CN103133860A - Metal nitrogen hydride hydrogen storage material solid hydrogen source system - Google Patents
Metal nitrogen hydride hydrogen storage material solid hydrogen source system Download PDFInfo
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- CN103133860A CN103133860A CN2011103842506A CN201110384250A CN103133860A CN 103133860 A CN103133860 A CN 103133860A CN 2011103842506 A CN2011103842506 A CN 2011103842506A CN 201110384250 A CN201110384250 A CN 201110384250A CN 103133860 A CN103133860 A CN 103133860A
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- hydrogen
- metal nitrogen
- nitrogen hydride
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- 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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Abstract
The invention relates to a solid hydrogen source system with big-size hydrogen storage density and high heat exchange performance, and the solid hydrogen source system takes metal nitrogen hydride hydrogen storage material as hydrogen storage medium and is made of the metal nitrogen hydride hydrogen storage material and expanded graphite through compression forming and filling manufacture. The hydrogen source system is composed of a cylinder jar body, an annular block which is made of the metal nitrogen hydride hydrogen storage material/expanded graphite, a multi-hole gas-guide tube, a heating device and the like. System size hydrogen storage density is not less than 45-kilogram-hydrogen per cubic meter.
Description
Technical field
The invention belongs to the hydrogen storage technology in Hydrogen Energy field, relate to a kind ofly take metal nitrogen hydride hydrogen-storing material as hydrogen storage media, prepare the solid hydrogen source system of high volume hydrogen-storage density and high heat-exchanging performance.
Background technique
Safe, efficient, economic hydrogen storage technology is the major technique bottleneck that present Hydrogen Energy is utilized.In recent years, the novel light high power capacity storage hydrogen materials such as metal alanates, borohydride, metal nitrogen hydride hydrogen-storing material and amino borane compound, theoretical hydrogen-storage density be up to more than 5wt%, for the breakthrough of solid-state hydrogen storage technology has brought hope.Wherein metal nitrogen hydride system hydrogen storage material such as Li
2NH, Li
2Mg (NH)
2Be one of hydrogen storage material that receives publicity especially, its reversible capacity of hydrogen storage and release is up to 5.5wt%, and the hydrogen discharging temperature under the 1bar condition is 90 ℃ of left and right only, and cost is low with respect to other lightweight high power capacity storage hydrogen materials, therefore has a good application prospect.
Metal nitrogen hydride hydrogen-storing material powder density is about 0.36~0.6g/ml, and thermal conductivity is lower than 0.4W/m/K.Metal nitrogen hydride hydrogen-storing material is generally completed the hydrogen process of putting of inhaling under 100~200 ℃, therefore the requirement higher with extraneous exchange capability of heat proposition to hydrogen storage material.Be subjected to metal nitrogen hydride hydrogen-storing material powder density and the low impact of thermal conductivity, the solid-state hydrogen storage system of preparation take it as hydrogen storage media, volume hydrogen-storage density and temperature conductivity all can not satisfy usage requirement, therefore demand developing the making method of a kind of metal nitrogen hydride solid hydrogen source system urgently, make system with high volume hydrogen-storage density and high heat-exchanging performance.
Summary of the invention
The purpose of this invention is to provide a kind of metal nitrogen hydride solid hydrogen source system that has higher volumes hydrogen-storage density and high heat-exchanging performance concurrently.Utilize this metal nitrogen hydride solid hydrogen source system, its volume hydrogen-storage density is not less than 45kgH
2/ m
3, thermal conductivity is not less than 5W/m/K.
For achieving the above object, the present invention is by the following technical solutions:
a kind of metal nitrogen hydride hydrogen-storing material solid hydrogen source system, this metal nitrogen hydride solid hydrogen source system is that filling metal nitrogen hydride hydrogen-storing material mixes the ring block that is pressed into expanded graphite in tank body, the top of tank body has suitable for reading, suitable for reading be furnished with sealing cover body, be provided with the porous air pipe in tank body and between ring block, the outlet of porous air pipe is positioned at the place suitable for reading of tank body, in the air outlet of sealing cover body, filter sheet is installed, , porous air pipe and filter sheet, pneumatic tube, control valve is connected, be provided with temperature control heating device on the side face of tank wall.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described metal nitrogen hydride hydrogen-storing material is Li
2NH, Li
2Mg (NH)
2One or both in material.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described metal nitrogen hydride hydrogen-storing material mixes the ring block that is pressed into expanded graphite, wherein, expanded graphite content is 5~20wt%, and metal nitrogen hydride hydrogen-storing material content is 80~95wt%.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system; described metal nitrogen hydride hydrogen-storing material mixes the ring block that is pressed into expanded graphite be after adopting metal nitrogen hydride hydrogen-storing material and expanded graphite through mechanical lapping 30min~60min; under protection, adopt the pressure direct pressing of 200~700MPa to form by ring mould in argon gas or nitrogen atmosphere.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described metal nitrogen hydride hydrogen-storing material mixes the radial thermal conductivity that is pressed into ring block and is not less than 5W/m/K with expanded graphite, and the loading density in tank body is not less than 1.0g/ml.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, by the hydrogen that metal nitrogen hydride hydrogen-storing material generates, the volume hydrogen-storage density of this hydrogen is not less than 45kgH
2/ m
3
in metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described sealing cover body is by sealed cover, sealing spiral cover and seal washer form, wherein, described sealed cover covers on tank body by seal washer, and by described sealing spiral cover and suitable for reading being spirally connected of tank body, sealed cover is pressed on tank body, have the passage of pneumatic tube on the top of sealed cover, sealed cover is in-built described filter sheet, pneumatic tube leads directly on filter sheet by its passage, so that the porous air pipe in tank body is connected by filter sheet and pneumatic tube, the bottom of porous air pipe leads to the bottom in tank body.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described porous air pipe is positioned at the middle part of tank body, and the passage of the pneumatic tube on the top of described sealed cover also is positioned at the middle part of sealed cover.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described tank body is cylindric, cylindric also referred to as the hollow of an end opening; Sealed cover is circular body, and the sealing spiral cover is hollow circular ring body (also can be the dome body, but its middle part will have the pneumatic tube passage corresponding with the middle part of sealed cover); Seal washer is cirque body.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, the how empty metal tube of described porous air pipe for adopting powder metallurgy process to make, the aperture is about 1~5 micron, guarantees the unimpeded of gas.Wherein, adopt the similar foam of body of the how empty metal tube that powder metallurgy process makes.
In metal nitrogen hydride hydrogen-storing material solid hydrogen source of the present invention system, described control valve is ball valve.
The invention provides the making method of metal nitrogen hydride solid hydrogen source system, comprise following steps:
1) prefabricated cylinder tank body and corresponding sealed cover and sealing spiral cover with hollow of an end opening, cylinder tank body opening end is processed with the circular groove of placing seal washer, sealed cover center drilling (being the passage of pneumatic tube) and soldering stainless steel pneumatic tube, sealed cover is built-in with filter sheet;
2) the porous air pipe is fixed on hydrogen source system centre (being the center in tank body);
3) with 80~95wt% metal nitrogen hydride hydrogen-storing material and 5~20wt% expanded graphite after mechanical lapping 30~60min, compressing in the ring mould of packing under argon gas or nitrogen atmosphere protection, briquetting pressure 200~700MPa;
4) prefabricated profiled metal nitrogen hydride hydrogen-storing material/expanded graphite annular pressing block is packed in order (being in tank body) in the hydrogen source system;
5) copper or aluminium gasket are arranged in the circular groove of cylinder tank body opening end;
6) cover sealed cover and sealing spiral cover, the mode by rotary seal spiral cover crush seal packing ring realizes the gas seal between sealed cover and cylinder tank body;
7) end of ball valve is connected with stainless steel pneumatic tube on sealed cover;
8) temperature control heating device is installed.
The invention has the advantages that: powdery metal nitrogen hydride hydrogen-storing material, through mixes compressing filling making solid hydrogen source system with the expanded graphite of 5~20wt%, metal nitrogen hydride hydrogen source system bulk hydrogen-storage density is significantly improved, and the exchange capability of heat of system and external environment condition significantly strengthens.
Simultaneously, metal nitrogen hydride solid hydrogen source provided by the present invention system making method, can be used for the making of other solid hydrogen source systems take complex hydrides, borohydride hydrogen storage material etc. as hydrogen storage media, the compacting shape of hydrogen storage material and expanded graphite mixture can change arbitrarily according to hydrogen source system's shape designing requirement.
Description of drawings
Fig. 1 metal nitrogen of the present invention hydride solid hydrogen source system architecture schematic diagram.
Figure 23 .5Nm
3Volume Li
2Mg (NH)
2160 ℃ of Hydrogen desorption isotherms of hydrogen storage material hydrogen source system.
Figure 31 .2Nm
3Volume Li
2200 ℃ of Hydrogen desorption isotherms of NH hydrogen storage material hydrogen source system.
Embodiment
The present invention further illustrates in conjunction with the following example and accompanying drawing, but the present invention is not limited to following embodiment.
As shown in Figure 1, metal nitrogen hydride solid hydrogen source of the present invention system is that the interior filling metal nitrogen of cylinder tank body 7 hydride hydrogen-storing material of the hollow of at one end opening mixes compressing ring block 8 with expanded graphite; The opening end of cylinder tank body 7 is processed with the circular groove of placing seal washer 5, and place seal washer 5 (being done by aluminium or copper) in this circular groove, and corresponding sealed cover 3 is installed on seal washer 5 and is sealed spiral cover 4, sealing spiral cover 4 is the hollow circular ring shape, sealed cover 3 is circular body, its center has the passage of pneumatic tube, and the soldering stainless steel pneumatic tube, and sealed cover 3 is built-in with filter sheet 2; Middle part in tank body 7 is provided with porous air pipe 6, the bottom in the straight-through tank body 7 in porous air pipe 6 bottoms, and the filter sheet 2 on the straight-through sealed cover 3 in porous air pipe 6 tops, and join with pneumatic tube, pneumatic tube is provided with ball valve 1; Be provided with temperature control heating device 9 on the side face of tank body 7 outer walls.
Metal nitrogen hydride solid hydrogen source system architecture schematic diagram is hydrogen source one embodiment of system of the present invention, as shown in Figure 1, this solid-state hydrogen storage system comprises: ball valve 1, filter sheet 2, sealed cover 3, sealing spiral cover 4, aluminium or copper sealing washer 5, porous metals air pipe 6, cylinder tank body 7, several metal nitrogen hydride/expanded graphite ring block 8 and temperature control heating devices 9.Porous air pipe 6 is placed in the central position in cylinder tank body 7; Annular space is filled several metal nitrogen hydride/expanded graphite ring blocks 8; Connect the Stainless Steel Tube gas tank on sealed cover 3, interior location is equipped with filter sheet 2; One end of ball valve 1 is connected with Stainless Steel Tube, and the other end is air inlet/outlet.
After mechanical lapping 30~60min, under argon gas or nitrogen atmosphere protection, adopt 200~700MPa pressure to be pressed into ring block 8 in the ring mould of packing into 80~95wt% metal nitrogen hydride hydrogen-storing material and 5~20wt% expanded graphite; Porous air pipe 6 is fixed on cylinder tank body 7 centers, ring block 8 is inserted in annular space between 6 and 7; After filling was completed, rotary seal spiral cover 4 extruded aluminium or copper sealing washer 5 were realized the gas seal of 7 of sealed cover 3 and cylinder tank bodies.
Embodiment 2
80~82wt%Li
2Mg (NH)
2Metal nitrogen hydride and 18~20wt% expanded graphite after 40~60min mechanical lapping mixes, under the nitrogen atmosphere protection, are pressed into external diameter 100mm in the annular grinding tool of packing into, the ring block of internal diameter 8mm, Li
2Mg (NH)
2Metal nitrogen hydride/expanded graphite ring block bulk density rises to 1.24g/ml from compressing front 0.38g/ml, and the radial thermal conductivity that steady state method is measured rises to 8.5W/m/K from 0.3W/m/K.
With Li
2Mg (NH)
2Metal nitrogen hydride/expanded graphite annular is fast, is filled into long 800mm according to embodiment 1 method, and hydrogen capacity is 3.5Nm
3Solid-state hydrogen storage system.Hydrogen source system bulk hydrogen-storage density is reached for 56kgH
2/ m
3(Li
2Mg (NH)
2The material hydrogen storage capability is 5.6wt%), system is at 160 ℃, can emit fast 1.8Nm in 60 minutes
3Hydrogen was emitted 3.0Nm in 180 minutes
3Rise hydrogen, as shown in Figure 2.
Embodiment 3
85~90wt%Li
2NH metal nitrogen hydride and 10~15wt% expanded graphite, after 30~50min mechanical lapping mixes, under the nitrogen atmosphere protection, compacting outside diameter 70mm in the annular grinding tool of packing into, the ring block of inner circle 6mm, Li
2NH metal nitrogen hydride/expanded graphite ring block bulk density is brought up to 1.05g/ml from compressing front 0.35g/ml, and the radial thermal conductivity of measuring through steady state method rises to 5.6W/m/K from 0.3W/m/K.
With Li
2NH metal nitrogen hydride/expanded graphite annular is medium soon, is filled into long 600mm, hydrogen capacity 1.2Nm according to embodiment 1 method
3Solid-state hydrogen storage system.Hydrogen source system bulk hydrogen-storage density is 45kgH
2/ m
3(Li
2NH material hydrogen storage capability 5.0wt%).645 liters of hydrogen are put in 60 minutes fast in 200 ℃ of systems, and 180 minutes put 1025 liters of hydrogen, as shown in Figure 3.
Claims (10)
1. metal nitrogen hydride hydrogen-storing material solid hydrogen source system, it is characterized in that: this metal nitrogen hydride solid hydrogen source system is that filling metal nitrogen hydride hydrogen-storing material mixes the ring block that is pressed into expanded graphite in tank body, the top of tank body has suitable for reading, suitable for reading be furnished with sealing cover body, be provided with the porous air pipe in tank body and between ring block, the outlet of porous air pipe is positioned at the place suitable for reading of tank body, in the air outlet of sealing cover body, filter sheet is installed, porous air pipe and filter sheet, pneumatic tube, control valve is connected, be provided with temperature control heating device on the side face of tank wall.
2. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 1 system, it is characterized in that: described metal nitrogen hydride hydrogen-storing material is Li
2NH, Li
2Mg (NH)
2One or both in material.
3. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 1 system, it is characterized in that: described metal nitrogen hydride hydrogen-storing material mixes the ring block that is pressed into expanded graphite, wherein, expanded graphite content is 5~20wt%, and metal nitrogen hydride hydrogen-storing material content is 80~95wt%.
4. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 1 system; it is characterized in that: described metal nitrogen hydride hydrogen-storing material mixes the ring block that is pressed into expanded graphite be after adopting metal nitrogen hydride hydrogen-storing material and expanded graphite through mechanical lapping 30min~60min; under protection, adopt the pressure direct pressing of 200~700MPa to form by ring mould in argon gas or nitrogen atmosphere.
5. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 1 system, it is characterized in that: described metal nitrogen hydride hydrogen-storing material mixes the radial thermal conductivity that is pressed into ring block and is not less than 5W/m/K with expanded graphite, and the loading density in tank body is not less than 1.0g/ml.
6. according to claim 1-5 described metal nitrogen hydride hydrogen-storing material solid hydrogen source systems, it is characterized in that: in described metal nitrogen hydride hydrogen-storing material solid hydrogen source system, by the hydrogen that metal nitrogen hydride hydrogen-storing material generates, the volume hydrogen-storage density of this hydrogen is not less than 45kgH
2/ m
3
7. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 1 system, it is characterized in that: described sealing cover body is by sealed cover, sealing spiral cover and seal washer form, wherein, described sealed cover covers on tank body by seal washer, and by described sealing spiral cover and suitable for reading being spirally connected of tank body, sealed cover is pressed on tank body, have the passage of pneumatic tube on the top of sealed cover, sealed cover is in-built described filter sheet, pneumatic tube leads directly on filter sheet by its passage, so that the porous air pipe in tank body is connected by filter sheet and pneumatic tube, the bottom of porous air pipe leads to the bottom in tank body.
8. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 7 system, it is characterized in that: described porous air pipe is positioned at the middle part of tank body, and the passage of the pneumatic tube on the top of described sealed cover also is positioned at the middle part of sealed cover.
9. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 7 system, it is characterized in that: described tank body is cylindric; Sealed cover is circular body, and the sealing spiral cover is the hollow circular ring body; Seal washer is cirque body.
10. metal nitrogen hydride hydrogen-storing material solid hydrogen source according to claim 1 system, it is characterized in that: the how empty metal tube of described porous air pipe for adopting powder metallurgy process to make, the aperture is 1~5 micron.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104654004A (en) * | 2013-11-25 | 2015-05-27 | 北京有色金属研究总院 | Metal nitrogen hydride hydrogen storage tank |
CN105387341A (en) * | 2015-11-18 | 2016-03-09 | 北京有色金属研究总院 | Metal hydride hydrogen storage tank |
CN111022912A (en) * | 2020-02-18 | 2020-04-17 | 扬州大学 | Metal hydride hydrogen storage tank with low cost, high hydrogen absorption and desorption speed and high safety |
CN113401865A (en) * | 2021-05-09 | 2021-09-17 | 四川大学 | Metal hydride reactor with modular filling composite compaction unit bodies |
CN114046444A (en) * | 2021-08-02 | 2022-02-15 | 有研工程技术研究院有限公司 | Solid hydrogen storage device |
CN110282601B (en) * | 2019-08-06 | 2022-06-17 | 贵州工程应用技术学院 | Device is prepared to hydrogen storage material that graphite alkene mixes |
CN116357886A (en) * | 2023-04-07 | 2023-06-30 | 华北电力大学 | Foam metal hydrogen storage bottle for heat pipe heat exchange and heat transfer method |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113401865A (en) * | 2021-05-09 | 2021-09-17 | 四川大学 | Metal hydride reactor with modular filling composite compaction unit bodies |
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CN116357886A (en) * | 2023-04-07 | 2023-06-30 | 华北电力大学 | Foam metal hydrogen storage bottle for heat pipe heat exchange and heat transfer method |
CN116357886B (en) * | 2023-04-07 | 2024-01-16 | 华北电力大学 | Foam metal hydrogen storage bottle for heat pipe heat exchange and heat transfer method |
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Application publication date: 20130605 |