CN111288291B - High-pressure hydrogen storage bottle - Google Patents
High-pressure hydrogen storage bottle Download PDFInfo
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- CN111288291B CN111288291B CN202010097555.8A CN202010097555A CN111288291B CN 111288291 B CN111288291 B CN 111288291B CN 202010097555 A CN202010097555 A CN 202010097555A CN 111288291 B CN111288291 B CN 111288291B
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- 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
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/005—Storage of gas or gaseous mixture at high pressure and at high density condition, e.g. in the single state phase
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- 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
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/10—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge with provision for protection against corrosion, e.g. due to gaseous acid
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- 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
- F17C2203/0602—Wall structures; Special features thereof
- F17C2203/0612—Wall structures
- F17C2203/0626—Multiple walls
- F17C2203/0631—Three or more walls
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- 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
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- 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
- F17C2203/0658—Synthetics
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- 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
- F17C2203/0658—Synthetics
- F17C2203/0663—Synthetics in form of fibers or filaments
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- 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
- F17C2203/0658—Synthetics
- F17C2203/0663—Synthetics in form of fibers or filaments
- F17C2203/067—Synthetics in form of fibers or filaments helically wound
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- 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
- F17C2209/00—Vessel construction, in particular methods of manufacturing
- F17C2209/21—Shaping processes
- F17C2209/2154—Winding
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- 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
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- 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
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0107—Single phase
- F17C2223/0123—Single phase gaseous, e.g. CNG, GNC
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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
Abstract
The invention belongs to the technical field of hydrogen storage bottles, and particularly relates to a high-pressure hydrogen storage bottle which is characterized by comprising the following components: the liner comprises a liner, a first fiber layer and a second fiber layer, wherein the first fiber layer is wound on the outer surface of the liner, and the second fiber layer is wound on the surface of one side, far away from the liner, of the first fiber layer; the first fiber layer is made of carbon nanotube fibers, and the second fiber layer is made of fibers except for the carbon nanotube fibers. The high-pressure hydrogen storage bottle provided by the invention has the advantages that the first fiber layer and the second fiber layer are matched with each other, so that the toughness of the tank body is improved, the working pressure and the impact resistance of the tank body are enhanced, the storage stability is improved, and the high-pressure hydrogen storage bottle is particularly suitable for storing hydrogen.
Description
Technical Field
The invention relates to a hydrogen storage bottle, in particular to a high-pressure hydrogen storage bottle.
Background
With the development of hydrogen energy vehicles, not only is a light, compact, safe and economic storage mode required for hydrogen storage, but also the endurance requirement of the vehicle is met at least to 500 km, so that higher and higher requirements are provided for hydrogen storage technology. Although there are a wide variety of hydrogen storage technologies, none fully meets all the requirements of the automotive industry. In fact, finding a solution to the hydrogen storage problem is considered by many to be a primary challenge in hydrogen economy.
At present, hydrogen is mainly stored: as a compressed gas in a high pressure hydrogen storage cylinder; stored in a dewar or tank in liquid form (stored at-253 ℃); by absorption or reaction with a metal or compound to form a solid, or stored in another chemical form. Among them, high-pressure gaseous hydrogen storage has been widely used, low-temperature liquid hydrogen storage has been used in the fields of aerospace, etc., and organic liquid hydrogen storage and solid hydrogen storage are still in the demonstration stage.
High pressure gaseous hydrogen storage is one of the most common and widely used hydrogen storage methods, and uses a gas cylinder as a storage container to store gaseous hydrogen by a high pressure compression method. The hydrogen gas releasing device has the advantages of low cost, relatively low energy consumption, high hydrogen gas releasing speed regulated by the pressure reducing valve, high gas releasing and releasing speed, good dynamic response and capacity of instantly opening and closing hydrogen gas. Currently, high pressure hydrogen storage bottles can be mainly divided into four types: the gas cylinder comprises an all-metal gas cylinder (type I), a metal liner fiber hoop winding gas cylinder (type II), a metal liner fiber all-winding gas cylinder (type III) and a nonmetal liner fiber all-winding gas cylinder (type IV). The high-pressure hydrogen storage bottles are difficult to meet the hydrogen storage density requirement of a hydrogen fuel cell automobile, the winding fibers are usually wound by single carbon fibers, the uniformity of tows of the high-pressure hydrogen storage bottles is difficult to guarantee, and the problems of too many broken filaments, serious filament breakage, poor wettability with resin, unstable winding, easiness in slippage, and the like can be caused to cause the tows to be intertwined in practical application. And the single carbon fiber has limited performance, and cannot meet the requirement of a high-pressure hydrogen storage bottle with higher performance in the future.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a high-pressure hydrogen storage bottle, and aims to solve the problems that the performance of the existing high-pressure hydrogen storage bottle is improved in a limited way by winding a single fiber tow on the surface.
Means for solving the problems
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a high pressure hydrogen storage cylinder comprising: the liner comprises a liner, a first fiber layer and a second fiber layer, wherein the first fiber layer is wound on the outer surface of the liner, and the second fiber layer is wound on the surface of one side, far away from the liner, of the first fiber layer; the first fiber layer is made of carbon nanotube fibers, and the second fiber layer is made of fibers except for the carbon nanotube fibers.
Preferably, the first fiber layer comprises: the carbon nano tube fiber circumferential winding layers and the carbon nano tube fiber spiral winding layers are alternately arranged; and/or the presence of a gas in the gas,
the second fibrous layer comprises: the second fiber circumferential winding layers and the second fiber spiral winding layers are alternately arranged; and/or the presence of a gas in the gas,
the tensile modulus of the fibers in the second fiber layer is 5% to 10% lower than the tensile modulus of the fibers in the first fiber layer.
Preferably, the carbon nanotube fibers are carbon nanotube fibers soaked by resin;
the other fibers are other fibers soaked by resin.
Preferably, in the first fiber layer, the circumferential winding layer of the carbon nanotube fiber and the spiral winding layer of the carbon nanotube fiber are respectively provided with 2-10 layers; and/or the presence of a gas in the gas,
in the second fiber layer, the second fiber ring direction winding layer and the second fiber spiral winding layer are respectively provided with 2-10 layers.
Preferably, the thickness of the first fiber layer is 5-8 mm; and/or the presence of a gas in the gas,
the thickness of the second fiber layer is 4-7 mm.
Preferably, in the first fiber layer, the volume fraction of the carbon nanotube fibers is 60% to 70%; and/or the presence of a gas in the gas,
in the second fiber layer, the volume fraction of the other fibers is 60-70%; and/or the presence of a gas in the gas,
the volume of the carbon nanotube fiber accounts for more than 50% of the total volume of the first fiber layer and the second fiber layer.
Preferably, the included angle between the carbon nanotube fiber in the carbon nanotube fiber spiral winding layer and the central axis of the inner container is 10-20 degrees; and/or the presence of a gas in the gas,
and the included angle between the second fiber and the central shaft of the inner container in the second fiber spiral winding layer is 50-55 degrees.
Preferably, the carbon nanotube fiber comprises 3-4 carbon nanotube fiber bundles, and the carbon nanotube fiber bundles comprise 6000-8000 carbon nanotube fiber filaments; and/or the presence of a gas in the gas,
the resins in the first fiber layer and the second fiber layer are each independently selected from the group consisting of: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin.
Preferably, the inner container is a cylindrical metal inner container, and two ends of the metal inner container are arc-shaped; and/or the presence of a gas in the gas,
the inner container is a single-layer or composite-layer inner container; and/or the presence of a gas in the gas,
the thickness of the inner container is 3-6 mm.
Preferably, an adhesive layer is further included between the inner container and the first fiber resin layer, and/or,
the material of the bonding layer is selected from: at least one of polyurethane, acrylic, epoxy, chlorinated rubber, and/or,
the thickness of the bonding layer is 0.5-1.0 mm; and/or the presence of a gas in the gas,
and a bonding layer is also arranged between the inner container and the first fiber layer.
Effects of the invention
The high-pressure hydrogen storage bottle provided by the invention comprises a first fiber layer and a second fiber layer which are sequentially stacked on the outer surface of an inner container, wherein the first fiber layer is made of carbon nano tube fibers, and the second fiber layer is made of other fibers except the carbon nano tube fibers. The carbon nanotube fiber has good flexibility, certain elasticity, flexibility and smoothness, and can be tightly attached to the radian of the liner tank body and the liner and the second fiber layer, so that the toughness of the liner tank body is improved, and the impact bearing capacity of the tank body is enhanced. And the carbon nanotube fibers formed by the van der waals force among the carbon nanotubes in the first fiber layer are well infiltrated with the resin, so that the slippage of the fibers in the winding and resin melting and impregnating processes is effectively avoided, and the carbon nanotube fibers are uniformly dispersed, thereby ensuring that the first fiber layer can uniformly bear the load of the liner tank body, and simultaneously, the effective stress transfer can be carried out, so that the tank body has high strength and high modulus. In addition, the second fiber layers such as carbon fibers and the like are used as outer layers, so that effective stress transfer can be carried out, external impact can be borne, the first fiber layers are protected, and the defects of the conventional single-fiber high-pressure hydrogen storage bottle are overcome. The high-pressure hydrogen storage bottle provided by the invention has the advantages that the first fiber layer and the second fiber layer are matched with each other, so that the toughness of the tank body is improved, the working pressure and the impact resistance of the tank body are enhanced, the storage stability is improved, and the high-pressure hydrogen storage bottle is particularly suitable for storing hydrogen.
Drawings
Fig. 1 is a schematic cross-sectional view of a container provided by an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a first fiber layer and a second fiber layer of a container provided by an embodiment of the invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
As shown in fig. 1, an embodiment of the present invention provides a high pressure hydrogen storage cylinder, including: the liner comprises a liner, a first fiber layer and a second fiber layer, wherein the first fiber layer is wound on the outer surface of the liner, and the second fiber layer is wound on the surface of one side, far away from the liner, of the first fiber layer; the first fiber layer is made of carbon nanotube fibers, and the second fiber layer is made of fibers except for the carbon nanotube fibers.
The high-pressure hydrogen storage bottle provided by the embodiment of the invention comprises a first fiber layer and a second fiber layer which are sequentially stacked on the outer surface of an inner container, wherein the first fiber layer is made of carbon nanotube fibers, and the second fiber layer is made of other fibers except the carbon nanotube fibers. The carbon nanotube fiber has good flexibility, certain elasticity, flexibility and smoothness, and can be tightly attached to the radian of the liner tank body and the liner and the second fiber layer, so that the toughness of the liner tank body is improved, and the impact bearing capacity of the tank body is enhanced. And the carbon nanotube fibers formed by Van der Waals forces among the carbon nanotubes in the first fiber layer are well infiltrated with the resin, so that slippage of the fibers in the winding and resin melting and impregnation processes is effectively avoided, the carbon nanotube fibers are uniformly dispersed, the first fiber layer can uniformly bear the load of the liner tank body, and meanwhile, effective stress transfer can be carried out, so that the tank body has high strength and high modulus. In addition, the second fiber layers such as carbon fiber and the like are used as outer layers, so that effective stress transfer can be carried out, external impact can be borne, the first fiber layer is protected, and the defects of the conventional single-fiber high-pressure hydrogen storage bottle are overcome. According to the high-pressure hydrogen storage bottle provided by the embodiment of the invention, the first fiber layer and the second fiber layer are matched with each other, so that the toughness of the tank body is improved, the working pressure and the impact resistance of the tank body are enhanced, the storage stability is improved, and the high-pressure hydrogen storage bottle is particularly suitable for storing hydrogen.
In some embodiments, the carbon nanotube fibers are resin-impregnated carbon nanotube fibers. In some embodiments, the other fibers are other fibers impregnated with a resin. According to the embodiment of the invention, the carbon nanotube fiber or other fibers are soaked in the resin and then wound to form the fiber layer, so that the fiber can be further prevented from slipping in the winding process, the resin in the fiber soaked in the resin is uniformly distributed and has better bonding tightness with the liner, and the coating effect of the fiber layer is favorably improved.
In some embodiments, the resins in the first fiber layer and the second fiber layer are each independently selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin, wherein the resins have good thermosetting property, so that the fiber layer can be stably bonded on the surface of the liner, and the storage stability of the container is improved; the epoxy resin also has excellent corrosion resistance, can prevent the liner from being corroded, and prolongs the service life; in addition, the epoxy resin can function to conduct loads and protect fibers, etc.
In some embodiments, the fibers in the second fiber layer do not include carbon nanotube fibers, and may be any other fibers such as carbon fibers. In some embodiments, the tensile modulus of the fibers in the second fibrous layer is 5% to 10% lower than the tensile modulus of the fibers in the first fibrous layer. The tensile modulus of the first fiber layer sequentially laminated on the outer side of the inner container outer layer is 5% -10% higher than that of the second fiber layer arranged on the outer side of the inner container outer layer, the difference value of the tensile modulus is more beneficial to the transmission of stress generated by the inner container under high pressure between the two functional layers, reasonable stress sharing is realized, and meanwhile, the second fiber layer is ensured to have better external impact resistance and can effectively bear external impact.
As shown in fig. 2, in some embodiments, the first fibrous layer comprises: the carbon nanotube fiber circumferential winding layers and the carbon nanotube fiber spiral winding layers are alternately arranged. In some embodiments, the second fibrous layer comprises: the second fiber circumferential winding layers and the second fiber spiral winding layers are arranged alternately. The first fiber layer arranged on the outer side of the inner container comprises the carbon nano tube fiber annular winding layers and the carbon nano tube fiber spiral winding layers which are alternately arranged, the second fiber layer comprises the second fiber annular winding layers and the second fiber spiral winding layers which are alternately arranged, the annular winding layers can effectively eliminate annular stress generated by the inner container under internal pressure, the spiral winding layers can provide longitudinal stress for the inner container, and the annular stress and the longitudinal stress of the inner container can be eliminated simultaneously through the annular winding layers and the spiral winding layers which are alternately arranged, so that the overall performance of the inner container is improved.
In some embodiments, in the first fiber layer, the circumferential winding layer of carbon nanotube fibers and the spiral winding layer of carbon nanotube fibers are respectively provided with 2-10 layers. In some embodiments, the second fiber layer comprises 2-10 layers of the second fiber hoop winding layer and the second fiber spiral winding layer. According to the embodiment of the invention, 2-10 annular winding layers and spiral winding layers are alternately arranged, so that the annular and longitudinal stresses of the liner are better eliminated, the overall performance of the liner is improved, and the load of a carrier is improved.
In some embodiments, the first fibrous layer has a thickness of 5 to 8 millimeters. In some embodiments, the second fibrous layer has a thickness of 4 to 7 millimeters. According to the embodiment of the invention, the first fiber layer with the thickness of 5-8 mm and the second fiber layer with the thickness of 4-7 mm effectively ensure the load of the fiber layers on the internal stress of the liner tank body, so that the container can meet different high-pressure application environments, and is stable in storage and good in safety performance. If the thickness of the fiber layer is too thin, the fiber layer cannot effectively bear and dredge the internal stress of the tank body; if the thickness of the fiber layer is too thick, the manufacturing cost is increased, and meanwhile, the fiber layer wrapped outside the inner container can also apply excessive pressure to the inner container, which is also not beneficial to high-pressure storage of the tank body.
In some embodiments, the volume fraction of carbon nanotube fibers in the first fiber layer is 60% to 70%. In some embodiments, the second fiber layer has a volume fraction of second fibers of 60 to 70%. The volume fraction of fibers in the fiber resin layer coated outside the inner container is 60-70%, and the fibers in the volume ratio effectively ensure the reinforcing effect of the fibers in each fiber layer; in addition, the resin with the volume fraction of 30-40% in the fiber layer serves as a matrix, the effects of transferring load and protecting fibers are achieved, fibers are uniformly and stably distributed on the outer surface of the liner, fiber slippage in the lower fiber layer is prevented, the transmission and reinforcing effects of the first fiber layer and the second fiber layer on the stress of the tank body are further improved, and the storage stability of the tank body is improved. If the fiber volume ratio in the fiber layer is too low, the reinforcing effect of the fibers is limited; if the fiber content is too high, the resin matrix cannot effectively transmit the load to the fibers through the interface, at which time the fiber amount is large and the performance is poor.
In some embodiments, the volume of carbon nanotube fibers is greater than 50% of the total volume of the first fiber layer and the second fiber layer. The volume ratio of the carbon nanotube fibers in the fiber layer coated outside the inner container reaches 50%, so that the carbon nanotube fibers with the characteristics of good flexibility, elasticity, flexibility, smoothness and the like have a good enhancement effect on the internal stress of the inner container tank body, and the toughness and the load of the tank body are improved.
In some embodiments, the carbon nanotube fiber in the carbon nanotube fiber spiral winding layer forms an angle with the central axis of the inner container of 10 to 20 °. In the carbon nanotube fiber spiral winding layer provided by the embodiment of the invention, the carbon nanotube fiber is wound at a low angle of 10-20 degrees, the circumferential winding of the drum part is strengthened, the winding on the edge and the bottom of the liner is strengthened, the number of winding turns is reduced, and the fiber consumption is reduced by 40%.
In some embodiments, the second fibers in the second fiber spiral winding layer form an included angle of 50-55 degrees with the central axis of the liner. According to the embodiment of the invention, the winding angle of the fibers in the second fiber spiral winding resin layer is 50-55 degrees larger than that in the carbon nanotube fiber spiral winding layer, so that the transition edge of the cylinder part and the bottom of the liner can be further strengthened, and all parts of the liner are strengthened through the low-angle matching with the carbon nanotube fiber winding. And the second fibers are wound at an angle of 50-55 degrees, so that the second fiber layer can obtain the best stress, and the reinforcing effect on the inner container tank body is further improved.
In some embodiments, the carbon nanotube fiber comprises 3-4 carbon nanotube fiber bundles, and the carbon nanotube fiber bundles comprise 6000-8000 carbon nanotube fiber filaments. According to the embodiment of the invention, the carbon nanotube fiber bundle can be prepared by directly pulling out a carbon nanotube film with the width of 0.1-20 cm from a carbon nanotube array, twisting the carbon nanotube film according to the twist of 100-15000 tpm, combining 3-4 carbon nanotube fiber bundles into one carbon nanotube fiber in a doubling mode, and winding the inner container by using the carbon nanotube fiber to form the carbon nanotube fiber layer.
In some embodiments, the inner container is a cylindrical metal inner container, and two ends of the metal inner container are in arc shapes such as a semicircle or an ellipse. In some embodiments, the liner is a single or composite layer liner. In some embodiments, the inner container is selected from a seamless columnar aluminum alloy structure with the thickness of 3-6 mm. The inner container provided by the embodiment of the invention has good corrosion resistance, can be used for storing hydrogen, does not generate hydrogen embrittlement, and has good hydrogen storage stability.
In some embodiments, as shown in fig. 1, a bonding layer is further included between the inner container and the first fiber layer, the bonding layer can further enhance the bonding stability between the fiber layer and the inner container, the storage stability of the tank body is improved, and the inner container and the fiber layer can be isolated. In some embodiments, the material of the tie layer is selected from: at least one of polyurethane, acrylic resin, epoxy resin and chlorinated rubber. In some embodiments, the thickness of the bonding layer is 0.5 to 1.0 mm.
The high-pressure hydrogen storage bottle provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention also provides a preparation method of the high-pressure hydrogen storage bottle, which comprises the following steps:
s10, providing an inner container, and winding the carbon nanotube fibers soaked by the resin on the outer surface of the inner container to form a first fiber layer;
s20, obtaining second fibers soaked by resin, and winding the second fibers on the surface of one side, away from the liner, of the first fiber layer to form a second fiber layer; and curing to obtain the high-pressure hydrogen storage bottle.
According to the preparation method of the high-pressure hydrogen storage bottle provided by the embodiment of the invention, firstly, the carbon nanotube fibers and the second fibers are soaked in the resin in advance, and then the inner container is sequentially wound, so that the winding stability of the fibers can be improved, the fibers are prevented from being unevenly distributed and unbalanced in load of internal stress caused by slippage in the winding process, the curing process can be simplified, the fiber layer can be cured by heating, and the first fiber layer and the second fiber layer are sequentially formed on the outer surface of the inner container, so that the high-pressure hydrogen storage bottle is obtained. The preparation method of the high-pressure hydrogen storage bottle provided by the embodiment of the invention has the advantages of simple process and flexible and convenient operation, and is suitable for industrial large-scale production and application.
Specifically, in step S10, an inner container is provided, and the carbon nanotube fibers impregnated with the resin are wound around the outer surface of the inner container to form a first fiber layer. In some embodiments, the step of winding the carbon nanotube fiber impregnated with the resin around the outer surface of the inner container includes: and alternately performing circumferential winding and spiral winding on the carbon nanotube fiber soaked by the resin on the outer surface of the inner container to form an alternate lamination of the circumferential winding layer of the carbon nanotube fiber and the spiral winding layer of the carbon nanotube fiber. According to the embodiment of the invention, the carbon nanotube fiber soaked by resin is alternately annularly wound and spirally wound on the outer surface of the inner container to form the alternate lamination of the annularly wound layers and the spirally wound layers, the annularly wound layers can effectively eliminate the annular stress generated by the inner container under internal pressure, the spirally wound layers can provide longitudinal stress for the inner container, and the annular stress and the longitudinal stress of the inner container can be eliminated simultaneously through the alternately arranged annularly wound layers and spirally wound layers, so that the overall performance of the inner container is improved.
In some embodiments, the circumferential winding layer of carbon nanotube fibers and the spiral winding layer of carbon nanotube fibers are 2-10 layers respectively. In some embodiments, the first fibrous layer has a thickness of 5 to 8 millimeters. In some embodiments, the volume fraction of carbon nanotube fibers in the first fiber layer is 60% to 70%. In some embodiments, the volume of carbon nanotube fibers is greater than 50% of the total volume of the first fiber layer and the second fiber layer. In some embodiments, the carbon nanotube fiber in the carbon nanotube fiber spiral winding layer forms an angle with the central axis of the inner container of 10 to 20 °. In some embodiments, the carbon nanotube fiber comprises 3-4 carbon nanotube fiber bundles, and the carbon nanotube fiber bundles comprise 6000-8000 carbon nanotube fiber filaments. In some embodiments, the first fibrous layer is selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin. The technical effects of the above embodiments are discussed in detail in the foregoing, and are not described herein again.
Specifically, in step S20, obtaining second fibers soaked with resin, and winding the second fibers on a surface of the first fiber layer on a side away from the liner to form a second fiber layer; and curing to obtain the high-pressure hydrogen storage bottle. In some specific embodiments, the step of winding the second fibers on the surface of the first fiber layer on the side far away from the liner comprises: and alternately performing hoop winding and spiral winding on the surface of one side, far away from the inner container, of the first fiber layer by using the second fibers to form an alternate lamination of second fiber hoop winding layers and second fiber spiral winding layers. According to the embodiment of the invention, the second fibers soaked by the resin are alternately annularly wound and spirally wound on the outer surface of the inner container to form the alternate lamination of the annularly wound layers and the spirally wound layers, the annularly wound layers can effectively eliminate the annular stress generated by the inner container under internal pressure, the spirally wound layers can provide longitudinal stress for the inner container, and the annular stress and the longitudinal stress of the inner container can be eliminated simultaneously through the alternately arranged annularly wound layers and spirally wound layers, so that the overall performance of the inner container is improved.
In one embodiment, the curing conditions include: the inner container is respectively kept warm for 2-4 hours at the rotating speed of 5-10 r/min under the conditions of the temperature of 40-80 ℃, 80-100 ℃, 100-120 ℃ and 120-140 ℃. In the curing process of the embodiment of the invention, the liner rotates at a low speed of 5-10 r/min, so that the liner is heated uniformly, the curing process of resin coated in each direction is consistent, and resin delamination among fiber layers and generation of gaps are prevented. If the rotation speed is too fast, the local resin is not ready to be cured, resulting in uneven distribution of the resin. In addition, the resin is heated in a gradient heating mode, so that the resin is gradually softened and fully contacted with the fibers, and is gradually solidified to form a uniform fiber layer, and if the temperature is increased too fast, the fiber resin layer is easy to generate bubbles, so that the fiber resin layer becomes a stress concentration point, and the overall performance is reduced; if the temperature difference between adjacent stages is large, an excessively high exothermic peak is caused, and huge internal stress is generated to cause the defects of the inside and the appearance of the fiber resin layer, so that the balanced bearing of the internal stress of the fiber resin layer is influenced.
In some embodiments, a tie layer is further included between the liner and the first fibrous layer. In some embodiments, the material of the tie layer is selected from: at least one of polyurethane, acrylic resin, epoxy resin and chlorinated rubber. In some embodiments, the thickness of the bonding layer is 0.5 to 1.0 mm. The bonding layer can further enhance the combination stability of the fiber layer and the liner, improve the storage stability of the tank body and isolate the liner from the fiber layer, because the carbon nanotube fiber and the liner are both conductors, the liner is easy to generate electrochemical corrosion due to the direct contact of the carbon nanotube fiber and the liner, the bonding layer can prevent the liner from being corroded, prevent the liner from generating galvanic corrosion, and prolong the service life of the high-pressure hydrogen storage bottle.
In some embodiments, the second hoop wound layer of fiber and the second helical wound layer of fiber are 2-10 layers each. In some embodiments, the second fibrous layer has a thickness of 4 to 7 millimeters. In some embodiments, the second fiber layer has a volume fraction of second fibers of 60 to 70%. In some embodiments, the second fibers in the second fiber spiral winding layer form an included angle of 50-55 degrees with the central axis of the liner. In some embodiments, the resin in the second fibrous layer is selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin. The technical effects of the above embodiments of the present invention are discussed in detail in the foregoing, and are not described herein again.
In order to clearly understand the details of the above-described implementation and operation of the present invention by those skilled in the art and to clearly show the improved performance of the high pressure hydrogen storage cylinder according to the embodiments of the present invention, the above-described technical solution is illustrated by the following examples.
Example 1
A high pressure hydrogen storage cylinder comprising the steps of:
uniformly coating a layer of film adhesive on the surface of an aluminum alloy liner, wherein the thickness of the liner is 4.76 mm;
secondly, manufacturing a first fiber layer on the outer surface of the film adhesive, performing hoop winding and spiral winding by adopting a carbon nano tube fiber belt, sequentially and alternately performing hoop winding for 3 layers and spiral winding for 2 layers, wherein the winding angle of the spiral winding is 16.7 degrees, and the thickness of the first fiber layer is 5 mm.
The preparation of carbon fiber resin layer is carried out at the surface on first fibrous layer, adopts the carbon fiber area to carry out hoop winding and spiral winding, carries out hoop winding 3 layers and spiral winding 2 layers in proper order in turn, and spiral winding's winding angle is 45, and the thickness on carbon fiber resin layer is 4 mm.
And fourthly, using adhesive tape to perform circumferential winding, putting the high-pressure hydrogen storage bottle after winding forming into a curing furnace for heating and curing, rotating the high-pressure hydrogen storage bottle around the axis at the rotating speed of 5r/min during curing, respectively preserving the heat for 2 hours at 40 ℃, 80 ℃, 120 ℃ and 140 ℃, then naturally cooling, and removing the adhesive tape to obtain the high-pressure hydrogen storage bottle.
Comparative example 1
A hydrogen storage cylinder comprising the steps of:
uniformly coating a layer of film adhesive on the surface of an aluminum alloy liner, wherein the thickness of the liner is 4.76 mm;
secondly, manufacturing a first fiber layer on the outer surface of the film adhesive, performing hoop winding and spiral winding by adopting a carbon nano tube fiber tape, and sequentially and alternately performing hoop winding for 3 layers and spiral winding for 2 layers, wherein the winding angle of the spiral winding is 16.7 degrees, and the thickness of the first fiber layer is 5 mm.
And thirdly, manufacturing a second carbon nanotube fiber resin layer on the outer surface of the first fiber layer, performing hoop winding and spiral winding by adopting a carbon nanotube fiber belt, sequentially and alternately performing 3 layers of hoop winding and 2 layers of spiral winding, wherein the winding angle of the spiral winding is 45 degrees, and the thickness of the second carbon nanotube fiber resin layer is 4 mm.
And fourthly, using adhesive tape to perform circumferential winding, placing the hydrogen storage bottle after winding forming into a curing furnace for heating and curing, rotating the hydrogen storage bottle around the axis at the rotating speed of 5r/min during curing, respectively preserving the heat for 2 hours at 40 ℃, 80 ℃, 120 and 140 ℃, then naturally cooling, and removing the adhesive tape to obtain the hydrogen storage bottle.
Comparative example 2
A hydrogen storage cylinder comprising the steps of:
uniformly coating a layer of film adhesive on the surface of an aluminum alloy liner, wherein the thickness of the liner is 4.76 mm;
secondly, manufacturing a first fiber layer on the outer surface of the film adhesive, performing hoop winding and spiral winding by adopting a carbon fiber tape, sequentially and alternately performing hoop winding for 3 layers and spiral winding for 2 layers, wherein the winding angle of the spiral winding is 16.7 degrees, and the thickness of the first fiber layer is 5 mm.
And thirdly, manufacturing a second carbon fiber resin layer on the outer surface of the first fiber layer, performing hoop winding and spiral winding by adopting a carbon fiber belt, sequentially and alternately performing 3 layers of hoop winding and 2 layers of spiral winding, wherein the winding angle of the spiral winding is 45 degrees, and the thickness of the second carbon nanotube fiber resin layer is 4 mm.
And fourthly, using adhesive tape to perform circumferential winding, placing the hydrogen storage bottle after winding forming into a curing furnace for heating and curing, rotating the hydrogen storage bottle around the axis at the rotating speed of 5r/min during curing, respectively preserving the heat for 2 hours at 40 ℃, 80 ℃, 120 and 140 ℃, then naturally cooling, and removing the adhesive tape to obtain the hydrogen storage bottle.
Further, in order to verify the improvement of the high pressure hydrogen storage cylinders prepared in the examples of the present invention, the working pressure and burst pressure of the hydrogen storage cylinders provided in example 1 and comparative examples 1 and 2 were respectively tested, and the test results are shown in the following table 1:
TABLE 1
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Working pressure/MPa | 35 | 20 | 25 |
| Number of cycles of fatigue | ＞20000 | >8000 | >10000 |
From the above test results, it can be seen that the working pressure and burst pressure of the high pressure hydrogen storage cylinder prepared in example 1 of the present invention are significantly higher than those of comparative examples 1 and 2.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A high pressure hydrogen storage cylinder, comprising: the liner comprises a liner, a first fiber layer and a second fiber layer, wherein the first fiber layer is wound on the outer surface of the liner, and the second fiber layer is wound on the surface of one side, far away from the liner, of the first fiber layer; the first fiber layer is made of carbon nanotube fibers, and the second fiber layer is made of fibers except the carbon nanotube fibers;
the first fibrous layer comprises: the carbon nano tube fiber circumferential winding layers and the carbon nano tube fiber spiral winding layers are alternately arranged;
the second fibrous layer comprises: the second fiber circumferential winding layers and the second fiber spiral winding layers are alternately arranged;
the tensile modulus of the fibers in the second fiber layer is 5% -10% lower than that of the fibers in the first fiber layer;
the included angle between the carbon nanotube fiber and the central axis of the inner container in the carbon nanotube fiber spiral winding layer is 10-20 degrees;
the included angle between the second fibers in the second fiber spiral winding layer and the central axis of the liner is 50-55 degrees;
in the first fiber layer, the volume fraction of the carbon nanotube fibers is 60-70%;
in the second fiber layer, the volume fraction of the other fibers is 60-70%;
resin with the volume fraction of 30-40% in the fiber layer is used as a matrix;
the volume of the carbon nanotube fiber accounts for more than 50% of the total volume of the first fiber layer and the second fiber layer;
in the first fiber layer, the carbon nanotube fiber circumferential winding layer and the carbon nanotube fiber spiral winding layer are respectively provided with 2-10 layers;
in the second fiber layer, 2-10 layers of the second fiber annular winding layer and the second fiber spiral winding layer are respectively arranged;
the thickness of the first fiber layer is 5-8 mm;
the thickness of the second fiber layer is 4-7 mm.
2. A high pressure hydrogen storage cylinder according to claim 1,
the carbon nanotube fiber is soaked by resin; and/or the presence of a gas in the gas,
the other fibers are other fibers soaked by resin.
3. A high pressure hydrogen storage cylinder according to claim 2,
the carbon nanotube fiber comprises 3-4 carbon nanotube fiber bundles, and the carbon nanotube fiber bundles comprise 6000-8000 carbon nanotube fiber filaments; and/or the presence of a gas in the gas,
the resins in the first fiber layer and the second fiber layer are each independently selected from the group consisting of: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin.
4. A high pressure hydrogen storage cylinder according to claim 3,
the inner container is a cylindrical metal inner container, and two ends of the metal inner container are arc-shaped; and/or the presence of a gas in the gas,
the inner container is a single-layer or composite-layer inner container; and/or the presence of a gas in the gas,
the thickness of the inner container is 3-6 mm.
5. A high pressure hydrogen storage cylinder according to claim 4,
the inner container and the first fiber resin layer also comprise a bonding layer, and/or,
the material of the bonding layer is selected from: at least one of polyurethane, acrylic, epoxy, chlorinated rubber, and/or,
the thickness of the bonding layer is 0.5-1.0 mm; and/or the presence of a gas in the gas,
and a bonding layer is also arranged between the inner container and the first fiber layer.
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| CN112963723B (en) * | 2021-03-10 | 2022-07-08 | 深圳烯湾科技有限公司 | Manufacturing method of heating assembly for inner container of pressure gas storage container and pressure gas storage container |
| CN113696519B (en) * | 2021-07-06 | 2022-12-20 | 江阴市富仁高科股份有限公司 | Tool for controlling wall thickness of inner container of hydrogen storage tank to be uniform |
| CN113669618A (en) * | 2021-09-08 | 2021-11-19 | 江苏澳盛复合材料科技有限公司 | Plastic inner container of high-pressure gas storage bottle |
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