CN108689384B - Composite hydrogen storage material and preparation method and application thereof - Google Patents
Composite hydrogen storage material and preparation method and application thereof Download PDFInfo
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- CN108689384B CN108689384B CN201810960442.9A CN201810960442A CN108689384B CN 108689384 B CN108689384 B CN 108689384B CN 201810960442 A CN201810960442 A CN 201810960442A CN 108689384 B CN108689384 B CN 108689384B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 171
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 171
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000011232 storage material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910012375 magnesium hydride Inorganic materials 0.000 claims abstract description 42
- 238000000498 ball milling Methods 0.000 claims description 80
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000011056 performance test Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 20
- 238000003795 desorption Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WIIBPQPFQUYUGZ-UHFFFAOYSA-N [NiH2].[Mg] Chemical compound [NiH2].[Mg] WIIBPQPFQUYUGZ-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- -1 magnesium hydride iron Chemical compound 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention providesA composite hydrogen storage material comprises the following components in parts by weight: MgCNi310-40 parts by weight; MgH260-90 parts by weight. The composite hydrogen storage material has the advantages of low hydrogen release temperature, high hydrogen release rate and high hydrogen release amount. According to the records of the embodiments, the composite hydrogen storage material can reach 2.776 wt% hydrogen release amount in 20min at the hydrogen release temperature of 300 ℃, and according to TPD performance tests, the composite hydrogen storage material can begin to release hydrogen at 200 ℃, and is relatively pure MgH2The hydrogen evolution temperature was reduced by 160 ℃. The invention also provides a preparation method of the composite hydrogen storage material, and the preparation method is simple, the raw materials are easy to obtain, and the cost is low.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a composite hydrogen storage material and a preparation method and application thereof.
Background
With the continuous development of society, the demand of human beings on energy is more and more. At present, fossil energy such as coal, petroleum, natural gas and the like is still the main energy, but the fossil energy is non-renewable resource, has limited storage and low thermal efficiency, and meanwhile, the large amount of use of the fossil energy also causes serious environmental pollution problem. Therefore, the search for a new energy source to replace fossil energy is also a development trend of energy application. Hydrogen energy is used as a novel clean secondary energy source, has wide sources in the nature and draws attention of people, but the practical application of the hydrogen energy still has a plurality of problems at present, how to efficiently store hydrogen is one of key factors restricting the practical application of the hydrogen energy, and among a plurality of hydrogen storage materials, a magnesium-based hydrogen storage material is considered as one of ideal hydrogen storage materials due to the advantages of small density, large hydrogen storage content, rich storage capacity, low price and the like, but the pure magnesium hydride has larger generation enthalpy, poorer hydrogen absorption and desorption dynamic performance and higher hydrogen absorption and desorption temperature (generally above 300 ℃), thereby restricting the use of the magnesium-based hydrogen storage material.
How to improve the hydrogen storage performance of the magnesium-based hydrogen storage material has become a hot problem in the research field of magnesium-based hydrogen storage, and research shows that additive doping modification is to improve MgH2An effective method of hydrogen storage performance. The Chinese invention patent with the application number of 201410677464.6 discloses Pd-doped xMgH as a composite material2-TiH2Composite with pure MgH2Compared with the initial hydrogen discharge temperature, but no matter adding TiH alone2The hydrogen release amount of the added Pd is very small, and a good hydrogen release effect can be shown only when two additives are contained; and Pd is a noble metal, so that the application in a large range is difficult, and the practical value of the Mg-based composite hydrogen storage material is reduced. The Chinese patent with application number of 201310259727.7 discloses a magnesium hydride iron-containing sulfide composite hydrogen storage material and a preparation method thereof, wherein MgH is magnesium metal hydride MgH2The iron-containing sulfide consists of 10-30 wt% of iron-containing sulfide and pure MgH2Compared with the hydrogen absorption and desorption rate and the hydrogen absorption and desorption amount, the isothermal hydrogen desorption amount at 300 ℃ is only 1.2wt percent and cannot meet the practical application. Therefore, in the prior art, the magnesium-based hydrogen storage material is difficult to ensure that the hydrogen release temperature is reduced and the hydrogen release amount is high.
Disclosure of Invention
The invention aims to provide a composite hydrogen storage material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a composite hydrogen storage material which comprises the following components in parts by weight:
MgCNi310 to 40 parts by weight of
MgH260-90 parts by weight.
Preferably, the composite hydrogen storage material comprises the following components in parts by weight:
MgCNi320 to 30 parts by weight of
MgH270～80 parts by weight.
The invention also provides a preparation method of the composite hydrogen storage material, which comprises the following steps:
mixing MgCNi3And MgH2Mixing and ball milling to obtain the composite hydrogen storage material.
Preferably, the ball milling is carried out in an argon atmosphere, and the pressure of the argon is 0.05-0.15 MPa.
Preferably, the mass ratio of the ball materials of the ball milling is (25-40): 1, the rotating speed of the ball milling is 300-500 r/min.
Preferably, the ball milling time is 5-20 h.
Preferably, the ball milling is intermittent ball milling, and the intermittent ball milling is performed for 10-20 min each time, and the intermittent ball milling is performed for 10-20 min.
The invention also provides the application of the composite hydrogen storage material or the composite hydrogen storage material prepared by the preparation method in the field of hydrogen storage.
Preferably, the hydrogen release temperature of the composite hydrogen storage material is 200-330 ℃; the hydrogen absorption temperature of the composite hydrogen storage material is 100-200 ℃.
The invention provides a composite hydrogen storage material which comprises the following components in parts by weight: MgCNi310-40 parts by weight; MgH260-90 parts by weight. The composite hydrogen storage material is formed by MgCNi3During the composite activation process, MgH will be present2The magnesium nickel hydride with the induction function and the carbon substance with the lubrication function are generated in situ around the magnesium nickel hydride, thereby promoting MgH2Hydrogen absorption and desorption performance. So that the hydrogen-releasing device has the advantages of low hydrogen-releasing temperature, high hydrogen-releasing speed and high hydrogen-releasing quantity. According to the records of the embodiments, the composite hydrogen storage material can reach 2.776 wt% hydrogen release amount in 20min at the hydrogen release temperature of 300 ℃, and according to TPD performance tests, the composite hydrogen storage material can begin to release hydrogen at 200 ℃, and is relatively pure MgH2The hydrogen evolution temperature was reduced by 160 ℃.
The invention also provides a preparation method of the composite hydrogen storage material, and the preparation method is simple, the raw materials are easy to obtain, and the cost is low.
Drawings
FIG. 1 shows the composite hydrogen storage material and pure MgH prepared in example 12A comparative hydrogen desorption rate curve chart at 330 ℃ and 0.1 MPa;
FIG. 2 shows the composite hydrogen storage material and pure MgH prepared in example 22A graph of comparative hydrogen evolution rate at 320 ℃ and 0.1 MPa;
FIG. 3 shows the composite hydrogen storage material and pure MgH prepared in example 32A graph of comparative hydrogen evolution rate at 300 ℃ and 0.1 MPa;
FIG. 4 shows the composite hydrogen storage material and pure MgH prepared in example 42A graph of the comparative hydrogen absorption rate at 200 ℃ and 3 MPa;
FIG. 5 shows the composite hydrogen storage material and pure MgH prepared in example 52A graph of the comparative hydrogen absorption rate at 150 ℃ and 3 MPa;
FIG. 6 shows the composite hydrogen storage material and pure MgH prepared in example 62A graph of the comparative hydrogen absorption rate at 100 ℃ and 3 MPa;
FIG. 7 shows a composite hydrogen storage material and pure MgH prepared in example 72TPD of (a) versus a graph.
Detailed Description
The invention provides a composite hydrogen storage material which comprises the following components in parts by weight:
MgCNi310 to 40 parts by weight of
MgH260-90 parts by weight.
In the present invention, all the components of the raw materials are commercially available products well known to those skilled in the art, unless otherwise specified.
In the invention, the composite hydrogen storage material comprises 10-40 parts by weight of MgCNi3Preferably 20 to 30 parts by weight, and more preferably 22 to 28 parts by weight.
In the present invention, the MgCNi3During the composite activation process, MgH will be present2The magnesium nickel hydride with the induction function and the carbon substance with the lubrication function are generated in situ around the magnesium nickel hydride, thereby promoting MgH2Hydrogen absorption and desorption performance.
In the present invention, MgCNi is used3The composite hydrogen storage material comprises 60-90 parts by weight of MgH2Preferably 70 to 80 parts by weight, and more preferably 72 to 78 parts by weight.
In the present invention, the MgCNi3And MgH2The particle size of (b) is independently preferably < 100 mesh, more preferably < 80 mesh, most preferably < 60 mesh.
The invention also provides a preparation method of the composite hydrogen storage material, which comprises the following steps:
mixing the MgCNi3And MgH2Mixing and ball milling to obtain the composite hydrogen storage material.
In the present invention, the mixing is preferably performed under an argon atmosphere; the mixing process is not particularly limited in the present invention, and the mixing may be performed by a mixing process well known to those skilled in the art.
In the invention, the ball milling is preferably carried out in an argon atmosphere, and the pressure of the argon is preferably 0.05-0.15 MPa, more preferably 0.08-0.12 MPa, and most preferably 0.09-0.11 MPa. In the present invention, the argon gas is preferably high purity argon (purity ≥ 99.999%).
In the invention, the mass ratio of the ball materials of the ball mill is preferably (25-40): 1, more preferably (28 to 35): 1, most preferably (30-32): 1; the rotation speed of the ball milling is preferably 300-500 r/min, more preferably 350-450 r/min, and most preferably 380-420 r/min.
In the invention, the time for ball milling is preferably 5-20 h, more preferably 8-15 h, and most preferably 10-12 h.
In the invention, the ball milling is preferably intermittent ball milling, and the intermittent ball milling is preferably 10-20 min per ball milling and 10-20 min intermittent; more preferably, each ball milling is carried out for 12-18 min, and the intermission is 12-18 min; most preferably, the ball milling is carried out for 14-16 min each time, and the intermission time is 14-16 min.
In the present invention, the ball milling is preferably performed in a pulveresette 6 planetary ball mill; the ball-milled balls are preferably stainless steel balls.
In the invention, after the ball milling is finished, the mixed material is preferably cooled to room temperature in a ball milling tank, sampled and packaged.
The cooling process is not particularly limited, and the cooling process known to those skilled in the art may be employed to cool the mixture to room temperature.
In the present invention, the sampling and packaging process is preferably performed in a vacuum glove box; the packaging is preferably a vacuum sealed packaging.
The invention also provides the application of the composite hydrogen storage material or the composite hydrogen storage material prepared by the preparation method in the field of hydrogen storage.
In the invention, the hydrogen releasing temperature of the composite hydrogen storage material is preferably 200-330 ℃, and the hydrogen absorbing temperature of the composite hydrogen storage material is preferably 100-200 ℃.
The composite hydrogen storage material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 90 parts by weight of MgH2And 10 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 40:1, the rotating speed is 500r/min, high-purity argon gas of 0.1MPa is filled for ball milling, the ball milling time is 5h, each ball milling time is 15min, the interval is 10min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
Testing the hydrogen release performance: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for hydrogen release rate test. The test results are shown in FIG. 1, and it can be seen from the graph that the hydrogen evolution amount of the hydrogen storage composite material is pure MgH at a temperature of 330 ℃ for 10min23.55 times of the hydrogen release amount, and the hydrogen release amount can reach 5.199 wt.%. Therefore, the MgCNi provided by the invention3-MgH2The hydrogen release rate of the hydrogen storage composite material at 330 ℃ is obviously better than that of the hydrogen storage composite material without MgCNi3MgH of2。
Example 2
80 parts by weight of MgH2And 20 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 30:1, the rotating speed is 450r/min, high-purity argon gas of 0.1MPa is filled for ball milling, the ball milling time is 10h, each ball milling time is 10min, the interval time is 20min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
Testing the hydrogen release performance: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for hydrogen release rate test. The test results are shown in FIG. 2, which shows that the hydrogen release amount of the hydrogen storage composite material is pure MgH at 320 ℃ for 20min228.8 times of the total hydrogen content, and the hydrogen release amount can reach 4.814 wt.%. Therefore, the MgCNi provided by the invention3-MgH2The hydrogen release rate of the hydrogen storage composite material at 320 ℃ is obviously better than that of the hydrogen storage composite material without MgCNi3MgH of2。
Example 3
70 parts by weight of MgH2And 20 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 25:1, the rotating speed is 500r/min, high-purity argon gas of 0.1MPa is filled for ball milling, the ball milling time is 5h, each ball milling time is 15min, the interval is 20min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
Testing the hydrogen release performance: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for hydrogen release rate test. The test results are shown in fig. 3, which shows that at 300 ℃, the hydrogen release amount of the hydrogen storage composite material can reach 2.776 wt.% at 20min, and pure MgH2At which temperature substantially no hydrogen is released. Therefore, the MgCNi provided by the invention3-MgH2The hydrogen storage composite material effectively reduces MgH2The hydrogen discharge temperature of the catalyst improves MgH2The hydrogen desorption capacity of (1).
Example 4
80 parts by weight of MgH2And 20 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 30:1, the rotating speed is 450r/min, high-purity argon gas of 0.1MPa is filled for ball milling, the ball milling time is 10h, each ball milling time is 20min, the interval is 20min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
And (3) testing hydrogen absorption performance: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for hydrogen absorption rate test. The test results are shown in FIG. 4, which shows that the hydrogen absorption amount of the hydrogen storage composite material is pure MgH at a temperature of 200 ℃ for 20min22.5 times of the total amount of the hydrogen-absorbing agent, and the hydrogen absorption amount can reach 5.10 wt.%. Therefore, the MgCNi provided by the invention3-MgH2The hydrogen storage composite material can effectively absorb hydrogen at the temperature of 200 ℃, and MgH is obviously improved2Hydrogen absorption capacity of the catalyst.
Example 5
60 parts by weight of MgH2And 40 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 25:1, the rotating speed is 300r/min, ball milling is carried out by filling high-purity argon gas of 0.1MPa for 20h, each ball milling is carried out for 15min, the interval is 15min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
And (3) testing hydrogen absorption performance: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for hydrogen absorption rate test. The test results are shown in FIG. 5, which shows that at a temperature of 150 ℃ the hydrogen absorption amount of the hydrogen storage composite material is pure MgH at 25min23.3 times of the total amount of the catalyst, and the hydrogen absorption amount can reach 3.588 wt.%. Therefore, the MgCNi provided by the invention3-MgH2The hydrogen storage composite material can continuously absorb hydrogen at the temperature of 150 ℃, thereby obviously improving MgH2Hydrogen absorption capacity of the catalyst.
Example 6
70 parts by weight of MgH2And 30 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 30:1, the rotating speed is 450r/min, high-purity argon gas of 0.1MPa is filled for ball milling, the ball milling time is 10h, each ball milling time is 15min, the interval time is 15min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
And (3) testing hydrogen absorption performance: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for hydrogen absorption rate test. The test results are shown in FIG. 6, which shows that at 100 deg.C, the hydrogen absorption of the hydrogen storage composite material is 3.631 wt.% pure at 60min, and pure MgH2At which substantially no hydrogen is absorbed. Therefore, the MgCNi provided by the invention3-MgH2The hydrogen storage composite material can continuously absorb hydrogen at 100 ℃, compared with MgH2The hydrogen absorption capacity of the catalyst is improved qualitatively.
Example 7
Mixing 90 parts by weight of MgH2And 10 parts by weight of MgCNi3Mixing, transferring to a ball milling tank, ball milling by a Pulverisette 6 planetary ball mill, wherein the small balls are stainless steel balls, the mass ratio of the balls to the materials is 30:1, the rotating speed is 450r/min, high-purity argon gas of 0.1MPa is filled for ball milling, the ball milling time is 10h, each ball milling time is 15min, the interval time is 15min, cooling to the room temperature after the ball milling is finished, sampling, and carrying out vacuum sealing packaging.
And (3) TPD performance test: in a glove box filled with high-purity argon, 0.2g of the prepared hydrogen storage composite material is put into a sample tube of a P-C-T tester for TPD rate test. The test results are shown in FIG. 7, which shows that the composite hydrogen storage material can begin to release hydrogen at 200 deg.C, and the amount of hydrogen released is equal to that of pure MgH2Compared with the method, the initial hydrogen release temperature is reduced by 160 ℃ although the initial hydrogen release temperature is reduced.
From the above examples, it can be known that the composite hydrogen storage material of the present invention can reach 2.776 wt% hydrogen release amount in 20min at 300 ℃ hydrogen release temperature, and the TPD performance test shows that the composite hydrogen storage material can reach 2.776 wt% hydrogen release amountThe composite hydrogen storage material can begin to release hydrogen at 200 ℃, and is relatively pure MgH2The hydrogen release temperature is reduced by 160 ℃, and MgH is improved2The hydrogen desorption capacity of (1).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. A composite hydrogen storage material comprises the following components in parts by weight:
MgCNi320 to 30 parts by weight of
MgH270-80 parts by weight;
the preparation method of the composite hydrogen storage material comprises the following steps:
mixing MgCNi3And MgH2Mixing, and performing ball milling to obtain a composite hydrogen storage material;
the ball milling is carried out in an argon atmosphere, and the pressure of the argon is 0.05-0.15 MPa;
the ball-milling ball material mass ratio is (25-40): 1, the rotating speed of the ball milling is 300-500 r/min;
the ball milling time is 10-12 h;
the ball milling is intermittent ball milling, wherein the intermittent ball milling is performed for 10-20 min each time, and the intermittent ball milling is performed for 10-20 min.
2. A method of making the composite hydrogen storage material of claim 1, comprising the steps of:
mixing MgCNi3And MgH2Mixing, and performing ball milling to obtain a composite hydrogen storage material;
the ball milling is carried out in an argon atmosphere, and the pressure of the argon is 0.05-0.15 MPa;
the ball-milling ball material mass ratio is (25-40): 1, the rotating speed of the ball milling is 300-500 r/min;
the ball milling is intermittent ball milling, wherein the intermittent ball milling is performed for 10-20 min each time, and the intermittent ball milling is performed for 10-20 min.
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