CN109609791A - A kind of static state hydrogen compressed complex phase hydrogen bearing alloy and the preparation method and application thereof - Google Patents
A kind of static state hydrogen compressed complex phase hydrogen bearing alloy and the preparation method and application thereof Download PDFInfo
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- CN109609791A CN109609791A CN201811617846.4A CN201811617846A CN109609791A CN 109609791 A CN109609791 A CN 109609791A CN 201811617846 A CN201811617846 A CN 201811617846A CN 109609791 A CN109609791 A CN 109609791A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B37/00—Pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B25/00 - F04B35/00
- F04B37/10—Pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B25/00 - F04B35/00 for special use
- F04B37/18—Pumps having pertinent characteristics not provided for in, or of interest apart from, groups F04B25/00 - F04B35/00 for special use for specific elastic fluids
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
Abstract
The present invention relates to a kind of static hydrogen compressed complex phase hydrogen bearing alloys and the preparation method and application thereof, belong to Hydrogen Technology field.The complex phase hydrogen bearing alloy is prepared through master alloy, and master alloy includes first kind alloy or the second class alloy, and first kind alloy is AB2Type alloy and AB5The composite alloy of type alloy, the second class alloy are AB type alloy and AB5The composite alloy of type alloy.The complex phase hydrogen bearing alloy has more mild activation temperature and pressure, while the hydrogen storage property of alloy is good.Preparation method includes: to prepare master alloy, then melting, heat treatment.This method is simple and easy, is conducive to that the complex phase hydrogen bearing alloy haveing excellent performance is made.It is used for preparing static hydrogen compressor, is conducive to overcome and purchases the disadvantages such as maintenance cost is high, the service life is short, volume is big, power consumption is high, water consume is more and energy efficiency is low existing for mechanical hydrogen compressor at present.
Description
Technical field
The invention belongs to Hydrogen Technology fields, and in particular to a kind of static hydrogen compressed complex phase hydrogen bearing alloy and its preparation
Method and application.
Background technique
With the development of hydrogen fuel fuel cell electric vehicle, the research and construction of Hydrogen Energy infrastructure have caused each state
The common concern of family, but that there are volumes is big, quality weight, power consumption is high, water consume is more, energy efficiency is low for traditional mechanical hydrogen compressor
The disadvantages of, relevant core technology is firmly rested in the developed capitalist countries such as American-European-Japanese, cause the construction of hydrogenation stations at
This exception is expensive.
Summary of the invention
One of the objects of the present invention is to provide a kind of static hydrogen compressed complex phase hydrogen bearing alloy, complex phase hydrogen bearing alloy tools
There are more mild activation temperature and pressure, while the hydrogen storage property of alloy is good.
The second object of the present invention is to provide a kind of preparation method of above-mentioned static hydrogen compressed complex phase hydrogen bearing alloy, be somebody's turn to do
Method is simple and easy, is conducive to that the complex phase hydrogen bearing alloy haveing excellent performance is made.
The third object of the present invention is to provide a kind of application of above-mentioned static hydrogen compressed complex phase hydrogen bearing alloy, such as can
It is used for preparing static hydrogen compressor, is conducive to overcome and purchases maintenance cost height, longevity existing for mechanical hydrogen compressor at present
Order the disadvantages such as short, volume is big, power consumption is high, water consume is more and energy efficiency is low.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of static hydrogen compressed complex phase hydrogen bearing alloy, the complex phase hydrogen bearing alloy prepare through master alloy and
, master alloy includes first kind alloy or the second class alloy, and first kind alloy is AB2Type alloy and AB5The compound conjunction of type alloy
Gold, the chemical general formula of first kind alloy are Ti0.5Zr0.5(Fe0.1Cr0.3Mn0.1)2+xLa(Ni0.2Mn0.1)5(x=0.1-0.5)；The
Two class alloys are AB type alloy and AB5The composite alloy of type alloy, the chemical general formula of the second class alloy are TiFe0.8Mn0.2+
yLa0.8Ce0.2Ni5(y=0.005-0.05).
The present invention also proposes a kind of preparation method of above-mentioned static hydrogen compressed complex phase hydrogen bearing alloy, comprising the following steps:
Master alloy is prepared, then melting, is heat-treated.
In some embodiments, it prepares master alloy and fusion process includes: by the component requirements of complex phase hydrogen bearing alloy
Then electric arc melting mixes first kind alloy and the second class alloy to prepare first kind alloy and the second class alloy respectively,
Second of electric arc melting.
It further, also successively include third time electric arc melting and the 4th electric arc melting after second of electric arc melting, the
Electric arc melting, the condition of the 4th electric arc melting are identical as the condition of second of electric arc melting three times.
It in some preferred embodiments, further include to second between second of electric arc melting and third time electric arc melting
The alloy product obtained after secondary electric arc melting is carried out cooling for the first time and is overturn for the first time, third time electric arc melting and the 4th electricity
It further include that second of cooling and second of overturning is carried out to the alloy product obtained after third time electric arc melting between arc melting, the
It further include carrying out third time cooling to the alloy product obtained after the 4th electric arc melting and turning over for the third time after four electric arc meltings
Turn.
In other embodiments, prepare master alloy and fusion process include: by the component requirements of complex phase hydrogen bearing alloy,
The corresponding elemental metals of the element contained in complex phase hydrogen bearing alloy are mixed, then unify melting, then by the conjunction of melting
Complex phase hydrogen bearing alloy is made in golden liquid.
The present invention also proposes a kind of application of above-mentioned static hydrogen compressed complex phase hydrogen bearing alloy, such as can be used for preparing
Static hydrogen compressor.
The beneficial effect of static state hydrogen compressed complex phase hydrogen bearing alloy provided by the present application and the preparation method and application thereof includes:
Static state hydrogen compressed provided by the present application has more mild activation temperature and pressure with complex phase hydrogen bearing alloy, simultaneously
The hydrogen storage property of alloy is good.Preparation method is simple and easy, is conducive to that the complex phase hydrogen bearing alloy haveing excellent performance is made.By its
Be used to prepare static hydrogen compressor, be conducive to overcome purchased existing for mechanical hydrogen compressor at present maintenance cost is high, the service life is short,
The disadvantages such as volume is big, power consumption is high, water consume is more and energy efficiency is low.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the schematic diagram of static hydrogen compressed multiphase structure absorption hydrogen process in the application；
Fig. 2 is TFM+0.02AB in the application test example 15Alloy before activation, after activation and after 4 suctions hydrogen releases recycle
XRD spectrum；
Fig. 3 is TFM+yAB in the application test example 25(y=0.005) scanning electron microscope (SEM) photograph；
Fig. 4 is TFM+yAB in the application test example 25(y=0.01) scanning electron microscope (SEM) photograph；
Fig. 5 is TFM+yAB in the application test example 25(y=0.015) scanning electron microscope (SEM) photograph；
Fig. 6 is TFM+yAB in the application test example 25(y=0.02) scanning electron microscope (SEM) photograph.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Have below to the static hydrogen compressed of the embodiment of the present invention with complex phase hydrogen bearing alloy and the preparation method and application thereof
Body explanation.
Static state hydrogen compressed provided by the present application is prepared with complex phase hydrogen bearing alloy through master alloy.Inventor is through studying for a long period of time
It was found that it is low to inhale hydrogen pressure in low temperature using metal hydride, hydrogen release pressure high feature when high temperature, may be implemented to hydrogen into
Row is pressurized and substitutes mechanical hydrogen compressor, reaches very high target.And the core of hydrogen pressure metal hydride hydrogen contracting technology
It is hydrogen compression material.Though currently, Ti-Mn system AB2The hydrogen release pressure of output 45MPa can be achieved in type hydrogen storage alloy at 100 DEG C,
Hydrogen release pressure of the Ti-Zr base hydrogen storage alloy at 45 DEG C can reach 65MPa, but these alloys all there is inhale hydrogen release lag greatly with
And phenomena such as activation difficulty.
In consideration of it, master alloy includes first kind alloy or the second class alloy in the application, first kind alloy is AB2Type alloy
With AB5The composite alloy of type alloy, the second class alloy are AB type alloy and AB5The composite alloy of type alloy.Wherein, the first kind is closed
The chemical general formula of gold is Ti0.5Zr0.5(Fe0.1Cr0.3Mn0.1)2+xLa(Ni0.2Mn0.1)5(x=0.1-0.5, molar ratio), the second class
The chemical general formula of alloy is TiFe0.8Mn0.2+yLa0.8Ce0.2Ni5(y=0.005-0.05, molar ratio).
It include LaNi in first kind alloy5It include LaNi in type phase and Laves phase and/or the second class alloy5Type phase and
Contain the different phase component of at least two classes in TiFe phase namely every class alloy.
Suction hydrogen phenomenon can occur at a lower temperature and in the short period for above-mentioned static state hydrogen compressed complex phase hydrogen bearing alloy,
Hydrogen storage content is higher, has the advantages that reduce activation temperature and improves absorption hydrogen dynamic performance.
Above-mentioned static state hydrogen compressed for example may comprise steps of with the preparation method of complex phase hydrogen bearing alloy: preparation is female to close
Gold, then melting, heat treatment.
Wherein, it prepares master alloy and any one in following two technology path can be used in melting step.
Master alloy is prepared in the first route and fusion process includes: by the component requirements of complex phase hydrogen bearing alloy, for the first time
Then electric arc melting mixes first kind alloy and the second class alloy to prepare first kind alloy and the second class alloy respectively, and second
Secondary electric arc melting.
The condition of above-mentioned first time electric arc melting and second of electric arc melting may be the same or different.When identical,
Temperature during melting all can be 1200-1600 DEG C, such as 1200 DEG C, 1300 DEG C, 1400 DEG C, 1500 DEG C or 1600 DEG C,
It can be 1250 DEG C, 1350 DEG C, 1450 DEG C or 1550 DEG C etc., can also be any temperature value within the scope of 1200-1600 DEG C.
In some preferred embodiments, each alloy keeps the temperature 2-5min after melting completely, such as 2min, 3min, 4min
Or 5min etc..
In some preferred embodiments, the melting of first kind alloy and the second class alloy is in inert gas shielding
Under the conditions of carry out, inert gas may include the gaseous mixture of argon gas or helium or both arbitrary proportion.
Further, it may also include third time electric arc melting after second of electric arc melting, further, second of electric arc
It can successively include but is not limited to third time electric arc melting and the 4th electric arc melting etc. after melting.Preferably, third time electric arc
The condition of melting and the 4th electric arc melting is identical as the condition of second of electric arc melting.It is worth explanation, it can be according to reality
It needs, continues more electric arc melting after the 4th electric arc melting.
It in some preferred embodiments, further include to second between second of electric arc melting and third time electric arc melting
The alloy product obtained after secondary electric arc melting is carried out cooling for the first time and is overturn for the first time；Similarly, third time electric arc melting with
It further include that second of cooling and second are carried out to the alloy product obtained after third time electric arc melting between 4th electric arc melting
Secondary overturning；It further, further include that the is carried out to the alloy product that obtains after the 4th electric arc melting after the 4th electric arc melting
Cooling three times and third time is overturn.
By the overturning step between adjacent double arc-melting, the uniform of alloy structure and ingredient can be effectively improved
Property.
Master alloy is prepared in second of route and fusion process may include: to incite somebody to action by the component requirements of complex phase hydrogen bearing alloy
The corresponding elemental metals of the element contained in complex phase hydrogen bearing alloy are mixed, and then unify melting, then by the alloy of melting
Complex phase hydrogen bearing alloy is made in liquid.
A kind of ibid route, in second of route, the temperature during melting may be 1200-1600 DEG C.Alloy is complete
2-5min can also be kept the temperature after full-fusing.
Further, the aluminium alloy of melting pass through with revolving speed for 800-1500rpm (such as 800rpm, 1000rpm, 1200rpm or
1500rpm etc.) rotation water-cooled copper roller complex phase hydrogen bearing alloy is made.In some embodiments, what water cooled copper roller was got rid of answers
Phase hydrogen storage alloy with a thickness of 0.4-0.6mm (such as 0.4mm, 0.45mm, 0.5mm, 0.55mm or 0.6mm).
It is worth noting that the melting mode in the application is not limited only to using electric arc melting, it can also be using other molten
Refining mode, but preferably electric arc melting, reason are: and electric arc melting clamps pot using water-cooled copper, can effectively avoid material in height
Occur to react to bring into pincers pot pollution impurity when warm melting into alloy, the low-alloyed activation of drop and hydrogen storage property etc. occurs
Phenomenon.
In the application, heat treatment can be to prepare resulting alloy and be put into vacuum heat treatment furnace and make annealing treatment,
In the process, it high-purity argon gas (such as purity is not less than 99.999%) can be used to be protected to aoxidize to avoid alloy.
Wherein, annealing can be in the condition of 900-1000 DEG C (such as 900 DEG C, 920 DEG C, 950 DEG C, 980 DEG C or 1000 DEG C)
Lower heat preservation 1.5-2.5h (1.5h, 1.8h, 2h, 2.2h or 2.5h etc.).It is air-cooled with furnace after annealing.
Further, further include milling step after heat treatment, the alloy after heat treatment can be crushed and alloy powder is made.
It holds, the application can adjust alloy according to actual needs by multi-element alloyed and element substitution method
Thermodynamic property to realize the lifting of alloy hydrogen absorption and desorption plateau pressure, and obtains the performance of needs.On the other hand, pass through by
AB5Type hydrogen storage alloy In-situ reaction in melting enters AB or AB2In type alloy, Ti-La intermediate compound is formed.In the mistake for inhaling hydrogen
The surface La is initially formed stable hydride LaH at room temperature in journey1.8.Rare earth La is easier to be activated and activation process can produce
Raw bigger volume expansion causes a large amount of fresh TiFe phase surfaces thus to produce so as to cause there is micro-flaw in alloy
It is raw.After Ni element enters lattice phase, facilitate H2Molecule is decomposed to form H atom in alloy surface and enters among lattice.It is above-mentioned because
Element is conducive to generate positive influence to the activity function of alloy.The schematic diagram of multiphase structure absorption hydrogen process is as shown in Figure 1.
In addition, the application also proposed a kind of application of above-mentioned static hydrogen compressed complex phase hydrogen bearing alloy, such as can be by it
Be used to prepare static hydrogen compressor, be conducive to overcome purchased existing for mechanical hydrogen compressor at present maintenance cost is high, the service life is short,
The disadvantages such as volume is big, power consumption is high, water consume is more and energy efficiency is low.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Respectively according to Ti0.5Zr0.5Fe0.2Cr0.6Mn0.2Alloy sheet (i.e. x=0), Ti0.5Zr0.5Fe0.2Cr0.6Mn0.2La0.1
Ni0.1Mn0.05Alloy sheet (i.e. x=0.1) and Ti0.5Zr0.5Fe0.2Cr0.6Mn0.2La0.5Ni0.5Mn0.25Alloy sheet (i.e. x=0.5)
Component requirements, the corresponding elemental metals of the element wherein contained are mixed, then under 1400 DEG C of smelting temperature melt
Refining, keeps the temperature 5min after alloy melts completely.Then the aluminium alloy of melting is got rid of with the water-cooled copper roller that revolving speed is 1200rpm rotation
At alloy sheet.And then be put into vacuum heat treatment furnace, 2h is kept the temperature under 950 DEG C and high-purity argon gas protection, it is air-cooled with furnace after annealing.
Alloy sheet after heat treatment is crushed to and crossed 50 meshes, alloy is put into hydrogen storage property analyzer and carries out activation survey
Examination.
When activation, it is filled with 8MPa hydrogen at 50 DEG C, and records the slippage of Hydrogen Vapor Pressure at any time, to obtain material
Starting inhale the hydrogen time, sucking/placing hydrogen amount etc., the results are shown in Table 1:
1 measurement result of table
| Alloy | Hydrogen time (s) is inhaled in starting | 100s inhales hydrogen (wt%) | 200s inhales hydrogen (wt%) | 300s inhales hydrogen (wt%) |
| X=0 | It does not find to inhale hydrogen phenomenon | 0 | 0 | 0 |
| X=0.1 | 80 | 0.6 | 1.42 | 1.65 |
| X=0.5 | 30 | 1.25 | 1.65 | 1.78 |
As it can be seen from table 1 material is in experiment condition not using (namely the case where x=0) before the complex phase technology of the application
Under occur inhale hydrogen phenomenon, illustrate not activating under the experiment condition.Using the x=0.1 of the complex phase technology of the application
It with x=0.5 alloy, is had occurred in 80s and 30s inhale hydrogen phenomenon respectively, while hydrogen storage content can respectively reach in 300s
Thus 1.65wt% and 1.78wt% illustrates that complex phase hydrogen bearing alloy provided herein is reducing activation temperature and improving conjunction
It is really effective that gold inhales hydrogen dynamic performance aspect.
Embodiment 2
The component requirements for pressing complex phase hydrogen bearing alloy, prepare TiFe respectively0.8Mn0.2Alloy and La0.8Ce0.2Ni5Alloy.Preparation
It is that 5min is kept the temperature after alloy melts completely in 1400 DEG C of smelting temperature melting of lower first time using electric arc melting mode.
The TiFe0.8Mn that will then have been prepared in 1:0.005 and 1:0.05 (molar ratio) ratio respectively0.2Alloy and
La0.8Ce0.2Ni5Alloy mixing carries out second of electric arc melting with condition identical with first time electric arc melting, then to obtaining
Alloy product first it is cooling and overturn for the first time, then successively third time electric arc melting, second is cooling and second overturns,
(condition of third time electric arc melting and the 4th electric arc melting is equal for 4th electric arc melting, third time cooling and third time overturning
It is identical as the condition of second of electric arc melting).And then resulting alloy object is put into vacuum heat treatment furnace, it is in 950 DEG C and high
2h is kept the temperature under straight argon gas shielded, it is air-cooled with furnace after annealing.
Alloy sheet after heat treatment is crushed to and crossed 50 meshes, alloy is put into hydrogen storage property analyzer and carries out activation survey
Examination.
When activation, it is filled with 3MPa hydrogen at 30 DEG C, and records the slippage of Hydrogen Vapor Pressure at any time, to obtain material
Starting inhale the hydrogen time, sucking/placing hydrogen amount etc., the results are shown in Table 2:
2 measurement result of table
| Alloy | Hydrogen time (s) is inhaled in starting | 100s inhales hydrogen (wt%) | 200s inhales hydrogen (wt%) | 300s inhales hydrogen (wt%) |
| TiFe0.8Mn0.2 | 100 | 0 | 0.1 | 0.35 |
| 1:0.005 | 60 | 0.52 | 1.45 | 1.55 |
| 1:0.05 | 30 | 0.82 | 1.60 | 1.65 |
From table 2 it can be seen that not using the TiFe of the application complex phase technology0.8Mn0.2Although alloy can be relatively mild
Activation is realized under experiment condition, but the starting suction hydrogen time is about 100s, and after 300s, the hydrogen-sucking amount amplification of material is not
Obviously.But in the alloy of 1:0.005 ratio, the alloy starting suction hydrogen time shorten to about 60s, compared to not using multiphase structure
TiFe0.8Mn0.2Absorption hydrogen dynamics greatly improves, and hydrogen-sucking amount is up to 1.55wt% when 300s.1:0.05 the alloy of ratio rises
Beginning to inhale the hydrogen time is only 30s, and when 200s is basically completed suction hydrogen step.Illustrate that multiphase structure technology provided herein is certain
The kinetic activation energy for facilitating reduction AB type Ti-Fe base hydrogen storage alloy, improves the suction hydrogen dynamic performance of alloy.
Embodiment 3
The present embodiment the difference from embodiment 1 is that: by the corresponding elemental metals of element contained in alloy to be prepared into
Row mixing, the then melting under 1200 DEG C of smelting temperature keep the temperature 3min after alloy melts completely.Then by the alloy of melting
Liquid gets rid of into alloy sheet with the water-cooled copper roller that revolving speed is 800rpm rotation.And then be put into vacuum heat treatment furnace, it is in 900 DEG C and high-purity
2.5h is kept the temperature under argon gas protection, it is air-cooled with furnace after annealing.Alloy sheet after heat treatment is crushed and crosses 40 meshes.
Embodiment 4
The present embodiment the difference from embodiment 1 is that: by the corresponding elemental metals of element contained in alloy to be prepared into
Row mixing, the then melting under 1600 DEG C of smelting temperature keep the temperature 2min after alloy melts completely.Then by the alloy of melting
Liquid gets rid of into alloy sheet with the water-cooled copper roller that revolving speed is 1500rpm rotation.And then be put into vacuum heat treatment furnace, it is in 1000 DEG C and high
1.5h is kept the temperature under straight argon gas shielded, it is air-cooled with furnace after annealing.Alloy sheet after heat treatment is crushed and crosses 80 meshes.
Embodiment 5
The present embodiment the difference from example 2 is that: press the component requirements of complex phase hydrogen bearing alloy, prepare respectively
TiFe0.8Mn0.2Alloy and La0.8Ce0.2Ni5Alloy.Preparation is using electric arc melting mode, the under 1200 DEG C of smelting temperature
Melting once keeps the temperature 3min after alloy melts completely.
The TiFe0.8Mn that will then have been prepared in 1:0.005 and 1:0.05 (molar ratio) ratio respectively0.2Alloy and
La0.8Ce0.2Ni5Alloy mixing carries out second of electric arc melting with condition identical with first time electric arc melting, then to obtaining
Alloy product first it is cooling and overturn for the first time, then successively third time electric arc melting, second is cooling and second overturns,
(condition of third time electric arc melting and the 4th electric arc melting is equal for 4th electric arc melting, third time cooling and third time overturning
It is identical as the condition of second of electric arc melting).And then resulting alloy object is put into vacuum heat treatment furnace, it is in 900 DEG C and high
2.5h is kept the temperature under straight argon gas shielded, it is air-cooled with furnace after annealing.
Alloy sheet after heat treatment is crushed to and crossed 40 meshes, alloy is put into hydrogen storage property analyzer and carries out activation survey
Examination.
Embodiment 6
The present embodiment the difference from example 2 is that: press the component requirements of complex phase hydrogen bearing alloy, prepare respectively
TiFe0.8Mn0.2Alloy and La0.8Ce0.2Ni5Alloy.Preparation is using electric arc melting mode, the under 1600 DEG C of smelting temperature
Melting once keeps the temperature 2min after alloy melts completely.
The TiFe0.8Mn that will then have been prepared in 1:0.005 and 1:0.05 (molar ratio) ratio respectively0.2Alloy and
La0.8Ce0.2Ni5Alloy mixing carries out second of electric arc melting with condition identical with first time electric arc melting, then to obtaining
Alloy product first it is cooling and overturn for the first time, then successively third time electric arc melting, second is cooling and second overturns
(condition of third time electric arc melting is identical as the condition of second of electric arc melting).And then resulting alloy object is put into Vacuum Heat
In treatment furnace, 1.5h is kept the temperature under 1000 DEG C and high-purity argon gas protection, it is air-cooled with furnace after annealing.
Alloy sheet after heat treatment is crushed to and crossed 80 meshes, alloy is put into hydrogen storage property analyzer and carries out activation survey
Examination.
Test example 1
With TFM+0.02AB5(wherein TFM refers to TiFeMn class alloy, with TiFe in this test example for alloy0.8Mn0.2
For alloy), measure the alloy before activation, activation after and 4 suction hydrogen release loop conditions, XRD spectrum it is as shown in Figure 2.
Map respectively represents XRD spectrum, the XRD spectrum after activation and the 4 suction hydrogen release circulations before alloy activation from the bottom to top in Fig. 2
XRD spectrum afterwards.By the figure it can be seen that the main phase of alloy is still TiFe phase, had also appeared in addition to this suspected of among La-Ti
The characteristic peak of phase, the object phase peak relative to most strong diffraction maximum relative intensity through activation processing after reduce the phenomenon that,
Later alloy is activated to keep substantially not at the object phase peak after 4 times are inhaled hydrogen release relative to the relative intensity of most strong diffraction maximum
Become.It is believed that the generation of La-Ti intermediate product, facilitates the promotion of alloy activation performance.
Test example 2
With TFM+yAB5For (y=0.005,0.01,0.015,0.02) alloy (wherein TFM refers to TiFeMn class alloy,
Equally with TiFe in this test example0.8Mn0.2For alloy), alloy in above-mentioned 4 is observed with scanning electron microscope, scanning electricity
Mirror figure difference is as seen in figures 3-6.By Fig. 3-6 it can be seen that when y is more than or equal to 0.01, occur in SEM image more obvious
Brilliant white form and aspect.As y=0.02, it can be seen that apparent larger brilliant white reunion phase.It is logical to go out in TFM+0.02AB5 alloy
Existing brilliant white form and aspect and matrix mutually take different points to carry out EDS analysis test, find brilliant white region essential element ingredient
For La, and there are a certain amount of Ni, while there is also Ni elements in matrix phase.La reunites in alloy surface to be bonded with Ti
La-Ti intermediate compound.Subsequent La in conjunction with H, forms La-H hydride in alloy surface, and H diffusion transfer enters in La-Ti
Between region, finally diffuse among TiFe alloy lattice, lead to the formation of TiFe hydride.Since La is forming hydride mistake
Cheng Zhong has bigger volume expansion, so leading to the generation of micro-crack in alloying pellet, has more so as to cause TiFe alloy
More fresh surfaces generates, and further promotes the activity function of alloy.
In conclusion static state hydrogen compressed provided by the present application complex phase hydrogen bearing alloy have more mild activation temperature and
Pressure, while the hydrogen storage property of alloy is good.Preparation method is simple and easy, is conducive to that the complex phase hydrogen storage haveing excellent performance is made
Alloy.It is used for preparing static hydrogen compressor, is conducive to overcome and purchases maintenance cost existing for mechanical hydrogen compressor at present
The high, disadvantages such as the service life is short, volume is big, power consumption is high, water consume is more and energy efficiency is low.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of static state hydrogen compressed complex phase hydrogen bearing alloy, which is characterized in that the complex phase hydrogen bearing alloy prepare through master alloy and
, the master alloy includes first kind alloy or the second class alloy, and the first kind alloy is AB2Type alloy and AB5Type alloy
Composite alloy, the chemical general formula of the first kind alloy are Ti0.5Zr0.5(Fe0.1Cr0.3Mn0.1)2+xLa(Ni0.2Mn0.1)5(x=
0.1-0.5)；The second class alloy is AB type alloy and AB5The chemistry of the composite alloy of type alloy, the second class alloy is logical
Formula is TiFe0.8Mn0.2+yLa0.8Ce0.2Ni5(y=0.005-0.05).
2. static state hydrogen compressed complex phase hydrogen bearing alloy according to claim 1, which is characterized in that in the first kind alloy
Including LaNi5It include LaNi in type phase and Laves phase and/or the second class alloy5Type phase and TiFe phase.
3. the preparation method of static state hydrogen compressed complex phase hydrogen bearing alloy as described in claim 1, which is characterized in that including following
Step: preparing master alloy, then melting, heat treatment.
4. preparation method according to claim 3, which is characterized in that prepare master alloy and fusion process includes: by complex phase
The component requirements of hydrogen bearing alloy, first time electric arc melting to prepare the first kind alloy and the second class alloy respectively, so
After mix the first kind alloy and the second class alloy, second of electric arc melting.
5. the preparation method according to claim 4, which is characterized in that first time electric arc melting and second electric arc melting
Condition is identical, and the temperature during melting is 1200-1600 DEG C；
Preferably, each alloy keeps the temperature 2-5min after melting completely；
Preferably, the melting of the first kind alloy and the second class alloy is carried out under the conditions of inert gas shielding,
The inert gas includes argon gas or helium.
6. the preparation method according to claim 4, which is characterized in that also successively include third time after second of electric arc melting
Electric arc melting and the 4th electric arc melting, third time electric arc melting, the condition of the 4th electric arc melting are molten with second of electric arc
The condition of refining is identical；
Preferably, between second of electric arc melting and third time electric arc melting further include conjunction to obtaining after second of electric arc melting
Golden product is carried out cooling for the first time and is overturn for the first time, further includes to the between third time electric arc melting and the 4th electric arc melting
The alloy product obtained after electric arc melting three times carries out second of cooling and second of overturning, further includes after the 4th electric arc melting
Third time cooling is carried out to the alloy product obtained after the 4th electric arc melting and third time is overturn.
7. preparation method according to claim 3, which is characterized in that prepare master alloy and fusion process includes: by complex phase
The component requirements of hydrogen bearing alloy mix the corresponding elemental metals of element contained in the complex phase hydrogen bearing alloy, then
Unified melting, is then made complex phase hydrogen bearing alloy for the aluminium alloy of melting；
Temperature during melting is 1200-1600 DEG C；
Preferably, alloy keeps the temperature 2-5min after melting completely.
8. preparation method according to claim 7, which is characterized in that it is 800- that the aluminium alloy of melting, which is passed through with revolving speed,
The complex phase hydrogen bearing alloy is made in the water-cooled copper roller of 1500rpm rotation；
Preferably, the complex phase hydrogen bearing alloy with a thickness of 0.4-0.6mm.
9. preparation method according to claim 3, which is characterized in that heat treatment includes: under conditions of 900-1000 DEG C
Keep the temperature 1.5-2.5h.
10. the application of static state hydrogen compressed complex phase hydrogen bearing alloy as claimed in claim 1 or 2, which is characterized in that the static state
Hydrogen compressed is used to prepare static hydrogen compressor with complex phase hydrogen bearing alloy.
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