating pressure 0.6Pa, sputtering power 150W, sputter coating time are 180 seconds.Plated film mistake
It is 5Hz that journey sample, which vibrates ware vibration frequency, and Pd films cladding Mg is made77Y23Alloying pellet, i.e. Pd@Mg77Y23Hydrogen bearing alloy.
EDAX results show Pd@Mg prepared by above-mentioned steps77Y23Hydrogen bearing alloy kernel composition ratio is Mg76.8Y23.2,
Illustrate that female ingot composition and design proportioning are essentially identical；It is observed in conjunction with particle cross section microscopic appearance, it is known that Pd film thicknesses are about
5nm meets design requirement.
Fig. 3 is Pd@Mg77Y23The Dynamic isotherms of hydrogen absorption that alloy is depressed in 350 DEG C, 2MPa hydrogen for the first time compares, and can see
It arrives, Pd@Mg prepared by the above process77Y23Hydrogen bearing alloy ratio Mg77Y23Absorption hydrogen ability improves 23%, and hydrogen-absorption speed improves
30% (to reach in terms of saturation hydrogen-sucking amount 80%).And during subsequent hydrogen release, Pd@Mg77Y23Hydrogen bearing alloy hydrogen discharging rate
Compare Mg77Y23Alloy speeded for 42% (to reach in terms of hydrogen desorption capacity 80%).
Embodiment 2
Prepare 100~120 μm of grain graininess, cladding Pd film thicknesses 10nm, composition Pd@Mg77Y23Hydrogen bearing alloy
1) dispensing
With purity design ingredient Mg is pressed in 99.5% or more metal Mg and metal Y77Y23Dispensing is carried out, and considers one
Fixed scaling loss (scaling loss of Y is set as 5wt%, Mg scaling loss 15wt%)；
2) alloy melting
Mg-Y master alloys are prepared using high vacuum high-frequency induction smelting furnace.The raw material that step 1) prepares is placed in high vacuum height
In the graphite crucible of frequency induction melting furnace, it is evacuated to background vacuum and is higher than 5 × 10-4Pa, then through with purity >=99.999%
Argon gas carries out 3 prepurgings to furnace chamber, then begins to warm up：Power supply preheated crucible is first opened after 20 seconds, adjustment electric current makes to 120A
Alloy block is completely melt；Then melting electric current is improved to 240A, is kept for 2 minutes, is waited for that Mg and y alloy molten liquid are mixed at high temperature
After closing uniformly, melt is poured into copper cold-crucible and is condensed, certain ingredients as cast condition mother's Mg-Y ingot is obtained.
3) break process
Mechanical Crushing will be carried out through Mg-Y master alloy ingots made of step 2) into fritter, then be put and be ground into the agate mortar
Fine powder is screened by 120 mesh, and the alloying pellet that granularity is 100~120 microns is made.To avoid particle from aoxidizing in air, break
Broken processing procedure is completed in glove box.
4) magnetron sputtering Pd films
Choose cathode of the Pd targets of diameter 60mm, purity >=99.9% as magnetron sputtering coater.It will be made through step 3)
At kernel alloying pellet be placed on the sample in magnetron sputtering coater vibration ware in.Sample vibrates ware schematic diagram such as Fig. 1 institutes
Show.
Sputter coating parameter, which is arranged, is：Background vacuum 1 × 10-3Pa, using the argon gas of purity >=99.99% as sputtering gas
Body, argon flow amount 50sccm, operating pressure 0.6Pa, sputtering power 150W, sputter coating time are 360 seconds.Plated film mistake
It is 5Hz that journey sample, which vibrates ware vibration frequency, and Pd films cladding Mg is made77Y23Alloying pellet, i.e. Pd@Mg77Y23Hydrogen bearing alloy.
EDAX results show Pd@Mg prepared by above-mentioned steps77Y23Hydrogen bearing alloy kernel composition ratio is Mg76.9Y23.1,
Illustrate that female ingot composition and design proportioning are essentially identical；According to inductively coupled plasma atomic emission spectrum (ICP-AES) ingredient
It is about 10nm to measure Pd contents and combine granule-morphology estimation Pd film thicknesses, meets design requirement.
Hydrogen desorption kinetics curve is inhaled from hydrogen bearing alloy it is found that Pd@Mg prepared by the above process77Y23Hydrogen bearing alloy ratio Mg77Y23
Absorption hydrogen ability improves 27%, and hydrogen-absorption speed improved for 33% (to reach in terms of saturation hydrogen-sucking amount 80%).And it is put in subsequent
During hydrogen, Pd@Mg77Y23Hydrogen bearing alloy hydrogen discharging rate ratio Mg77Y23Alloy speeded for 46% (to reach in terms of hydrogen desorption capacity 80%).
Embodiment 3
Prepare 60~80 μm of grain graininess, cladding Pd film thicknesses 20nm, composition Pd@Mg77Y23Hydrogen bearing alloy
1) dispensing
With purity design ingredient Mg is pressed in 99.5% or more metal Mg and metal Y77Y23Dispensing is carried out, and considers one
Fixed scaling loss (scaling loss of Y is set as 5wt%, Mg scaling loss 15wt%)；
2) alloy melting
Mg-Y master alloys are prepared using high vacuum high-frequency induction smelting furnace.The raw material that step 1) prepares is placed in high vacuum height
In the graphite crucible of frequency induction melting furnace, it is evacuated to background vacuum and is higher than 5 × 10-4Pa, then through with purity >=99.999%
Argon gas carries out 3 prepurgings to furnace chamber, then begins to warm up：Power supply preheated crucible is first opened after 20 seconds, adjustment electric current makes to 120A
Alloy block is completely melt；Then melting electric current is improved to 240A, is kept for 2 minutes, is waited for that Mg and y alloy molten liquid are mixed at high temperature
After closing uniformly, melt is poured into copper cold-crucible and is condensed, certain ingredients as cast condition mother's Mg-Y ingot is obtained.
3) break process
Mechanical Crushing will be carried out through Mg-Y master alloy ingots made of step 2) into fritter, then be put and be ground into the agate mortar
Fine powder is screened by 200 mesh, and the alloying pellet that granularity is 60~80 microns is made.To avoid particle from aoxidizing in air, it is crushed
Processing procedure is completed in glove box.
4) magnetron sputtering Pd films
Choose cathode of the Pd targets of diameter 60mm, purity >=99.9% as magnetron sputtering coater.It will be made through step 3)
At kernel alloying pellet be placed on the sample in magnetron sputtering coater vibration ware in.Sample vibrates ware schematic diagram such as Fig. 1 institutes
Show.
Sputter coating parameter, which is arranged, is：Background vacuum 1 × 10-3Pa, using the argon gas of purity >=99.99% as sputtering gas
Body, argon flow amount 50sccm, operating pressure 0.6Pa, sputtering power 150W, sputter coating time are 180 seconds.Plated film mistake
It is 5Hz that journey sample, which vibrates ware vibration frequency, and Pd films cladding Mg is made77Y23Alloying pellet, i.e. Pd@Mg77Y23Hydrogen bearing alloy.
EDAX results show Pd@Mg prepared by above-mentioned steps77Y23Hydrogen bearing alloy kernel composition ratio is Mg76.8Y23.2,
Illustrate that female ingot composition and design proportioning are essentially identical；It is observed in conjunction with particle cross section microscopic appearance, it is known that Pd film thicknesses are about
20nm meets design requirement.
Hydrogen desorption kinetics curve is inhaled from hydrogen bearing alloy it is found that Pd@Mg prepared by the above process77Y23Hydrogen bearing alloy ratio Mg77Y23
Absorption hydrogen ability improves 31%, and hydrogen-absorption speed improved for 35% (to reach in terms of saturation hydrogen-sucking amount 80%).And it is put in subsequent
During hydrogen, Pd@Mg77Y23Hydrogen bearing alloy hydrogen discharging rate ratio Mg77Y23Alloy speeded for 48% (to reach in terms of hydrogen desorption capacity 80%).
Embodiment 4
Prepare 100~120 μm of grain graininess, cladding Pd film thicknesses 30nm, composition Pd@Mg77Y23Hydrogen bearing alloy
1) dispensing
With purity design ingredient Mg is pressed in 99.5% or more metal Mg and metal Y77Y23Dispensing is carried out, and considers one
Fixed scaling loss (scaling loss of Y is set as 5wt%, Mg scaling loss 15wt%)；
2) alloy melting
Mg-Y master alloys are prepared using high vacuum high-frequency induction smelting furnace.The raw material that step 1) prepares is placed in high vacuum height
In the graphite crucible of frequency induction melting furnace, it is evacuated to background vacuum and is higher than 5 × 10-4Pa, then through with purity >=99.999%
Argon gas carries out 3 prepurgings to furnace chamber, then begins to warm up：Power supply preheated crucible is first opened after 20 seconds, adjustment electric current makes to 120A
Alloy block is completely melt；Then melting electric current is improved to 240A, is kept for 2 minutes, is waited for that Mg and y alloy molten liquid are mixed at high temperature
After closing uniformly, melt is poured into copper cold-crucible and is condensed, certain ingredients as cast condition mother's Mg-Y ingot is obtained.
3) break process
Mechanical Crushing will be carried out through Mg-Y master alloy ingots made of step 2) into fritter, then be put and be ground into the agate mortar
Fine powder is screened by 120 mesh, and the alloying pellet that granularity is 100~120 microns is made.To avoid particle from aoxidizing in air, break
Broken processing procedure is completed in glove box.
4) magnetron sputtering Pd films
Choose cathode of the Pd targets of diameter 60mm, purity >=99.9% as magnetron sputtering coater.It will be made through step 3)
At kernel alloying pellet be placed on the sample in magnetron sputtering coater vibration ware in.Sample vibrates ware schematic diagram such as Fig. 1 institutes
Show.
Sputter coating parameter, which is arranged, is：Background vacuum 1 × 10-3Pa, using the argon gas of purity >=99.99% as sputtering gas
Body, argon flow amount 50sccm, operating pressure 0.6Pa, sputtering power 150W, sputter coating time are 360 seconds.Plated film mistake
It is 5Hz that journey sample, which vibrates ware vibration frequency, and Pd films cladding Mg is made77Y23Alloying pellet, i.e. Pd@Mg77Y23Hydrogen bearing alloy.
EDAX results show Pd@Mg prepared by above-mentioned steps77Y23Hydrogen bearing alloy kernel composition ratio is Mg76.9Y23.1,
Illustrate that female ingot composition and design proportioning are essentially identical；According to inductively coupled plasma atomic emission spectrum (ICP-AES) ingredient
It is about 30nm to measure Pd contents and combine granule-morphology estimation Pd film thicknesses, meets design requirement.
Hydrogen desorption kinetics curve is inhaled from hydrogen bearing alloy it is found that Pd@Mg prepared by the above process77Y23Hydrogen bearing alloy ratio Mg77Y23
Absorption hydrogen ability improves 28%, and hydrogen-absorption speed improved for 32% (to reach in terms of saturation hydrogen-sucking amount 80%).And it is put in subsequent
During hydrogen, Pd@Mg77Y23Hydrogen bearing alloy hydrogen discharging rate ratio Mg77Y23Alloy speeded for 45% (to reach in terms of hydrogen desorption capacity 80%).
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, the ordinary skill people of fields
Member, which should be appreciated that, can be modified or replaced equivalently the specific implementation mode of the present invention with reference to above-described embodiment, these
Without departing from any modification of spirit and scope of the invention or equivalent replacement apply pending claims it
It is interior.
Claims (6)
1. a kind of high-performance hydrogen bearing alloy Pd Mg-Y, it is characterised in that interior nuclear composition is Mg100-xYxAlloying pellet, x be 20~
25, outer surface is coated with the Pd films of uniform thickness；
The granularity of kernel Mg-Y is 50~150 microns；
Pd film thicknesses are 5~30nm.
2. the preparation method of hydrogen bearing alloy Pd@Mg-Y as described in claim 1, comprises the following steps：
A, dispensing：Metal Mg and metal Y is 3 according to molar ratio:1~4:1 ratio dispensing；
B, master alloy is prepared：Raw material is placed in the graphite crucible of smelting furnace, is vacuumized, furnace chamber is purged 3~5 times with argon gas,
Then heating obtains uniformly mixed Mg and y alloy molten liquid, and melting charge is poured into copper cold-crucible and is condensed, as cast condition is obtained
Mg-Y master alloy ingots；
C, Mg-Y master alloy ingots made of step b are crushed, crosses the screening of 100~300 mesh, it is 50~150 microns that granularity, which is made,
Alloying pellet；
D, using Pd targets as the cathode of magnetron sputtering coater, alloying pellet made from step c is placed on magnetron sputtering coater
Sample vibrates in ware, is coated with Pd films, obtains hydrogen bearing alloy Pd@Mg-Y.
3. the preparation method of hydrogen bearing alloy Pd@Mg-Y as claimed in claim 2, which is characterized in that metal Mg's and metal Y is pure
Degree is 99.5% or more.
4. the preparation method of hydrogen bearing alloy Pd@Mg-Y as claimed in claim 2, which is characterized in that the vacuum degree of the b step
Higher than 5 × 10-4Pa；Purge purity of argon >=99.999% of furnace chamber；After preheating 20~30 seconds, electric current is adjusted to 120~
Electric current is risen to 200~350A by 160A again after so that alloy block is melted, and is heated 2~3 minutes.
5. the preparation method of hydrogen bearing alloy Pd@Mg-Y as claimed in claim 2, it is characterised in that step c is in vacuum glove
It is completed in case.
6. the preparation method of hydrogen bearing alloy Pd@Mg-Y as claimed in claim 2, which is characterized in that cathode Pd described in step d
Target diameter is 60~80mm, purity >=99.9%；Background vacuum 1 × 10-3~2 × 10-3Pa, with the argon gas of purity >=99.99%
Sputter gas is 40~80sccm in argon flow amount, and pressure is under 0.5~0.8Pa, and sputtering power is sputtering under 120~200W
120~300 seconds；It is 5~20Hz that sample, which vibrates ware vibration frequency,.
Priority Applications (1)
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| CN108584870A (en) * | 2018-07-18 | 2018-09-28 | 宁波革创新材料科技有限公司 | A kind of preparation method of environmental protection hydrogen storage material |
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| CN109234695A (en) * | 2018-11-15 | 2019-01-18 | 杭州电子科技大学 | A kind of preparation method of nanocrystalline intermetallics hydrogen storage material |
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| CN103658641A (en) * | 2013-12-06 | 2014-03-26 | 上海交通大学 | Magnesium base composite hydrogen storage material and preparation method thereof |
| CN103668133A (en) * | 2013-09-09 | 2014-03-26 | 西北工业大学 | Method for Zr-based hydrogen storage alloy deposition of Pd film and plating solution for chemical plating |
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| CN103668133A (en) * | 2013-09-09 | 2014-03-26 | 西北工业大学 | Method for Zr-based hydrogen storage alloy deposition of Pd film and plating solution for chemical plating |
| CN103658641A (en) * | 2013-12-06 | 2014-03-26 | 上海交通大学 | Magnesium base composite hydrogen storage material and preparation method thereof |
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| CN108584870A (en) * | 2018-07-18 | 2018-09-28 | 宁波革创新材料科技有限公司 | A kind of preparation method of environmental protection hydrogen storage material |
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