CN110788330A - Aluminum-containing composite hydrogen storage alloy and preparation method thereof, composite solid hydrogen storage tank and hydrogen storage performance testing method - Google Patents

Aluminum-containing composite hydrogen storage alloy and preparation method thereof, composite solid hydrogen storage tank and hydrogen storage performance testing method Download PDF

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Publication number
CN110788330A
CN110788330A CN201911084134.5A CN201911084134A CN110788330A CN 110788330 A CN110788330 A CN 110788330A CN 201911084134 A CN201911084134 A CN 201911084134A CN 110788330 A CN110788330 A CN 110788330A
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hydrogen storage
hydrogen
aluminum
storage alloy
storage tank
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CN110788330B (en
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原建光
武英
张宝
阎有花
周少雄
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Jiangsu Collection Of Antai Chuang Ming Advanced Energy Materials Research Institute Co Ltd
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Jiangsu Collection Of Antai Chuang Ming Advanced Energy Materials Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G01N7/14—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference
    • G01N7/16—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference by heating the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/01—Shape
    • F17C2201/0104—Shape cylindrical
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/058—Size portable (<30 l)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0646—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0636—Metals
    • F17C2203/0648—Alloys or compositions of metals
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/01—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the phase
    • F17C2225/0107—Single phase
    • F17C2225/0123—Single phase gaseous, e.g. CNG, GNC
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/043—Pressure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/0439—Temperature
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/0473—Time or time periods
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/01—Purifying the fluid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2265/00—Effects achieved by gas storage or gas handling
    • F17C2265/04—Effects achieved by gas storage or gas handling using an independent energy source, e.g. battery
    • 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
    • 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
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/45—Hydrogen technologies in production processes

Abstract

The invention relates to an aluminum-containing composite hydrogen storage alloy and a preparation method thereof, a composite solid hydrogen storage tank and a hydrogen storage and discharge performance testing method. The aluminum-containing composite hydrogen storage alloy is prepared from 80-98% of hydrogen storage alloy powder and 2-20% of aluminum material in percentage by mass. The composite solid hydrogen storage tank provided by the invention discharges hydrogen at the hydrogen discharge flow rate of 8L/Min at 50 ℃, the hydrogen discharge time can reach 60Min, the hydrogen discharge amount can reach 480L, and the maximum hydrogen discharge amount can reach 90% of the hydrogen storage amount of the hydrogen storage tank.

Description

Aluminum-containing composite hydrogen storage alloy and preparation method thereof, composite solid hydrogen storage tank and hydrogen storage performance testing method
Technical Field
The invention belongs to the technical field of hydrogen storage material preparation, and particularly relates to an aluminum-containing composite hydrogen storage alloy prepared based on an aluminum material and hydrogen storage alloy, a preparation method of the aluminum-containing composite hydrogen storage alloy, a composite solid hydrogen storage tank prepared by using the aluminum-containing composite hydrogen storage alloy, and a method for testing the hydrogen storage performance of the composite solid hydrogen storage tank.
Background
Exhaustion of fossil energy and environmental pollution crisis force human to develop renewable clean energy. Hydrogen is a clean secondary energy source, and is an ideal carrier of renewable primary energy sources. In the 70 s of the 20 th century, the U.S. general automobile company proposed the concept of "hydrogen economy era" to describe the future use of hydrogen instead of petroleum and natural gas as the main energy economy supporting global economy. Therefore, the development and utilization of hydrogen energy has become a scientific field of particular interest to countries throughout the world. In the research and development aspect of hydrogen energy, three major problems of hydrogen generation, storage and utilization are faced at present. The storage of hydrogen is the key to the development and utilization of hydrogen energy, and the research of hydrogen storage technology is regarded as an important technical project in many developed countries at present. The storage and transportation of hydrogen can be divided into 3 types according to the storage method of hydrogen: the first is a gas hydrogen storage technology, which stores hydrogen gas in a high-pressure container after compression, and has the disadvantages of small volume and small hydrogen storage amount of a steel cylinder for storing hydrogen gas and explosion risk; the second is a liquid hydrogen storage technology, i.e. the liquefied hydrogen is stored in a heat-insulating container, the liquid hydrogen storage is generally applied to major projects such as aerospace, and the hydrogen can be liquefied only by cooling to about-253 ℃, so that the energy consumption is high, the liquid storage tank is large, a good heat-insulating device is needed for heat insulation, the leakage is easy, the requirement on the heat-insulating property of the storage tank is high, and the problems restrict the wide application of the hydrogen energy; the third is solid hydrogen storage technology, namely a solid hydrogen storage mode that hydrogen and hydrogen storage materials are combined in a physical or chemical mode, can effectively overcome the defects of a gas storage mode and a liquid storage mode, and has the advantages of large hydrogen storage volume density, high safety degree, convenient transportation and easy operation. With the application of the hydrogen storage alloy, hydrogen can be stored in the hydrogen storage alloy in the form of atoms or hydrides, and the hydrogen storage alloy has the advantages of high hydrogen storage density, relatively low requirements on high pressure resistance and heat insulation performance of a storage container, good safety and the like, and becomes a potential ideal mode for storing hydrogen.
In recent years, various researchers in various countries have made a lot of research works on solid-state hydrogen storage technology, so that solid-state hydrogen storage alloys have been rapidly developed and put into commercial use. The hydrogen storage tank using the hydrogen storage alloy as the storage medium has high storage density, can conveniently provide hydrogen sources for fuel cells used in various occasions, and is particularly suitable for providing safe and reliable hydrogen sources for mobile tools driven by various fuel cells, such as electric automobiles, electric motorcycles and electric bicycles.
However, the hydrogen storage alloy absorbs hydrogen and expands with about 25% volume, and the volume shrinks after hydrogen release, so after a plurality of hydrogen absorption and release cycles, the hydrogen storage alloy can be gradually pulverized, and meanwhile, the hydrogen storage alloy powder is easy to flow along with the flow of hydrogen in the hydrogen absorption and release process, so that the hydrogen storage alloy powder is accumulated, a hydrogen storage device loses gaps locally, and a hydrogen storage tank deforms, even cracks and damages in the hydrogen absorption and release process of the hydrogen storage alloy, thereby causing safety accidents. The hydrogen storage alloy powder has serious heat effect, and the heat of hydrogen absorption reaction can be timely transmitted out and the heat of hydrogen desorption reaction can be timely provided.
Therefore, it is highly desired to develop a composite hydrogen storage tank made of a hydrogen storage material which can effectively prevent the pulverization of the hydrogen storage alloy powder, improve the heat exchange performance, and release hydrogen at a stable flow rate.
Disclosure of Invention
The invention provides an aluminum-containing composite hydrogen storage alloy and a preparation method thereof.
The invention also provides a composite solid hydrogen storage tank made of the aluminum-containing composite hydrogen storage alloy and a method for testing the hydrogen storage performance of the composite solid hydrogen storage tank.
The technical scheme of the invention is as follows:
an aluminum-containing composite hydrogen storage alloy is prepared from 80-98% of hydrogen storage alloy powder and 2-20% of aluminum material by mass percent.
In the aluminum-containing composite hydrogen storage alloy, as a preferred embodiment, the aluminum material includes one or more of spherical aluminum powder, aluminum foil, and aluminum fiber;
more preferably, when the aluminum material is spherical aluminum powder, the aluminum-containing composite hydrogen storage alloy is a mixed powder of the spherical aluminum powder and the hydrogen storage alloy powder;
when the aluminum material is an aluminum foil, the aluminum-containing composite hydrogen storage alloy has a sandwich-like structure in which hydrogen storage alloy powder is sandwiched between adjacent strip-shaped aluminum foils, preferably, the number of layers of the strip-shaped aluminum foils in the aluminum-containing composite hydrogen storage alloy is 30-50, and the mass of each layer of the hydrogen storage alloy powder sandwiched between the adjacent strip-shaped aluminum foils is the same;
when the aluminum material is aluminum fiber, the aluminum-containing composite hydrogen storage alloy has a sandwich-like structure in which hydrogen storage alloy powder is sandwiched between adjacent aluminum fiber layers, preferably, the number of the aluminum fiber layers in the aluminum-containing composite hydrogen storage alloy is 30-50, and the mass of the hydrogen storage alloy powder in each layer sandwiched between the adjacent aluminum fiber layers is the same; the quality of each layer of aluminum fiber is the same; preferably, the particle size of the spherical aluminum powder is 1-200 μm;
preferably, the thickness of the aluminum foil is 0.2-0.5 mm;
preferably, the length of the aluminum fiber is 30-40mm, and the diameter of the aluminum fiber is 1-2 mm.
In the above aluminum-containing composite hydrogen storage alloy, as a preferred embodiment, the hydrogen storage alloy powder includes a rare earth-based AB5Type, titanium AB type2One or more of type and titanium vanadium solid solution type hydrogen storage alloy powder;
preferably, the average particle size of the hydrogen storage alloy powder is 75-300 μm;
preferably, the rare earth system AB5In the hydrogen occluding alloy powder of type A, the A side is composed of La and at least 1 of the elements group of Ce, Pr, Nd, Sm, Gd, Dy, Mg, Ti and Zr, and the B side metal is composed of Ni and Co, Mn, Cu, Fe, Si, Ge, Ti, Zr,At least 1 element selected from the group consisting of Sn, Cr, Zn, B, V, W, Mo, Ta and Nb.
The method for preparing the aluminum-containing composite hydrogen storage alloy comprises the following steps:
a step of preparing hydrogen storage alloy powder;
a step of preparing the aluminum material;
and preparing the aluminum-containing composite hydrogen storage alloy by matching the aluminum material with the hydrogen storage alloy powder.
In the above production method, as a preferred embodiment, the step of producing the hydrogen storage alloy powder includes:
smelting the raw materials of the hydrogen storage alloy powder to prepare a hydrogen storage alloy ingot, and then carrying out vacuum annealing homogenization treatment on the alloy ingot, wherein the smelting temperature is 1300-1500 ℃, the vacuum annealing homogenization treatment temperature is 800-1150 ℃, and the annealing time is 5-10 h; and then crushing and ball-milling the annealed hydrogen storage alloy ingot to obtain the hydrogen storage alloy powder.
In the above production method, as a preferred embodiment, in the step of preparing the aluminum-containing composite hydrogen storage alloy by blending the aluminum material with the hydrogen storage alloy powder,
when the aluminum material is spherical aluminum powder, mechanically stirring and mixing the hydrogen storage alloy powder and the spherical aluminum powder to obtain the aluminum-containing composite hydrogen storage alloy;
when the aluminum material is an aluminum foil, a hydrogen storage alloy powder layer is laid on one strip-shaped aluminum foil, then another strip-shaped aluminum foil is laid on the hydrogen storage alloy powder layer, and the hydrogen storage alloy powder layers except the uppermost layer are continuously laminated to the required number of layers in a manner of respectively clamping the hydrogen storage alloy powder layers between the adjacent strip-shaped aluminum foil layers, so that the aluminum-containing composite hydrogen storage alloy with the sandwich-like structure is formed; preferably, the number of layers of the strip-shaped aluminum foil in the aluminum-containing composite hydrogen storage alloy is 30-50; more preferably, the weight of each layer of hydrogen storage alloy powder interposed between adjacent strip-shaped aluminum foil layers is the same, and the size of the strip-shaped aluminum foil of each layer is the same;
when the aluminum material is aluminum fiber, firstly, laying an aluminum fiber layer by adopting the aluminum fiber, then laying a hydrogen storage alloy powder layer on the aluminum fiber layer, then laying another aluminum fiber layer on the hydrogen storage alloy powder layer, and continuously laminating to the required number of layers in a manner that all hydrogen storage alloy powder layers except the uppermost layer are clamped on the adjacent aluminum fiber layers, thereby forming the aluminum-containing composite hydrogen storage alloy with the sandwich type structure; preferably, the number of the aluminum fiber layers in the aluminum-containing composite hydrogen storage alloy is 30-50; more preferably, the weight of each layer of hydrogen occluding alloy powder interposed between adjacent aluminum fiber layers is the same; the weight of each layer of aluminum fiber is the same.
A composite solid hydrogen storage tank comprises a tank body and the aluminum-containing composite hydrogen storage alloy arranged in the tank body.
In the above composite solid hydrogen storage tank, the material of the tank body is preferably metal aluminum or aluminum alloy, and more preferably 616 aluminum alloy; further preferably, the can body includes a straight tube portion and an opening portion that is extended and narrowed from the straight tube portion;
more preferably, the composite solid-state hydrogen storage tank further comprises a filter and a valve, wherein the filter is embedded in the opening portion of the tank body, and the valve is mounted on the opening portion and used for closing or opening the opening portion of the tank body;
preferably, the inner diameter of the tank body of the hydrogen storage tank is 70-80mm, the outer diameter is 80-90mm, the length of the straight cylinder part is 275-285mm, and the volume is 1-1.5L; more preferably, the outer diameter of the body of the hydrogen storage tank is 85mm, the inner diameter is 85mm, the length of the straight cylinder part is 280mm, and the volume is 1L.
The method for testing the hydrogen storage performance of the composite solid-state hydrogen storage tank comprises the following steps:
installing the composite solid hydrogen storage tank into a hydrogen storage tank hydrogen charging and activating treatment device, and sequentially performing activation, hydrogen charging and hydrogen discharging performance tests on the aluminum-containing composite hydrogen storage alloy in the composite solid hydrogen storage tank;
preferably, the activating and charging comprises: controlling the temperature of the composite solid hydrogen storage tank within the range of 80-120 ℃, and simultaneously carrying out vacuum pumping treatment on the composite solid hydrogen storage tank for 5-10 h; filling hydrogen into the composite solid hydrogen storage tank, wherein the pressure of the hydrogen in the composite solid hydrogen storage tank is 2-10MPa, and the pressure holding time is 5-10 h;
preferably, the hydrogen discharge performance test comprises: controlling the hydrogen release temperature to be 5-50 ℃, controlling the hydrogen release flow rate to be 2-8L/min, monitoring the pressure value in the hydrogen storage tank in real time, and stopping hydrogen release time recording when the hydrogen release flow rate is reduced to a preset flow rate to obtain the hydrogen release time and the hydrogen release amount of the hydrogen storage tank at a specific speed;
obtaining the hydrogen release amount percentage of the hydrogen storage tank in a specific time according to the obtained ratio of the hydrogen release amount to the total hydrogen storage amount of the hydrogen storage tank;
preferably, the hydrogen discharge flow rate is controlled to be 8L/min at 50 ℃, and when the hydrogen discharge flow rate is reduced to 6L/min, the hydrogen discharge time recording is stopped.
In the above test method, as a preferred embodiment,
the hydrogen storage tank hydrogen filling and activating treatment device comprises: a vacuum pump, a gaseous hydrogen cylinder and a water bath;
the vacuum pump is connected with the composite solid-state hydrogen storage tank through a vacuum pumping pipeline and is used for vacuumizing the composite solid-state hydrogen storage tank, and preferably, a vacuum pumping switch valve is arranged on the vacuum pumping pipeline;
the gaseous hydrogen cylinder is connected with the composite solid hydrogen storage tank through a hydrogen charging pipeline and used for supplying hydrogen to the hydrogen storage tank, and preferably, a pressure reducing valve, a mass flow controller and a hydrogen charging switch valve are sequentially arranged on the hydrogen charging pipeline along the hydrogen flow direction;
the water bath is arranged outside the composite solid hydrogen storage tank and used for heating the composite solid hydrogen storage tank.
In the above test method, as a preferred embodiment, the hydrogen tank charging and activating treatment apparatus further includes: the pressure sensor is arranged on a hydrogen discharge pipeline, one end of the hydrogen discharge pipeline is connected with the composite solid hydrogen storage tank, and the pressure sensor is used for monitoring the real-time pressure of the composite solid hydrogen storage tank during hydrogen discharge; preferably, an electromagnetic valve, a mass flow controller, a back pressure valve, a hydrogen discharge switch valve and a one-way valve are sequentially arranged on the hydrogen discharge pipeline along the gas flowing direction.
The technical scheme of the invention has the effects that:
(1) the aluminum material has excellent heat conduction performance, reduces the crystal boundary migration and grain growth of the hydrogen storage alloy caused by the hydrogen absorption and desorption thermal effect, and thus improves the hydrogen absorption and desorption performance of the hydrogen storage alloy. The invention utilizes aluminum materials with different sizes and different forms to be compounded with the hydrogen storage alloy, and can effectively relieve the fine cracks and the alloy pulverization capability caused by volume expansion during hydrogen absorption due to volume shrinkage during dehydrogenation in the hydrogen absorption and desorption circulation process of the hydrogen storage alloy.
(2) The composite solid hydrogen storage tank provided by the invention has the characteristics of pulverization resistance, high heat conduction rate and excellent hydrogen absorption and desorption rate.
(3) The composite solid hydrogen storage tank provided by the invention has excellent hydrogen discharge dynamic performance, can stably provide hydrogen flow with a certain flow rate, and can completely meet the actual hydrogen supply requirement of a fuel cell.
(4) The composite solid hydrogen storage tank provided by the invention can be used in the fields of hydrogen purification, fuel cell hydrogen sources, fixed energy storage and the like.
(5) The composite solid hydrogen storage tank provided by the invention discharges hydrogen at the hydrogen discharge flow rate of 8L/Min at 50 ℃, the hydrogen discharge time can reach 60Min, the hydrogen discharge amount can reach 480L, and the maximum hydrogen discharge amount can reach 90% of the hydrogen storage amount of the hydrogen storage tank.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a cross-sectional view of a composite solid hydrogen storage canister provided by the present invention;
FIG. 2 is a top view of FIG. 1;
FIG. 3 is a schematic system diagram of a hydrogen storage tank charging and activating device according to the present invention;
FIG. 4 is a graph showing the change of the hydrogen desorption flow rate and the hydrogen desorption pressure with time of the aluminum-containing composite hydrogen occluding alloy containing 1 to 10 μm spherical aluminum powder in an amount of 15 wt% in the hydrogen storage tank (i.e., the aluminum-containing composite hydrogen occluding alloy of example 1);
FIG. 5 is a graph showing the change of the hydrogen desorption flow rate and the hydrogen desorption pressure with time of the aluminum-containing composite hydrogen occluding alloy using aluminum foil in the hydrogen storage tank (i.e., the aluminum-containing composite hydrogen occluding alloy of example 2).
Reference numerals:
1. a gaseous hydrogen cylinder, 2, a vacuum pump;
3. a composite solid hydrogen storage tank 31, a tank body 32, an aluminum-containing composite hydrogen storage alloy 33, a filter 34 and a valve;
41. the system comprises a vacuumizing switch valve, 42, a hydrogen charging switch valve, 43, a hydrogen discharging switch valve, 5, a mass flow controller, 6, a pressure reducing valve, 7, a pressure sensor, 8, an electromagnetic valve, 9, a back pressure valve, 10, a one-way valve and 11, a water bath.
Detailed Description
The invention will be described in detail below with reference to specific embodiments with reference to the attached drawings. The various examples are provided by way of explanation of the invention, and not limitation of the invention. In fact, it will be apparent to those skilled in the art that modifications and variations can be made in the present invention without departing from the scope or spirit thereof. For instance, features illustrated or described as part of one embodiment, can be used with another embodiment to yield a still further embodiment. It is therefore intended that the present invention encompass such modifications and variations as fall within the scope of the appended claims and equivalents thereof.
An aluminum-containing composite hydrogen storage alloy is prepared from 80-98% of hydrogen storage alloy powder and 2-20% of aluminum material by mass percent.
The aluminum material has excellent heat conduction performance, can reduce the crystal boundary migration and grain growth of the hydrogen storage alloy caused by the hydrogen absorption and desorption thermal effect, and can improve the hydrogen absorption and desorption performance of the hydrogen storage alloy, so that the aluminum material is selected to be matched with the hydrogen storage alloy for use, and the problem that the hydrogen storage alloy used in the existing hydrogen storage tank is gradually pulverized after being recycled for multiple times, and further the hydrogen storage tank is deformed or even damaged can be effectively solved.
The aluminum material selected by the invention comprises one or more of spherical aluminum powder, aluminum foil and aluminum fiber, wherein the spherical aluminum powder with the particle size of 1-200 mu m can be used, and the spherical aluminum powder with the particle size of 1-10 mu m is preferably adopted; the aluminum foil can be 0.2-0.5mm thick; the length of the aluminum fiber can be 30-40mm, and the diameter is 1-2 mm. The preferred aluminum material of the invention is convenient to operate, and more importantly, the aluminum material has good thermal conductivity, too large particles and too thick thickness or too large diameter, so that the thermal conductivity of the aluminum material is deteriorated, and the improvement of the performance of the aluminum-containing composite hydrogen storage alloy is not facilitated.
When the aluminum material is spherical aluminum powder, the aluminum-containing composite hydrogen storage alloy is mixed powder of the spherical aluminum powder and the hydrogen storage alloy powder;
when the aluminum material is an aluminum foil, the aluminum-containing composite hydrogen storage alloy has a sandwich-like structure in which hydrogen storage alloy powder is sandwiched between adjacent strip-shaped aluminum foils, preferably, the number of layers of the strip-shaped aluminum foils in the aluminum-containing composite hydrogen storage alloy is 30-50, and the mass of each layer of the hydrogen storage alloy powder sandwiched between the adjacent strip-shaped aluminum foils is the same; that is, the bottom layer is an aluminum foil layer, and then a hydrogen storage alloy powder layer, an aluminum foil layer, a hydrogen storage alloy powder layer are sequentially arranged from bottom to top, and so on, and stacked to a required height, more preferably, the top layer is a hydrogen storage alloy powder layer, and the number of layers of aluminum foil is the same as that of the hydrogen storage alloy powder.
When the aluminum material is aluminum fiber, the aluminum-containing composite hydrogen storage alloy has a sandwich-like structure in which hydrogen storage alloy powder is sandwiched between adjacent aluminum fiber layers, preferably, the number of the aluminum fiber layers in the aluminum-containing composite hydrogen storage alloy is 30-50, and the mass of the hydrogen storage alloy powder in each layer sandwiched between the adjacent aluminum fiber layers is the same; the quality of each layer of aluminum fiber is the same; that is, the bottom layer is an aluminum fiber layer, and then a hydrogen storage alloy powder layer, an aluminum fiber layer, a hydrogen storage alloy powder layer, and the like are stacked to a desired height from bottom to top, and more preferably, the top layer is a hydrogen storage alloy powder layer, and the number of layers of the aluminum fiber layer is the same as the number of layers of the hydrogen storage alloy powder.
The average particle size of the hydrogen storage alloy powder selected by the invention is 75-300 μm, preferably 80-90 μm or 100-200 μm, including rare earth AB5Type, titanium AB type2One or more of type and titanium vanadium solid solution type hydrogen storage alloy. Preferably AB thereof5In the rare earth type hydrogen occluding alloy, the A side is composed of La and at least 1 of the elements of Ce, Pr, Nd, Sm, Gd, Dy, Mg, Ti and Zr, and the B side metal is composed of Ni and at least 1 of the elements of Co, Mn, Cu, Fe, Si, Ge, Sn, Cr, Zn, B, V, W, Mo, Ta and Nb.
The method for preparing the aluminum-containing composite hydrogen storage alloy comprises the following steps:
a step of preparing hydrogen storage alloy powder; the method specifically comprises the steps of firstly smelting raw materials to prepare a hydrogen storage alloy ingot, then carrying out vacuum annealing homogenization treatment on the alloy ingot, controlling the smelting temperature to be 1300-1500 ℃, the annealing homogenization treatment temperature to be 800-1150 ℃, and the annealing time to be 5-10 h; and crushing and ball-milling the annealed hydrogen storage alloy ingot to obtain hydrogen storage alloy powder, wherein the particle size of the hydrogen storage alloy powder is 75-300 mu m.
Preparing an aluminum material:
the aluminum material is spherical aluminum powder, and the hydrogen storage alloy powder and the spherical aluminum powder are mechanically stirred and mixed (a stirrer can be used for stirring, the stirring time can be set to be 1-5h, 1h, 2h, 3h, 4h and 5h according to the amount of raw materials), and are filled into a hydrogen storage tank.
The aluminum material is aluminum foil, the aluminum foil can be 0.2-0.5mm thick (for example, 0.2mm, 0.3mm, 0.4mm, 0.5mm thick), and the length and width of the aluminum foil are divided according to the inner diameter and height of the hydrogen storage tank when the aluminum foil is divided. Equally dividing the aluminum foil into strips with set specifications, laying hydrogen storage alloy powder with equal weight on the equally divided strips, and putting the aluminum foil and the hydrogen storage alloy powder laid on the aluminum foil into a hydrogen storage tank at the same time. When the aluminum material is an aluminum foil, a hydrogen storage alloy powder layer is laid on one strip-shaped aluminum foil, then another strip-shaped aluminum foil is laid on the hydrogen storage alloy powder layer, and the hydrogen storage alloy powder layers except the uppermost layer are continuously laminated to the required number of layers in a manner of being respectively clamped between the adjacent strip-shaped aluminum foil layers, so that the aluminum-containing composite hydrogen storage alloy with a sandwich-like structure is formed, wherein the uppermost layer is the hydrogen storage alloy powder layer; preferably, the number of layers of the strip-shaped aluminum foil in the aluminum-containing composite hydrogen storage alloy is 30-50; more preferably, the weight of each layer of hydrogen storage alloy powder interposed between adjacent strip-shaped aluminum foil layers is the same, and the size of the strip-shaped aluminum foil of each layer is the same;
the aluminum material is aluminum fiber, the aluminum fiber and the hydrogen storage alloy powder with equal weight are sequentially and respectively placed into the hydrogen storage tank in turn (when the aluminum fiber and the hydrogen storage alloy powder are actually placed in the hydrogen storage tank, the aluminum fiber and the hydrogen storage alloy powder can be paved layer by layer), the length of the aluminum fiber can be 30-40mm, and the diameter of the aluminum fiber is 1-2 mm. When the aluminum material is aluminum fiber, firstly, laying an aluminum fiber layer by adopting the aluminum fiber, then laying a hydrogen storage alloy powder layer on the aluminum fiber layer, then laying another aluminum fiber layer on the hydrogen storage alloy powder layer, and continuously laminating to the required number of layers in a manner that all hydrogen storage alloy powder layers except the uppermost layer are clamped on the adjacent aluminum fiber layers, thereby forming the aluminum-containing composite hydrogen storage alloy with a sandwich-type structure, wherein the uppermost layer is the hydrogen storage alloy powder layer; preferably, the number of the aluminum fiber layers in the aluminum-containing composite hydrogen storage alloy is 30-50; more preferably, the weight of each layer of hydrogen occluding alloy powder interposed between adjacent aluminum fiber layers is the same; the weight of each layer of aluminum fiber is the same.
The aluminum material and the hydrogen storage alloy powder put into the hydrogen storage tank jointly form the aluminum-containing composite hydrogen storage alloy used in the hydrogen storage tank.
Compared with spherical, fibrous and flaky aluminum materials, the flaky aluminum material has the best mixed use effect with hydrogen storage alloy powder and the best heat conduction effect; secondly, the fibrous aluminum material can ensure that the alloy powder has larger gaps and has good heat and gas conducting effects when being mixed with the hydrogen storage alloy powder for use; and finally, the spherical aluminum powder is mixed with the hydrogen storage alloy powder, so that the bulk density is high, and the heat and gas conducting effects are relatively poor.
Fig. 1 is a sectional view of the composite solid hydrogen storage tank according to the present invention, and fig. 2 is a plan view of the hydrogen storage tank, which includes a tank 31, an aluminum-containing composite hydrogen storage alloy 32 disposed in the tank 31, a filter 33 (for preventing powder from entering a hydrogen charging or discharging pipeline), and a valve 34.
The material of the can body 31 is metal aluminum or aluminum alloy, preferably 616 type aluminum alloy; further preferably, the can 31 includes a straight tube portion and an opening portion that is extended and narrowed from the straight tube portion;
the filter 33 is embedded in the opening part of the can 31, and the valve 34 is installed on the opening part and used for closing or opening the opening part of the can 31; the aperture of the opening is 1/3 of the width of the columnar cavity, and the aluminum-containing composite hydrogen storage alloy is filled in the cavity of the hydrogen storage tank.
The inner diameter of the tank body 31 of the hydrogen storage tank is 70-80mm, the outer diameter is 80-90mm, the length of the straight cylinder part is 275-285mm, and the volume is 1-1.5L; more preferably, the can body 31 of the hydrogen storage tank has an outer diameter of 85mm, an inner diameter of 85mm, a length of the straight cylinder portion of 280mm, and a volume of 1L.
The method for testing the hydrogen storage performance of the composite solid hydrogen storage tank comprises the following steps:
and installing the composite solid hydrogen storage tank into a hydrogen storage tank hydrogen charging and activating treatment device, and sequentially performing activation, hydrogen charging and hydrogen discharging performance tests on the aluminum-containing composite hydrogen storage alloy in the composite solid hydrogen storage tank.
In the above test method, preferably, the activating and charging comprises: controlling the temperature of the composite solid hydrogen storage tank within the range of 80-120 ℃, and simultaneously carrying out vacuum pumping treatment on the composite solid hydrogen storage tank for 5-10 h; filling hydrogen into the composite solid hydrogen storage tank, wherein the pressure of the hydrogen in the composite solid hydrogen storage tank is 2-10MPa, and the pressure holding time is 5-10 h;
in the above test method, preferably, the hydrogen discharge performance test includes: controlling the hydrogen release temperature to be 5-50 ℃, controlling the hydrogen release flow rate to be 2-8L/min, monitoring the pressure value in the hydrogen storage tank in real time, stopping hydrogen release time recording when the hydrogen release flow rate is reduced to a preset flow rate (for example, the hydrogen release flow rate is 8L/min, and then the preset flow rate is 6L/min), and obtaining the hydrogen release time and the hydrogen release amount of the hydrogen storage tank in the time, wherein the hydrogen release time can be the hydrogen release time at the hydrogen release flow rate of 8L/min;
obtaining the hydrogen release amount percentage of the hydrogen storage tank in a specific time according to the obtained ratio of the hydrogen release amount to the total hydrogen storage amount of the hydrogen storage tank;
preferably, the hydrogen discharge flow rate is controlled to be 8L/min at 50 ℃, and when the hydrogen discharge flow rate is reduced to 6L/min, the hydrogen discharge time recording is stopped.
The hydrogen storage tank fills hydrogen and activation processing apparatus includes: a vacuum pump 2, a gaseous hydrogen cylinder 1 and a water bath 11;
the vacuum pump 2 is connected with the composite solid-state hydrogen storage tank 3 through a vacuumizing pipeline and is used for vacuumizing the composite solid-state hydrogen storage tank 3, and a vacuumizing switch valve 41 is arranged on the vacuumizing pipeline;
the gaseous hydrogen cylinder 1 is connected with the composite solid hydrogen storage tank 3 through a hydrogen charging pipeline and used for supplying hydrogen into the hydrogen storage tank 3, and preferably, a pressure reducing valve 6, a mass flow controller 5 and a hydrogen charging switch valve 42 are sequentially arranged on the hydrogen charging pipeline along the hydrogen flow direction;
the water bath 11 is disposed outside the composite solid-state hydrogen storage tank 3, and is used for heating the composite solid-state hydrogen storage tank 3.
The hydrogen storage tank hydrogen charging and activating treatment device also comprises a pressure sensor 7 which is arranged on the hydrogen discharge pipeline, one end of the hydrogen discharge pipeline is connected with the composite solid-state hydrogen storage tank 3, and the pressure sensor 7 is used for monitoring the real-time pressure during the hydrogen discharge of the composite solid-state hydrogen storage tank 3; preferably, an electromagnetic valve 8, a mass flow controller 5, a back pressure valve 9, a hydrogen discharge on-off valve 43 and a check valve 10 are arranged on the hydrogen discharge pipeline in sequence along the gas flow direction. The mass flow controller needs to have a certain pressure difference when measuring the flow, so a back pressure valve and a one-way valve are added to ensure that the front side and the rear side of the mass flow controller are in the range of the test pressure difference.
The gaseous hydrogen cylinder 1, the vacuum pump 2 and the pressure sensor 7 are connected with the composite solid hydrogen storage tank 3 through a gas path interface;
preferably, the air passage interface is connected with the opening of the composite solid hydrogen storage tank 3 through a metal braided hose and 1/4 quick connector.
The scheme of the invention, and the method and the result of the hydrogen storage performance detection by using the hydrogen storage tank provided by the invention are specifically described by the following specific examples.
The hydrogen storage alloys of the invention are all rare earth AB5A type alloy in which the A side is composed of La and at least 1 of the elements of Ce, Pr, Nd, Sm, Gd, Dy, Mg, Ti and Zr, and the B side metal is composed of Ni and at least 1 of the elements of Co, Mn, Cu, Fe, Si, Al, Sn, Cr, Zn, B, V, W, Mo, Ta and Nb as raw materials. The hydrogen occluding alloy used in the following examples and comparative examples was La0.9Ce0.1Ni4.7Co0.1Mn0.1Al0.1(the subscripts of each element represent the molar ratio of each element).
In the following examples, in order to facilitate the test of the hydrogen storage performance of the hydrogen storage tanks, hydrogen storage tanks having an outer diameter of 85mm, an inner diameter of 85mm, a straight cylinder portion of 280mm in length and a capacity of 1L were used. According to the size of the hydrogen storage tank, when the aluminum foil is divided, the aluminum foil with the thickness of 0.2-0.5mm can be used and divided into strips with the length of 270-275mm and the width of 75-85mm, the aluminum foil with the length of 270mm and the width of 80mm can be preferred, and the sizes of all the aluminum foils used in one hydrogen storage tank are preferably consistent. The method for putting the aluminum foil into the tank body can be that the tank body is cut, then the aluminum foil is laid in, and then the cut tank body is welded and sealed.
The specific preparation method of the hydrogen occluding alloy powder used in the following examples was:
pretreatment of raw materials: polishing to remove surface oxides of the raw material rare earth metal, and drying moisture in the raw material metal such as nickel;
vacuum induction melting: adding Al into raw material metal according to the sequence of melting point and boiling point from bottom to top (bottom melting point and boiling point are highest)2O3Vacuumizing a crucible to 0.001-0.01 Pa, then baking and washing the crucible, filling inert gas to 0.04-0.05 MPa, adjusting power to start smelting, controlling the melt temperature to be 1300-1500 ℃, refining for 3-10 minutes after molten steel is completely melted, pouring into a water-cooled copper mold, and cooling for 40min and taking out;
and (3) heat treatment: and (3) carrying out heat treatment at the temperature of 800-1150 ℃ for 5-10h by using a high vacuum annealing furnace to finally obtain the hydrogen storage alloy block.
Preparing hydrogen storage alloy powder: and under the nitrogen protection atmosphere, carrying out high-energy crushing on the hydrogen storage alloy blocks to prepare powder by adopting 5MPa high-pressure gas nitrogen formed by compression of an air compressor, and grinding and screening by adopting a multi-layer rotary vibration screen after crushing to finally obtain hydrogen storage alloy powder with the granularity of 75-300 mu m.
Example 1
Preparing an aluminum material: spherical aluminum powder with the particle size of 1-10 mu m is selected as the aluminum material.
Preparing aluminum-containing composite hydrogen storage alloy powder: 3200g of the hydrogen storage alloy powder is taken, 565g of spherical aluminum powder is weighed, the aluminum powder accounts for 15% of the total mass of the composite material (namely the hydrogen storage alloy powder and the aluminum powder), the spherical aluminum powder and the aluminum powder are mixed by a stirrer for 2 hours, then all the aluminum-containing composite hydrogen storage alloy powder is filled into a hydrogen storage tank body, and the aluminum-containing composite hydrogen storage alloy powder accounts for about 80% of the volume of the hydrogen storage tank body.
Charging hydrogen and activating the aluminum-based hydrogen storage alloy powder in the hydrogen storage tank: the hydrogen storage tank is arranged on a hydrogen filling and activating treatment device of the hydrogen storage tank, the hydrogen storage tank is placed in a heating sleeve, the temperature is controlled at 90 ℃, the hydrogen storage tank is connected with a vacuum pump, a ball valve and the vacuum pump are opened, air in the hydrogen storage tank is pumped out, the vacuumizing time is 6 hours, then the hydrogen storage tank is filled with 2MPa hydrogen, and the pressure is kept for 6 hours.
Testing hydrogen storage performance: and (3) carrying out a hydrogen discharge performance test on the activated hydrogen storage tank, controlling the hydrogen discharge temperature at 50 ℃, controlling the hydrogen discharge flow rate at 8L/min, and stopping recording the time when the hydrogen discharge rate is lower than 6L/min, wherein the time at this moment is the time when the hydrogen storage tank can discharge hydrogen.
Fig. 4 is a graph showing the change of the hydrogen discharge flow and the hydrogen discharge pressure of the composite solid-state hydrogen storage tank with time in this embodiment, and it can be seen from the graph that the hydrogen discharge of the hydrogen storage tank can reach 45min at a hydrogen discharge flow rate of 8L/min, the hydrogen discharge amount reaches 360L, the hydrogen discharge amount accounts for 71.8% of the total hydrogen storage amount, the hydrogen flow rate is stable, and the hydrogen discharge performance is good. In addition, the hydrogen releasing pressure of the hydrogen storage tank is mainly stabilized between 0.1 MPa and 0.5MPa, and the hydrogen releasing pressure is relatively stable.
Example 2
Preparing an aluminum material: an aluminum foil with the thickness of 0.3mm is selected as the composite aluminum material, and the composite aluminum material is equally divided into strips with the length of 270mm and the width of 80 mm.
Preparing aluminum-based hydrogen storage alloy powder: weighing 80g of hydrogen storage alloy powder, paving the hydrogen storage alloy powder on an aluminum foil, continuously paving the aluminum foil with the same size on the alloy powder, continuously weighing the hydrogen storage alloy powder with the same mass, paving the hydrogen storage alloy powder on the aluminum foil, sequentially carrying out the operations until the number of layers of the aluminum foil and the hydrogen storage alloy powder reaches 40, namely the uppermost layer is a hydrogen storage alloy powder layer, completely filling 40 layers of aluminum foil alloy powder in a hydrogen storage tank with an opening at the top of a straight cylinder in a sandwich manner, and then sealing the hydrogen storage tank.
Charging hydrogen and activating the aluminum-based hydrogen storage alloy powder in the hydrogen storage tank:
the hydrogen storage tank is arranged on a hydrogen filling and activating treatment device of the hydrogen storage tank, the hydrogen storage tank is placed in a heating sleeve, the temperature is controlled at 90 ℃, the hydrogen storage tank is connected with a vacuum pump, a ball valve and the vacuum pump are opened, air in the hydrogen storage tank is pumped out, the vacuumizing time is 6 hours, then the hydrogen storage tank is filled with 2MPa hydrogen, and the pressure is kept for 6 hours.
Testing hydrogen storage performance: and (3) carrying out a hydrogen discharge performance test on the activated hydrogen storage tank, controlling the hydrogen discharge temperature at 50 ℃, controlling the hydrogen discharge flow rate at 8L/min, and stopping recording the time when the hydrogen discharge rate is lower than 6L/min, wherein the time at this moment is the time when the hydrogen storage tank can discharge hydrogen.
Fig. 5 is a graph showing the change of the hydrogen discharge flow and the hydrogen discharge pressure of the aluminum-material hydrogen storage alloy composite hydrogen storage tank with time in this embodiment, and it can be seen from the graph that the hydrogen discharge of the hydrogen storage tank can reach 57min at a hydrogen discharge flow rate of 8L/min, the hydrogen discharge amount reaches 456L, the hydrogen discharge amount accounts for 90.8% of the total hydrogen storage amount, the hydrogen flow rate is stable, and the hydrogen discharge performance is excellent. In addition, the hydrogen releasing pressure of the hydrogen storage tank is mainly stabilized between 0.1 MPa and 0.5MPa, and the hydrogen releasing pressure is stable.
Example 3
Preparing an aluminum material: the aluminum fiber with the fiber length of 30-40mm and the diameter of 1-2mm is selected as the composite aluminum material.
Preparing aluminum-based hydrogen storage alloy powder: 565g of aluminum fiber, 3200g of hydrogen storage alloy powder, wherein the mass of the aluminum fiber accounts for 15 percent of the total mass of the composite material. The preparation process comprises the following steps: respectively dividing 40 parts of aluminum fiber and hydrogen storage alloy powder, firstly weighing 14.125g of aluminum fiber, 1/40 of aluminum fiber accounting for the total mass of the aluminum fiber, filling the aluminum fiber and the hydrogen storage alloy powder into a hydrogen storage tank, then weighing 80g of hydrogen storage alloy powder, filling the hydrogen storage tank with the hydrogen storage alloy powder layer by layer in an alternating and circulating manner, and filling 40 layers of aluminum fiber and hydrogen storage alloy powder layer respectively until all the materials are filled into the hydrogen storage tank.
Charging hydrogen and activating the aluminum-based hydrogen storage alloy powder in the hydrogen storage tank:
the hydrogen storage tank is arranged on a hydrogen filling and activating treatment device of the hydrogen storage tank, the hydrogen storage tank is placed in a heating sleeve, the temperature is controlled at 90 ℃, the hydrogen storage tank is connected with a vacuum pump, a ball valve and the vacuum pump are opened, air in the hydrogen storage tank is pumped out, the vacuumizing time is 6 hours, then the hydrogen storage tank is filled with 2MPa hydrogen, and the pressure is kept for 6 hours.
Testing hydrogen storage performance: and (3) carrying out a hydrogen discharge performance test on the activated hydrogen storage tank, controlling the hydrogen discharge temperature at 50 ℃, controlling the hydrogen discharge flow rate at 8L/min, and stopping recording the time when the hydrogen discharge rate is lower than 6L/min, wherein the time at this moment is the time when the hydrogen storage tank can discharge hydrogen.
The aluminum material hydrogen storage alloy composite hydrogen storage tank prepared in the embodiment: at the temperature of 50 ℃, the hydrogen can be discharged for 49min at the hydrogen discharge flow rate of 8L/min, the hydrogen discharge amount reaches 392L, the hydrogen discharge amount accounts for 78.1 percent of the total hydrogen storage amount, the hydrogen flow rate is stable, and the hydrogen discharge performance is excellent. In addition, the hydrogen releasing pressure of the hydrogen storage tank is mainly stabilized between 0.1 MPa and 0.5MPa, and the hydrogen releasing pressure is stable.
Comparative example 1 and examples 4 to 8
The preparation processes of comparative example 1 and examples 4 to 8 listed in table 1 are the same as those given in example 1, and comparative example 1 and examples 4 to 8 are different from example 1 in that the contents and particle sizes of the spherical aluminum powders selected are different, and specific parameters are shown in table 1 below.
TABLE 1 content, particle size and Hydrogen evolving Effect of spherical aluminum powder in comparative example 1 and examples 4 to 8
Figure BDA0002264862050000141
As can be seen from Table 1, in comparative example 1, in which spherical aluminum powder was not added, the hydrogen evolution time was the shortest and the volume and percentage of hydrogen evolved were the smallest. The hydrogen release time of the examples 4-8 added with spherical aluminum powder is increased to different degrees, but is less than that of the example 1, and the hydrogen release volume and percentage are reduced.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
The above is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An aluminum-containing composite hydrogen storage alloy is characterized in that the aluminum-containing composite hydrogen storage alloy is made of 80-98% of hydrogen storage alloy powder and 2-20% of aluminum material in percentage by mass.
2. The aluminum-containing composite hydrogen occluding alloy as recited in claim 1,
the aluminum material comprises one or more of spherical aluminum powder, aluminum foil and aluminum fiber;
preferably, when the aluminum material is spherical aluminum powder, the aluminum-containing composite hydrogen storage alloy is a mixed powder of the spherical aluminum powder and the hydrogen storage alloy powder;
when the aluminum material is an aluminum foil, the aluminum-containing composite hydrogen storage alloy has a sandwich-like structure in which hydrogen storage alloy powder is sandwiched between adjacent strip-shaped aluminum foils, preferably, the number of layers of the strip-shaped aluminum foils in the aluminum-containing composite hydrogen storage alloy is 30-50, and the mass of each layer of the hydrogen storage alloy powder sandwiched between the adjacent strip-shaped aluminum foils is the same;
when the aluminum material is aluminum fiber, the aluminum-containing composite hydrogen storage alloy has a sandwich-like structure in which hydrogen storage alloy powder is sandwiched between adjacent aluminum fiber layers, preferably, the number of the aluminum fiber layers in the aluminum-containing composite hydrogen storage alloy is 30-50, and the mass of the hydrogen storage alloy powder in each layer sandwiched between the adjacent aluminum fiber layers is the same; the quality of each layer of aluminum fiber is the same; preferably, the particle size of the spherical aluminum powder is 1-200 μm;
preferably, the thickness of the aluminum foil is 0.2-0.5 mm;
preferably, the length of the aluminum fiber is 30-40mm, and the diameter of the aluminum fiber is 1-2 mm.
3. The aluminum-containing composite hydrogen occluding alloy according to claim 1 or 2,
the hydrogen storage alloy powder comprises rare earth AB5Type, titanium AB type2One or more of type and titanium vanadium solid solution type hydrogen storage alloy powder;
preferably, the average particle size of the hydrogen storage alloy powder is 75-300 μm;
preferably, the rare earth system AB5In the hydrogen occluding alloy powder of type A, the A-side metal is composed of La and at least 1 of the elements of the group of Ce, Pr, Nd, Sm, Gd, Dy, Mg, Ti and Zr, and the B-side metal is composed of Ni and at least 1 of the elements of the group of Co, Mn, Cu, Fe, Si, Ge, Sn, Cr, Zn, B, V, W, Mo, Ta and Nb.
4. A method for preparing the aluminum-containing composite hydrogen storage alloy of any one of claims 1 to 3, comprising the steps of:
a step of preparing hydrogen storage alloy powder;
a step of preparing the aluminum material;
and preparing the aluminum-containing composite hydrogen storage alloy by matching the aluminum material with the hydrogen storage alloy powder.
5. The method of claim 4,
the step of preparing the hydrogen storage alloy powder includes:
smelting the raw materials of the hydrogen storage alloy powder to prepare a hydrogen storage alloy ingot, and then carrying out vacuum annealing homogenization treatment on the alloy ingot, wherein the smelting temperature is 1300-1500 ℃, the vacuum annealing homogenization treatment temperature is 800-1150 ℃, and the annealing time is 5-10 h; and then crushing and ball-milling the annealed hydrogen storage alloy ingot to obtain the hydrogen storage alloy powder.
6. The method of claim 4,
in the step of preparing the aluminum-containing composite hydrogen storage alloy by compounding the aluminum material with the hydrogen storage alloy powder,
when the aluminum material is spherical aluminum powder, mechanically stirring and mixing the hydrogen storage alloy powder and the spherical aluminum powder to obtain the aluminum-containing composite hydrogen storage alloy;
when the aluminum material is an aluminum foil, a hydrogen storage alloy powder layer is laid on one strip-shaped aluminum foil, then another strip-shaped aluminum foil is laid on the hydrogen storage alloy powder layer, and the hydrogen storage alloy powder layers except the uppermost layer are continuously laminated to the required number of layers in a manner of respectively clamping the hydrogen storage alloy powder layers between the adjacent strip-shaped aluminum foil layers, so that the aluminum-containing composite hydrogen storage alloy with the sandwich-like structure is formed; preferably, the number of layers of the strip-shaped aluminum foil in the aluminum-containing composite hydrogen storage alloy is 30-50; more preferably, the weight of each layer of hydrogen storage alloy powder interposed between adjacent strip-shaped aluminum foil layers is the same, and the size of the strip-shaped aluminum foil of each layer is the same;
when the aluminum material is aluminum fiber, firstly, laying an aluminum fiber layer by adopting the aluminum fiber, then laying a hydrogen storage alloy powder layer on the aluminum fiber layer, then laying another aluminum fiber layer on the hydrogen storage alloy powder layer, and continuously laminating to the required number of layers in a manner that all hydrogen storage alloy powder layers except the uppermost layer are clamped on the adjacent aluminum fiber layers, thereby forming the aluminum-containing composite hydrogen storage alloy with the sandwich type structure; preferably, the number of the aluminum fiber layers in the aluminum-containing composite hydrogen storage alloy is 30-50; more preferably, the weight of each layer of hydrogen occluding alloy powder interposed between adjacent aluminum fiber layers is the same; the weight of each layer of aluminum fiber is the same.
7. A composite solid hydrogen storage tank, comprising a tank body and the aluminum-containing composite hydrogen storage alloy according to any one of claims 1 to 3 disposed in the tank body;
preferably, the material of the tank body is metal aluminum or aluminum alloy, and more preferably 616 aluminum alloy; further preferably, the can body includes a straight tube portion and an opening portion that is extended and narrowed from the straight tube portion;
more preferably, the composite solid-state hydrogen storage tank further comprises a filter and a valve, wherein the filter is embedded in the opening portion of the tank body,
the valve is arranged on the opening part and is used for closing or opening the opening part of the tank body;
preferably, the inner diameter of the tank body of the hydrogen storage tank is 70-80mm, the outer diameter is 80-90mm, the length of the straight cylinder part is 275-285mm, and the volume is 1-1.5L; more preferably, the outer diameter of the body of the hydrogen storage tank is 85mm, the inner diameter is 85mm, the length of the straight cylinder part is 280mm, and the volume is 1L.
8. The method for testing the hydrogen storage performance of the composite solid-state hydrogen storage tank according to claim 7, characterized by comprising the steps of:
installing the composite solid hydrogen storage tank into a hydrogen storage tank hydrogen charging and activating treatment device, and sequentially performing activation, hydrogen charging and hydrogen discharging performance tests on the aluminum-containing composite hydrogen storage alloy in the composite solid hydrogen storage tank;
preferably, the activating and charging comprises: controlling the temperature of the composite solid hydrogen storage tank within the range of 80-120 ℃, and simultaneously carrying out vacuum pumping treatment on the composite solid hydrogen storage tank for 5-10 h; filling hydrogen into the composite solid hydrogen storage tank, wherein the pressure of the hydrogen in the composite solid hydrogen storage tank is 2-10MPa, and the pressure holding time is 5-10 h;
preferably, the hydrogen discharge performance test comprises: controlling the hydrogen release temperature to be 5-50 ℃, controlling the hydrogen release flow rate to be 2-8L/min, monitoring the pressure value in the hydrogen storage tank in real time, and stopping hydrogen release time recording when the hydrogen release flow rate is reduced to a preset flow rate to obtain the hydrogen release time and the hydrogen release amount of the hydrogen storage tank at a specific speed;
obtaining the hydrogen release amount percentage of the hydrogen storage tank in a specific time according to the obtained ratio of the hydrogen release amount to the total hydrogen storage amount of the hydrogen storage tank;
preferably, the hydrogen discharge flow rate is controlled to be 8L/min at 50 ℃, and when the hydrogen discharge flow rate is reduced to 6L/min, the hydrogen discharge time recording is stopped.
9. The test method according to claim 8,
the hydrogen storage tank hydrogen filling and activating treatment device comprises: a vacuum pump, a gaseous hydrogen cylinder and a water bath;
the vacuum pump is connected with the composite solid-state hydrogen storage tank through a vacuum pumping pipeline and is used for vacuumizing the composite solid-state hydrogen storage tank, and preferably, a vacuum pumping switch valve is arranged on the vacuum pumping pipeline;
the gaseous hydrogen cylinder is connected with the composite solid hydrogen storage tank through a hydrogen charging pipeline and used for supplying hydrogen to the hydrogen storage tank, and preferably, a pressure reducing valve, a mass flow controller and a hydrogen charging switch valve are sequentially arranged on the hydrogen charging pipeline along the hydrogen flow direction;
the water bath is arranged outside the composite solid hydrogen storage tank and used for heating the composite solid hydrogen storage tank.
10. The test method according to claim 9, wherein the hydrogen storage tank hydrogen charging and activation processing device further comprises:
the pressure sensor is arranged on a hydrogen discharge pipeline, one end of the hydrogen discharge pipeline is connected with the composite solid hydrogen storage tank, and the pressure sensor is used for monitoring the real-time pressure of the composite solid hydrogen storage tank during hydrogen discharge; preferably, an electromagnetic valve, a mass flow controller, a back pressure valve, a hydrogen discharge switch valve and a one-way valve are sequentially arranged on the hydrogen discharge pipeline along the gas flowing direction.
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