CN107574363B - A kind of ferromagnetic Fe-Dy hydrogen storage material and preparation method thereof - Google Patents
A kind of ferromagnetic Fe-Dy hydrogen storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ferromagnetic Fe-Dy hydrogen storage materials, are raw material by Fe and rare earth β-diketone complex, and it is Fe that chemical formula, which is made, through electric arc melting and heat treatment17Dy2Fe-Dy hydrogen storage material, have Th2Ni17The ferrimagnet of the crystal structure of six side of type, saturation magnetization are 62 ~ 100Am2/ kg, Curie temperature are 90 ~ 100 DEG C, and hydrogen storage property is 0.1 ~ 0.2wt.%.Preparation method comprises the steps of: that 1) weighing Fe and Dy melting by chemical formula is prepared into Fe17Dy2Alloy；2) alloy of preparation is heat-treated and Fe-Dy hydrogen storage material is made.As hydrogen storage material in application, having magnetic phase transition characteristic, the hydrogen storage content when being higher than Curie temperature is 0.11 ~ 0.14 wt.%, and the hydrogen storage content in Curie temperature is increased to 0.18 ~ 0.2 wt.% instead.Hydrogen storage material Curie temperature of the invention is low and operating temperature is near Curie temperature.
Description
Technical field
The invention belongs to field of new materials, are related to energy new material, and in particular to a kind of ferromagnetic Fe-Dy hydrogen storage material
And preparation method thereof.
Background technique
It includes T that rare earth element (R), which is combined the R-T compound formed with magnesium-yttrium-transition metal (T) the two,2R、T3R、T17R2、T23R6
Compound Deng, the type is hot since the interaction of 3d-4f electronic shell shows excellent magnetostriction, magneto-resistor, magnetic
Can and obtained extensive research.However, the performance in terms of people only focus on its magnetics in the past, and for other aspects performance
It studies less.Nowadays with the development of society and advancement of technology, to the requirement of material and not merely it is confined on one side,
Its all various performance must just be probed into simultaneously by playing the performance of material various aspects comprehensively and taking into account the maximization of utilization rate.
As energy and material widely used on our times, hydrogen storage material plays its important work in every field
With.Hydrogen storage material mainly includes magnesium-based, five major class of carbon-based, ammonia boryl, nano hydrogen-storage material and rare earth hydrogen storage material at present.
Magnesium-base hydrogen storage material have it is resourceful, it is cheap, light weight and it is pollution-free the features such as, the material is in addition to good storage
There are also certain electromagnetic shielding performances outside hydrogen performance.Carbon-based material can be made repeatedly due to insensitive to a small amount of gaseous impurity
With, thus be a kind of extraordinary hydrogen storage material, in addition, the material be also found to have concurrently other than with hydrogen storage property it is certain
Thermal shock resistance；However active carbon adsorption hydrogen storage is the characterization of adsorption just presented at low temperature, at room temperature
As a result unsatisfactory.Nano material is other than with hydrogen storage property, and since the material specific surface energy is high, there are a large amount of tables
Planar defect, the unsaturated dangling bond of height, higher chemical reactivity and the small-size effect of itself, skin effect, quantum
Dimensional effect etc., to make it also while have the characteristics such as excellent light, electricity, heat concurrently.Thus, this few major class hydrogen storage material is not only all
With good hydrogen storage property, while also showing other unique functional characteristics.So far, hydrogen storage property and other performance
The research combined is not paid close attention to, more the interdependence without finding hydrogen storage property and other performance.
The prior art finds T23R6There is type compound magnetic property after hydrogen storage property and hydrogen storage corresponding change also has occurred
Change, but is not found influence of the Curie temperature to hydrogen storage property.Meanwhile T23R6There are the higher skills of Curie temperature for type compound
Art problem.Although the problem can reduce its Curie temperature, generate therewith new by adding the third element, such as Mn
The technical issues of be exactly Mn in fusion process there are volatile, cause composition not easy to control, single-phase compounds are more difficult to be made.
T17R2Type compound itself has lower Curie temperature, and there is no need to adulterate other elements to reduce its Curie's temperature
Degree.And the usage amount of rare earth is compared with T23R6Type compound reduces half, to considerably reduce cost.
The present invention will have ferromagnetic T17R2The operating temperature of type hydrogen storage material is reduced to Curie temperature, studies its Curie
Hydrogen storage property near temperature has very important significance to the relevance for probing into hydrogen storage property and magnetic property.
Summary of the invention
The object of the present invention is to provide a kind of ferromagnetic Fe-Dy hydrogen storage materials and preparation method thereof.
It has been investigated that the Fe in the present invention17Dy2Hydrogen storage material 95 DEG C (± 5 DEG C) below have ferromagnetism, and
The hydrogen storage content that hydrogen storage material can be significantly improved during magnetic phase transition occurs near Curie temperature, this can substantially reduce hydrogen storage
The operating temperature of material approaches and room temperature.
The purpose of the present invention is the magnetic property of material and hydrogen storage property to be effectively combined together, for hydrogen storage material from now on
Development and application open a new channel.Compared with traditional hydrogen storage material, material of the invention not only has good
Hydrogen storage property, and operating temperature is greatly lowered, close to room temperature, preparation process is simple and diversified, so that the hydrogen storage material has
There are wider application field and huge application value.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of ferromagnetic Fe-Dy hydrogen storage material is raw material by Fe and rare earth β-diketone complex, through electric arc melting and heat treatment obtainedization
Formula is Fe17Dy2Fe-Dy hydrogen storage material, have Th2Ni17The crystal structure of six side of type, is ferrimagnet, and is saturated magnetic
Change intensity is 62 ~ 100 Am2/ kg, Curie temperature is 90 ~ 100 DEG C and hydrogen storage property is 0.1 ~ 0.2 wt.%.
The preparation method of Fe-Dy hydrogen storage material comprises the steps of:
Step 1) is according to chemical formula Fe17Dy2, Fe and rare earth β-diketone complex are weighed, is prepared into Fe for the sample prepared is smelting17Dy2
Alloy, the method for smelting are that arc melting method, discharge plasma sintering method (SPS), mechanical alloying method or solid phase are anti-
Answer any one in sintering process；
The Fe that step 2 prepares step 1)17Dy2Alloy is put into quartz ampoule after progress vacuum sealing, at 600 ~ 1000 DEG C
Under the conditions of, it is heat-treated 20 ~ 150 hours, is then placed in mixture of ice and water cooling obtained Fe-Dy hydrogen storage material rapidly.
Fe-Dy hydrogen storage material is as hydrogen storage material in application, having magnetic phase transition characteristic, higher than Curie temperature
Hydrogen storage content at 120 ~ 300 DEG C is 0.11 ~ 0.14 wt.%, and the hydrogen storage content in Curie temperature is increased to 0.18 ~ 0.2 instead
wt.%。
In order to study the magnetic property of Fe-Dy hydrogen storage material, to Fe17Dy2Alloy tests hysteresis loop, the intensity of magnetization respectively
Variation with temperature curve.The result shows that ferromagnetic Fe17Dy2Alloy has 60 ~ 100 Am2The intensity of magnetization of/kg, 95 DEG C
The Curie temperature of (± 5 DEG C).
In order to study its structure, above-mentioned Fe-Dy hydrogen storage material XRD test, Rietveld structure refinement have been subjected to respectively
And scanning electron microscope test, the results showed that Fe-Dy hydrogen storage material has Th2Ni17Six side's single-phase crystal-structure of type, and test
Data can be fitted well with calculated value.In addition, the sample topography figure of scanning electron microscope test also shows the conjunction
Gold be it is single-phase, this is consistent with XRD result.
In order to study the magnetic property of Fe-Dy material and the relevance of hydrogen storage property, distinguished using PCT analysis by absorption of gases instrument
The alloy is tested in 300 DEG C, 120 DEG C, 100 DEG C, 80 DEG C of hydrogen storage property, the results showed that, the Fe17Dy2Alloy is at 300 DEG C
Hydrogen storage content is 0.12 ~ 0.14 wt.%, and the hydrogen storage content when 100 DEG C of temperature of magnetic phase transition occur is 0.15 ~ 0.18 wt.%.It is right
Than discovery, hydrogen storage content at 100 DEG C of near Curie temperature instead than 300 DEG C when hydrogen storage content also increase by 28% ~ 30%, illustrate this
The transformation of magnetism of material helps to improve hydrogen storage property.
The present invention compared with the existing technology, has the advantage that
1, Fe-Dy hydrogen storage material can remarkably promote the raising of hydrogen storage content in the magnetic phase transition that its near Curie temperature occurs,
The operating temperature of hydrogen storage material is greatly lowered near 100 DEG C in this；
2, ferromagnetic Fe17Dy2Hydrogen storage material is 0.12 ~ 0.14 wt.% in 300 DEG C of hydrogen storage content, the storage at 100 DEG C
Hydrogen amount is 0.15 ~ 0.18 wt.%, and in the case where dropping 200 DEG C at the working temperature, anti-increasing 28% ~ 30% does not drop in hydrogen storage content；
3, hydrogen storage property and magnetic property are effectively combined together by the Fe-Dy hydrogen storage material, and obtain magnetic property
Be conducive to improve the beneficial outcomes of hydrogen storage property；
4, pass through electric arc melting, discharge plasma sintering (SPS), mechanical alloying or solid phase reaction sintering etc. any one
Kind of method obtains the compound, preparation method is simple, flexibly, uniform ingredients, possess better practical application foreground；
5, Fe-Dy hydrogen storage material element containing there are two types of, sample is simple, and is free of readily volatilized material, simple easily to make
It is standby；
6 and LaNi5、T23R6Type rare earth hydrogen storage material is compared, and the content of rare earth greatly reduces in alloy, thus raw material at
Originally it is greatly lowered.
Therefore, the present invention has broad application prospects in hydrogen storage material field.
Detailed description of the invention
Fig. 1 is Fe17Dy2The single-phase XRD spectrum of alloy；
Fig. 2 is Fe17Dy2Single-phase XRD structure refinement figure；
Fig. 3 is Fe17Dy2Alloy amplifies 2000 times of shape appearance figure under a scanning electron microscope；
Fig. 4 is Fe17Dy2Hysteresis loop before and after absorption hydrogen；
Fig. 5 is Fe17Dy2The change curve of Curie temperature before and after absorption hydrogen；
Fig. 6 is Fe17Dy2The hydrogen-absorbing ability test curve of alloy at different temperatures；
Fig. 7 is Fe17Dy2The hydrogen storage content of the hydrogen storage content of alloy actual measurement and conventional hydrogen storage material varies with temperature the comparison of trend
Figure.
Specific embodiment
The present invention is described in further detail the content of present invention in conjunction with Figure of description, but be not pair by embodiment
Restriction of the invention.
Embodiment
A kind of preparation method of ferromagnetic Fe-Dy hydrogen storage material comprises the steps of:
Step 1) is according to chemical formula Fe17Dy2, weighing Fe is 1.4899g, Dy 0.51g, using the side of vacuum arc melting
Method is by the sample preparation prepared at Fe17Dy2Alloy；
The Fe that step 2 prepares step 1)17Dy2Alloy vacuum sealing is put into 800 DEG C of annealing furnace in quartz ampoule
Heat treatment 100 hours, is put into mixture of ice and water after heat treatment and cools down rapidly, and Fe-Dy hydrogen storage material is made.
By above-mentioned Fe-Dy hydrogen storage material carry out XRD test, method particularly includes: the oxide skin for removing surface, wear into fine powder into
Row test, test results are shown in figure 1, and Fe-Dy hydrogen storage material has Th2Ni17The single-phase crystal-structure of type cube.
Further to study its structure, Rietveld structure refinement is carried out to its XRD spectral line, as shown in Figure 2, the results showed that
Experimental data can be fitted well with calculated value, the shape appearance figure of sem test be also displayed as well it is single-phase, such as
Shown in Fig. 3, this is consistent with the XRD result of Fig. 1.
Include the following aspects to study the magnetic property of Fe-Dy hydrogen storage material:
1) 5-15mg sample is chosen, carries out magnetism testing, test results are shown in figure 4, and the maximum external magnetic field of application is
The magnetic moment of 2T, Fe-Dy hydrogen storage material basically reaches saturation, and saturation magnetization with higher under 0.4T external magnetic field
(M s) ~ 62Am2/ kg, the saturation magnetization after inhaling hydrogen increase to ~ 95 Am2/kg；
2) sample for choosing 5-15mg or so again carries out the test that the intensity of magnetization varies with temperature, test result such as Fig. 5
Shown, the Curie temperature of Fe-Dy hydrogen storage material is about 95 DEG C (± 5 DEG C), is existed near Curie temperature more apparent ferromagnetic
Property is to paramagnetic sex reversal.
In order to study the hydrogen storage property of Fe-Dy hydrogen storage material and the relevance of magnetic property, PCT survey is carried out at different temperatures
Examination, test results are shown in figure 6, the results showed that the Fe-Dy hydrogen storage material is 0.14 wt.% in 300 DEG C of hydrogen storage content, 120
DEG C hydrogen storage content is 0.11 wt.%, and hydrogen storage content when temperature drops to 80 DEG C is 0.09 wt.%.But turn in ferromagnetism to paramagnetism
Hydrogen storage content at 100 DEG C of the near Curie temperature of change significantly improves, and hydrogen storage content is 0.18 wt.% at this time, and anti-increasing does not drop in hydrogen storage content.
Illustrate that the magnetic phase transition of material can be obviously promoted the raising of hydrogen storage content.
Fig. 7 is that the hydrogen storage content of Fe-Dy hydrogen storage material actual measurement varies with temperature the comparison of trend with conventional material hydrogen storage content
Figure.It is apparent that the hydrogen storage content of conventional hydrogen storage material usually declines with the decline of operating temperature from figure, and
Ferromagnetic Fe-Dy hydrogen storage material is significantly improved in the hydrogen storage content of near Curie temperature, illustrates the magnetic that ferrimagnet occurs
Phase transition may advantageously facilitate the raising of hydrogen storage content, and the operating temperature of hydrogen storage material can be greatly lowered near 100 DEG C in this.
The above description is merely a specific embodiment, and the effect of embodiment indicates that substance of the invention
Content, but do not limited the scope of protection of the present invention with this.Those skilled in the art should understand that being disclosed in the present invention
New material system in, can modify to technical solution of the present invention or composition is equivalently replaced, should all cover
Within protection scope of the present invention, without departing from the essence of technical solution of the present invention and protection scope.
Claims (1)
1. a kind of application of ferromagnetic Fe-Dy hydrogen storage material as hydrogen storage material, it is characterised in that: Fe-Dy hydrogen storage material tool
There is magnetic phase transition characteristic, the hydrogen storage content when being higher than 120 ~ 300 DEG C of Curie temperature is 0.11 ~ 0.14 wt.%, in Curie temperature
When hydrogen storage content be increased to 0.18 ~ 0.2wt.% instead；The Fe-Dy hydrogen storage material is raw material by Fe and rare earth β-diketone complex, molten through electric arc
It is Fe that refining and heat treatment, which are prepared into chemical formula,17Dy2Fe-Dy hydrogen storage material；The Fe-Dy hydrogen storage material has Th2Ni17Type six
The crystal structure of side；The Fe-Dy hydrogen storage material is ferrimagnet, and saturation magnetization is 62 ~ 100Am2/ kg, Curie
Temperature is 90 ~ 100 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532102A (en) * | 2009-04-13 | 2009-09-16 | 河南科技大学 | Rare-earth series hydrogen storage alloy |
| CN102709535A (en) * | 2012-06-21 | 2012-10-03 | 广西大学 | Fe-based hydrogen storage alloy electrode material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532102A (en) * | 2009-04-13 | 2009-09-16 | 河南科技大学 | Rare-earth series hydrogen storage alloy |
| CN102709535A (en) * | 2012-06-21 | 2012-10-03 | 广西大学 | Fe-based hydrogen storage alloy electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Effect of Mn Doping on the Structural，Magnetic，and Magnetocaloric Effect of Fe17Dy2 Compounds";Y.B.Guo et al;《J Supercond Nov Magn》;20170629;第31卷;第265-268页 |
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Application publication date: 20180112 Assignee: GUANGXI WUZHOU MICRO-MAGNET TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF ELECTRONIC TECHNOLOGY Contract record no.: X2022450000243 Denomination of invention: A ferromagnetic Fe Dy hydrogen storage material and its preparation method Granted publication date: 20190823 License type: Common License Record date: 20221206 |