CN107574363A - A kind of ferromagnetic Fe Dy hydrogen storage materials and preparation method thereof - Google Patents
A kind of ferromagnetic Fe Dy hydrogen storage materials and preparation method thereof Download PDFInfo
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- CN107574363A CN107574363A CN201710776881.XA CN201710776881A CN107574363A CN 107574363 A CN107574363 A CN 107574363A CN 201710776881 A CN201710776881 A CN 201710776881A CN 107574363 A CN107574363 A CN 107574363A
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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 materials, there is Th2Ni17The ferrimagnet of the crystal structure of the side of type six, saturation magnetization are 62 ~ 100Am2/ kg, Curie temperature are 90 ~ 100 DEG C, and hydrogen storage property is 0.1 ~ 0.2wt.%.Its preparation method comprises the steps of：1）Fe and Dy meltings, which are weighed, by chemical formula is prepared into Fe17Dy2Alloy；2）Fe Dy hydrogen storage materials are made in the alloy heat treatment of preparation.During application as hydrogen storage material, there is magnetic phase in version characteristic, hydrogen storage content when higher than Curie temperature is 0.11 ~ 0.14 wt.%, and the hydrogen storage content in Curie temperature brings up to 0.18 ~ 0.2 wt.% on the contrary.The hydrogen storage material Curie temperature of the present invention is low and operating temperature is near Curie temperature.
Description
Technical field
The invention belongs to field of new materials, is related to energy new material, and in particular to a kind of ferromagnetic Fe-Dy hydrogen storage materials
And preparation method thereof.
Background technology
The two R-T compound combined to form of rare earth element (R) and magnesium-yttrium-transition metal (T) includes T2R、T3R、T17R2、T23R6
Compound Deng, the type is hot because 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 side performance
Study less.Nowadays with the development of society and the progress of technology, requirement to material simultaneously is not merely confined on one side,
Comprehensive maximization for playing the performance of material each side and taking into account utilization rate must just probe into its all many performance simultaneously.
As widely used energy and material on our times, hydrogen storage material plays its important work in every field
With.Hydrogen storage material mainly includes magnesium-based, carbon-based, ammonia boryl, nano hydrogen-storage material and the major class of rare earth hydrogen storage material five at present.
Magnesium-base hydrogen storage material has aboundresources, cheap, light weight and it is pollution-free the features such as, the material is except with good storage
There is certain capability of electromagnetic shielding 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 in addition to hydrogen storage property it is certain
Thermal shock resistance；But active carbon adsorption hydrogen storage is the characterization of adsorption just presented at low temperature, at ambient temperature
As a result it is unsatisfactory., because the material specific surface energy is high, substantial amounts of table be present in addition to hydrogen storage property in nano material
Planar defect, the unsaturated dangling bond of height, higher chemical reactivity and the small-size effect of itself, skin effect, quantum
Dimensional effect etc., so that it also has the characteristics such as excellent light, electricity, heat concurrently simultaneously.Thus, this few major class hydrogen storage material is not only all
With good hydrogen storage property, while also show other unique functional characteristics.So far, hydrogen storage property and other performance
The research being combined is not paid close attention to, more without the interdependence for finding hydrogen storage property and other performance.
Prior art finds T23R6Magnetic property also becomes there occurs corresponding after type compound has hydrogen storage property and hydrogen storage
Change, but be not found influence of the Curie temperature to hydrogen storage property.Meanwhile T23R6The higher skill of Curie temperature be present in type compound
Art problem.Although the problem can reduce its Curie temperature, produce therewith new by adding the third element, such as Mn
Technical problem be exactly that Mn exists volatile in fusion process, cause composition to be difficult to control, single-phase compounds are more difficult to be made.
T17R2Type compound has relatively low Curie temperature in itself, therefore need not adulterate other elements and reduce its Curie's temperature
Degree.And the usage amount of rare earth is compared with T23R6Type compound reduces half, so as 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, the relevance for probing into hydrogen storage property and magnetic property is had very important significance.
The content of the invention
It is an object of the invention 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 has a ferromagnetism below at 95 DEG C (± 5 DEG C), and
Near Curie temperature occurs that the hydrogen storage content of hydrogen storage material can be significantly improved during magnetic phase in version, and this can substantially reduce hydrogen storage
The operating temperature convergence and room temperature of material.
The purpose of the present invention is together with the magnetic property of material is effectively combined with hydrogen storage property, for hydrogen storage material from now on
Development and application open a new passage.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 technology is simple and diversified so that the hydrogen storage material has
There are wider application field and huge application value.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is as follows：
A kind of ferromagnetic Fe-Dy hydrogen storage materials, it is raw material by Fe and rare earth β-diketone complex, chemical formula is made through electric arc melting and heat treatment
For Fe17Dy2Fe-Dy hydrogen storage materials, there is Th2Ni17The crystal structure of the side of type six, is ferrimagnet, and saturated magnetization is strong
Spend for 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 materials comprises the steps of：
Step 1）According to chemical formula Fe17Dy2, Fe and rare earth β-diketone complex are weighed, is prepared into Fe by the sample prepared is smelting17Dy2Alloy,
Described method of smelting is arc melting method, discharge plasma sintering method (SPS), mechanical alloying method or solid phase reaction sintering
Any one in method；
Step 2）By step 1）The Fe of preparation17Dy2Alloy is put into quartz ampoule after progress vacuum sealing, in 600 ~ 1000 DEG C of conditions
Under, it is heat-treated 20 ~ 150 hours, is then placed in mixture of ice and water rapid cooling and Fe-Dy hydrogen storage materials are made.
During application of the Fe-Dy hydrogen storage materials as hydrogen storage material, there is magnetic phase in version 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 brings up to 0.18 ~ 0.2 on the contrary
wt.%。
In order to study the magnetic property of Fe-Dy hydrogen storage materials, to Fe17Dy2Alloy tests hysteresis curve, the intensity of magnetization respectively
Variation with temperature curve.As a result ferromagnetic Fe is shown17Dy2Alloy has 60 ~ 100 Am2/ kg the intensity of magnetization, 95 DEG C
The Curie temperature of (± 5 DEG C).
In order to study its structure, above-mentioned Fe-Dy hydrogen storage materials XRD tests, Rietveld structure refinements have been subjected to respectively
And scanning electron microscope test, the results showed that Fe-Dy hydrogen storage materials have Th2Ni17The side's single-phase crystal-structure of type six, and test
Data can be fitted well with calculated value.In addition, the sample topography figure of scanning electron microscope test displays that the conjunction
Gold is single-phase, and this is consistent with XRD results.
In order to study the relevance of the magnetic property of Fe-Dy materials and 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 the temperature of magnetic phase in version occurs is 0.15 ~ 0.18 wt.%.It is right
Than finding, hydrogen storage content in 100 DEG C of near Curie temperature on the contrary than 300 DEG C when hydrogen storage content also increase by 28% ~ 30%, illustrate this
The transformation of magnetism of material is favorably improved hydrogen storage property.
The present invention has advantages below relative to prior art：
1st, Fe-Dy hydrogen storage materials can remarkably promote the raising of hydrogen storage content in the magnetic phase in version that its near Curie temperature occurs, and this is big
The operating temperature of amplitude reduction hydrogen storage material is near 100 DEG C；
2nd, ferromagnetic Fe17Dy2Hydrogen storage material is 0.12 ~ 0.14 wt.% in 300 DEG C of hydrogen storage content, the hydrogen storage content at 100 DEG C
For 0.15 ~ 0.18 wt.%, in the case of dropping 200 DEG C at the working temperature, anti-increasing 28% ~ 30% does not drop in hydrogen storage content；
3rd, together with hydrogen storage property is effectively combined by the Fe-Dy hydrogen storage materials with magnetic property, and it is favourable to obtain magnetic property
In the beneficial outcomes for improving hydrogen storage property；
4th, any one sides such as electric arc melting, discharge plasma sintering (SPS), mechanical alloying or solid phase reaction sintering are passed through
Method obtains the compound, and preparation method is simple, flexible, uniform ingredients, possesses more preferable practical application foreground；
5th, the Fe-Dy hydrogen storage materials contain two kinds of elements, and sample is simple, and are free of readily volatilized material, simple easily to prepare；
6 and LaNi5、T23R6Type rare earth hydrogen storage material is compared, and the content of alloy middle rare earth greatly reduces, therefore cost of material is big
Amplitude reduction.
Therefore, the present invention has broad application prospects in hydrogen storage material field.
Brief description of the drawings
Fig. 1 is Fe17Dy2The single-phase XRD spectrum of alloy；
Fig. 2 is Fe17Dy2Single-phase XRD structure refinements figure；
Fig. 3 is Fe17Dy2Alloy amplifies 2000 times of shape appearance figure under a scanning electron microscope；
Fig. 4 is Fe17Dy2Hysteresis curve 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 alloy actual measurement and the hydrogen storage content of conventional hydrogen storage material vary with temperature the comparison diagram of trend.
Embodiment
The present invention is described in further detail, but be not pair by embodiment with reference to Figure of description to present invention
The restriction of the present invention.
Embodiment
A kind of preparation method of ferromagnetic Fe-Dy hydrogen storage materials comprises the steps of：
Step 1）According to chemical formula Fe17Dy2, it is 1.4899g, Dy 0.51g to weigh Fe, is incited somebody to action using the method for vacuum arc melting
The sample preparation prepared is into Fe17Dy2Alloy；
Step 2）By step 1）The Fe of preparation17Dy2Alloy vacuum sealing is put into 800 DEG C of annealing furnace at heat in quartz ampoule
Reason 100 hours, is put into mixture of ice and water after heat treatment and cools down rapidly, and Fe-Dy hydrogen storage materials are made.
Above-mentioned Fe-Dy hydrogen storage materials are subjected to XRD tests, specific method is：The oxide skin on surface is removed, fine powder is worn into and enters
Row test, test result is as shown in figure 1, Fe-Dy hydrogen storage materials have Th2Ni17The single-phase crystal-structure of type cube.
Further to study its structure, Rietveld structure refinements are 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 it is single-phase well, such as
Shown in Fig. 3, this is consistent with Fig. 1 XRD results.
In order to study the magnetic property of Fe-Dy hydrogen storage materials, the following aspects is included：
1）Choose 5-15mg samples, carry out magnetism testing, test result as shown in figure 4, application maximum external magnetic field be 2T,
The magnetic moment of Fe-Dy hydrogen storage materials basically reaches saturation under 0.4T external magnetic fields, and has higher saturation magnetization（M s）~
62Am2/ kg, inhaling the saturation magnetization after hydrogen increases to ~ 95 Am2/kg；
2）Again 5-15mg or so sample is chosen, carries out the test that the intensity of magnetization varies with temperature, test result such as Fig. 5 institutes
Show, the Curie temperature of Fe-Dy hydrogen storage materials is about 95 DEG C (± 5 DEG C), more obvious ferromagnetism be present near Curie temperature
To paramagnetic sex reversal.
In order to study the relevance of the hydrogen storage property of Fe-Dy hydrogen storage materials and magnetic property, PCT surveys are carried out at different temperatures
Examination, test result are as shown in Figure 6, the results showed that the Fe-Dy hydrogen storage materials are 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 during 100 DEG C of the near Curie temperature of change significantly improves, and now hydrogen storage content is 0.18 wt.%, and anti-increasing does not drop in hydrogen storage content.
The raising of hydrogen storage content can be obviously promoted by illustrating the magnetic phase in version of material.
Fig. 7 is that the hydrogen storage content of Fe-Dy hydrogen storage materials actual measurement varies with temperature the contrast of trend with conventional material hydrogen storage content
Figure.It is apparent that the hydrogen storage content of conventional hydrogen storage material is typically to decline with the decline of operating temperature from figure, and
Ferromagnetic Fe-Dy hydrogen storage materials are significantly improved in the hydrogen storage content of near Curie temperature, illustrate the magnetic that ferrimagnet occurs
Phase in version 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 foregoing is only a specific embodiment of the invention, and the effect of embodiment indicates that the substance of the present invention
Content, but protection scope of the present invention is not limited with this.It will be understood by those within the art that disclosed in the present invention
New material system in, technical scheme can be modified or to composition carry out equivalent substitution, should all cover
Within protection scope of the present invention, without departing from the essence and protection domain of technical solution of the present invention.
Claims (7)
- A kind of 1. ferromagnetic Fe-Dy hydrogen storage materials, it is characterised in that：It is raw material by Fe and rare earth β-diketone complex, through electric arc melting and heat It is Fe that processing, which is prepared into chemical formula,17Dy2Fe-Dy hydrogen storage materials.
- 2. Fe-Dy hydrogen storage materials according to claim 1, it is characterised in that：The Fe-Dy hydrogen storage materials have Th2Ni17 The crystal structure of the side of type six.
- 3. ferromagnetism according to claim 1, it is characterised in that：The Fe-Dy hydrogen storage materials are ferrimagnets, and full It is 62 ~ 100Am with the intensity of magnetization2/ kg, Curie temperature is 90 ~ 100 DEG C, and hydrogen storage property is 0.1 ~ 0.2wt.%.
- 4. the preparation method of Fe-Dy hydrogen storage materials according to claim 1, it is characterised in that comprise the steps of：Step 1）According to chemical formula Fe17Dy2, Fe and rare earth β-diketone complex are weighed, is prepared into Fe by the sample prepared is smelting17Dy2Alloy；Step 2）By step 1）The Fe of preparation17Dy2Alloy is heat-treated obtained Fe-Dy hydrogen storage materials under certain condition.
- 5. preparation method according to claim 4, it is characterised in that：Step 1）Described method of smelting is electric arc melting Any one in method, discharge plasma sintering method (SPS), mechanical alloying method or solid phase reaction sintering process.
- 6. preparation method according to claim 4, it is characterised in that：Step 2）The heat treatment condition is by Fe17Dy2Close Gold is put into quartz ampoule after progress vacuum sealing, under the conditions of 600 ~ 1000 DEG C, is heat-treated 20 ~ 150 hours, is then placed in frozen water Cooled down rapidly in mixture.
- 7. application of the Fe-Dy hydrogen storage materials according to claim 1 as hydrogen storage material, it is characterised in that：Fe-Dy hydrogen storages Material has magnetic phase in version characteristic, and hydrogen storage content when higher than 120 ~ 300 DEG C of Curie temperature is 0.11 ~ 0.14 wt.%, is being occupied In temperature when hydrogen storage content bring up to 0.18 ~ 0.2 wt.% on the contrary.
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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 |
|---|
| Y.B.GUO ET AL: ""Effect of Mn Doping on the Structural，Magnetic，and Magnetocaloric Effect of Fe17Dy2 Compounds"", 《J SUPERCOND NOV MAGN》 * |
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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 |