CN111251631A - High pressure hydrogen storage cylinder and method of manufacturing the same - Google Patents
High pressure hydrogen storage cylinder and method of manufacturing the same Download PDFInfo
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- CN111251631A CN111251631A CN202010097350.XA CN202010097350A CN111251631A CN 111251631 A CN111251631 A CN 111251631A CN 202010097350 A CN202010097350 A CN 202010097350A CN 111251631 A CN111251631 A CN 111251631A
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- carbon nanotube
- nanotube fiber
- hydrogen storage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
- B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/0227—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using pressure vessels, e.g. autoclaves, vulcanising pans
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/56—Winding and joining, e.g. winding spirally
- B29C53/58—Winding and joining, e.g. winding spirally helically
- B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
- B29C53/602—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels for tubular articles having closed or nearly closed ends, e.g. vessels, tanks, containers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/80—Component parts, details or accessories; Auxiliary operations
- B29C53/84—Heating or cooling
- B29C53/845—Heating or cooling especially adapted for winding and joining
Abstract
The invention belongs to the technical field of hydrogen storage, and particularly relates to a method for manufacturing a high-pressure hydrogen storage bottle, which comprises the following steps: obtaining a cylindrical carbon nanotube fiber braided fabric, wherein the cylindrical carbon nanotube fiber braided fabric is of an integrated structure and has no seam in the longitudinal direction; and (3) obtaining a liner, sleeving the cylindrical carbon nanotube fiber braided fabric on the outer surface of the liner, and curing to obtain the high-pressure hydrogen storage bottle with the outer surface wound with the carbon nanotube fiber. The high-pressure hydrogen storage bottle with the carbon nanotube fiber wound on the outer surface can be obtained by curing the cylindrical carbon nanotube fiber braided fabric which has an integral structure and is seamless in the longitudinal direction after being sleeved on the outer surface of the inner container, the circumferential pressure resistance of the container can be effectively improved by tightly combining the cylindrical carbon nanotube fiber braided fabric and the inner container, and the high-pressure hydrogen storage bottle is suitable for storing hydrogen, good in storage stability, high in pressure resistance, simple in preparation process and easy to operate.
Description
Technical Field
The invention belongs to the technical field of high-pressure containers, and particularly relates to a high-pressure hydrogen storage bottle and a manufacturing method thereof.
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 available today, 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.
Currently, hydrogen is stored mainly: as a compressed gas in a vessel; stored in liquid form in a dewar or tank (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 demonstration stages.
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 tanks can be mainly divided into four types: the gas cylinder comprises an all-metal gas cylinder (type I), a metal liner fiber circumferential winding gas cylinder (type II), a metal liner fiber full winding gas cylinder (type III) and a nonmetal liner fiber full winding gas cylinder (type IV). The full winding mode of the fiber has the annular winding and the spiral winding. In actual production, the circumferential winding is generally wound in the central area of the gas cylinder, so that the circumferential stress generated by the internal pressure of the gas cylinder can be eliminated. The high-pressure hydrogen storage tanks are difficult to meet the hydrogen storage density requirement of a hydrogen fuel cell automobile, winding fibers are usually wound by carbon fibers, the uniformity of tows of the high-pressure hydrogen storage tanks 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 tow interlacing and the like can occur in practical application. Therefore, the rigidity of the tank body in the radial direction is relatively limited to be improved, and the fiber bundles are easy to slip in the winding and resin melting and impregnation processes, so that the fiber bundles are intertwined, and the reinforcing effect is influenced. The carbon fiber tows are stacked or the tension is controlled unevenly in the hoop winding process, so that the stress distribution of the tank body is uneven.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a method for manufacturing a high-pressure hydrogen storage bottle, which aims to solve the technical problems that the existing surface is poor in uniformity of annularly wound fiber tows, more broken filaments are generated, the yarn breakage is serious, the wettability with resin is poor, the winding is unstable, the slippage is easy to generate, the tows are intertwined, and the like.
It is another object of the present invention to provide a container.
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 method of making a high pressure hydrogen storage cylinder comprising the steps of:
obtaining a cylindrical carbon nanotube fiber braided fabric, wherein the cylindrical carbon nanotube fiber braided fabric is of an integrated structure and has no seam in the longitudinal direction;
and (3) obtaining a liner, sleeving the cylindrical carbon nanotube fiber braided fabric on the outer surface of the liner, and curing to obtain the high-pressure hydrogen storage bottle with the outer surface wound with the carbon nanotube fiber.
Preferably, in the same radial direction, the circumferential length of the cylindrical carbon nanotube fiber braided fabric is 97-99.5% of the circumferential length of the inner container; and/or the presence of a gas in the gas,
the thickness of the cylindrical carbon nanotube fiber braided fabric is 4-15 mm.
Preferably, the curing process comprises: and sequentially arranging demoulding cloth and a vacuum bag on the surface of one side of the cylindrical carbon nanotube fiber braided fabric, which is far away from the inner container, sealing the vacuum bag to enable the cylindrical carbon nanotube fiber braided fabric and the demoulding cloth to be packaged in the vacuum bag, and then heating and curing the cylindrical carbon nanotube fiber braided fabric in a vacuum environment to obtain the high-pressure hydrogen storage bottle coated with the carbon nanotube fibers.
Preferably, the conditions for heat-curing the cylindrical carbon nanotube fiber braid under a vacuum environment include: the inner container is respectively kept warm for 2-4 hours at the rotating speed of 5-10 r/min under the temperature conditions of 40-80 ℃, 80-100 ℃, 100-120 ℃ and 120-140 ℃.
Preferably, the carbon nanotube fiber is a carbon nanotube fiber prepared by directly pulling out a carbon nanotube fiber filament from a carbon nanotube array; and/or the presence of a gas in the gas,
the step of obtaining a cylindrical carbon nanotube fiber braid comprises: weaving the carbon nanotube fibers into the cylindrical carbon nanotube fiber woven fabric after the carbon nanotube fibers are subjected to first resin soaking treatment; and/or the presence of a gas in the gas,
and a bonding layer is also arranged between the inner container and the cylindrical carbon nanotube fiber braided fabric.
Preferably, the length of the carbon nanotube in the carbon nanotube array is 200-500 microns, and the diameter is 6-10 nanometers; and/or the presence of a gas in the gas,
the material of the bonding layer is selected from: at least one of polyurethane, acrylic acid, epoxy resin and chlorinated rubber; and/or the presence of a gas in the gas,
the thickness of the bonding layer is 0.5-1.0 mm.
Preferably, before the step of curing, the method further comprises the steps of: and spirally winding a fiber belt soaked with second resin on the surface of one side of the cylindrical carbon nanotube fiber braided fabric far away from the inner container.
Preferably, the included angle between the fiber belt and the central axis of the inner container is 10-45 degrees; and/or the presence of a gas in the gas,
the fiber band is selected from at least one of carbon nanotube fiber, carbon fiber, glass fiber and Kevlar fiber.
Preferably, the first resin and the second resin are each independently selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin.
Accordingly, the high-pressure hydrogen storage bottle is manufactured by the manufacturing method of the high-pressure hydrogen storage bottle.
Effects of the invention
The invention provides a method for manufacturing a high-pressure hydrogen storage bottle, which comprises the steps of sleeving a cylindrical carbon nanotube fiber braided fabric which has an integral structure and is free of seam in the longitudinal direction on the outer surface of an inner container, and then curing to obtain the high-pressure hydrogen storage bottle with the carbon nanotube fiber wound on the outer surface. On one hand, the cylindrical carbon nanotube fiber braided fabric is formed by braiding carbon nanotube fibers with excellent mechanical property, has good elasticity, elasticity and smoothness, and can be tightly attached to the radian of the liner tank body, so that the toughness of the liner tank body is improved, and the impact bearing capacity of the tank body is enhanced. On the other hand, the cylindrical carbon nanotube fiber braided fabric is a cylindrical whole formed by braiding the carbon nanotube fibers, the carbon nanotube fibers in the cylindrical whole are uniformly and stably distributed, the load of the inner container stress can be borne uniformly, a plurality of interweaving points are formed in the braided fabric, the slippage of the fibers is effectively avoided, and the bearing capacity of the internal stress in the inner container tank body is further enhanced; and the cylindrical carbon nanotube fiber braided fabric has good elasticity, can provide a reaction force for the inner container, and further improves the high pressure resistance of the container. The container is suitable for storing hydrogen, and has good storage stability and high compressive strength.
The high-pressure hydrogen storage bottle provided by the invention is prepared by the method, and comprises the inner container and the cylindrical carbon nanotube fiber braided fabric sleeved on the outer surface of the inner container, on one hand, the cylindrical carbon nanotube fiber braided fabric has good elasticity, elasticity and smoothness, is a cylindrical whole body, and can be tightly attached to the radian of the inner container tank body, so that the toughness of the inner container tank body is improved, the impact bearing capacity of the tank body is enhanced, the slippage of the fiber can be prevented, and the bearing capacity of the internal stress in the inner container tank body is further enhanced; on the other hand, the cylindrical carbon nanotube fiber braided fabric has good elasticity, can provide a reaction force for the inner container, and further improves the high pressure resistance of the container. The container has excellent high pressure resistance, is particularly suitable for storing hydrogen, and has good storage stability and high compressive strength.
Drawings
Fig. 1 is a schematic structural diagram of a container according to an embodiment of the present 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.
The embodiment of the invention provides a method for manufacturing a high-pressure hydrogen storage bottle, which comprises the following steps:
obtaining a cylindrical carbon nanotube fiber braided fabric, wherein the cylindrical carbon nanotube fiber braided fabric is of an integrated structure and has no seam in the longitudinal direction;
and (3) obtaining a liner, sleeving the cylindrical carbon nanotube fiber braided fabric on the outer surface of the liner, and curing to obtain the high-pressure hydrogen storage bottle with the outer surface wound with the carbon nanotube fiber.
According to the manufacturing method of the high-pressure hydrogen storage bottle provided by the embodiment of the invention, the cylindrical carbon nanotube fiber braided fabric which is of an integral structure and has no seam in the longitudinal direction is sleeved on the outer surface of the inner container, and then the high-pressure hydrogen storage bottle with the carbon nanotube fiber wound on the outer surface can be obtained through curing treatment. On one hand, the cylindrical carbon nanotube fiber braided fabric is formed by braiding carbon nanotube fibers with excellent mechanical property, has good elasticity, elasticity and smoothness, and can be tightly attached to the radian of the liner tank body, so that the toughness of the liner tank body is improved, and the impact bearing capacity of the tank body is enhanced. On the other hand, the cylindrical carbon nanotube fiber braided fabric is a cylindrical whole formed by braiding the carbon nanotube fibers, the carbon nanotube fibers in the cylindrical whole are uniformly and stably distributed, the load of the inner container stress can be borne uniformly, a plurality of interweaving points are formed in the braided fabric, the slippage of the fibers is effectively avoided, and the bearing capacity of the internal stress in the inner container tank body is further enhanced; and the cylindrical carbon nanotube fiber braided fabric has good elasticity, can provide a reaction force for the inner container, and further improves the high pressure resistance of the container. The container provided by the embodiment of the invention is suitable for storing hydrogen, and has good storage stability and high compressive strength.
Specifically, in the same radial direction, the circumferential length of the cylindrical carbon nanotube fiber braided fabric is 97-99.5% of the circumferential length of the inner container. Because the cylindrical carbon nanotube fiber braided fabric has good elasticity, when the braided fabric with the diameter slightly smaller than that of the inner container is sleeved on the tank body, better reaction force can be provided for the inner container, and the high pressure resistance of the container is further improved. Specifically, in the above steps, since the diameter of the cylindrical carbon nanotube fiber braid is slightly smaller than the outer diameter of the inner container and the cylindrical carbon nanotube fiber braid is pre-impregnated with the resin, the cylindrical carbon nanotube fiber braid can be bonded to the surface of the inner container by heating to obtain the container, and the preparation process is simple and easy to operate.
In some embodiments, the step of sheathing the cylindrical carbon nanotube fiber braid on the outer surface of the inner container comprises: firstly, sleeving a cylindrical carbon nanotube fiber braided fabric outside a polytetrafluoroethylene hollow sleeve, wherein the polytetrafluoroethylene has a low friction coefficient and non-adhesiveness, the cylindrical carbon nanotube fiber braided fabric can be transferred to a corresponding position of an inner container to be nested, and the polytetrafluoroethylene hollow sleeve can be sleeved at the top of the inner container or directly sleeved on the outer surface of the inner container; then the polytetrafluoroethylene hollow sleeve is sleeved on the liner or the surface of the liner, and then the cylindrical carbon nanotube fiber braided fabric on the polytetrafluoroethylene hollow sleeve is transferred to the surface of the liner, because the cylindrical carbon nanotube fiber braided fabric is spread when being sleeved on the outer surface of the polytetrafluoroethylene hollow sleeve, the cylindrical carbon nanotube fiber braided fabric is gradually tightened to restore the original size when being transferred to the outer surface of the liner, and is tightly coated on the outer surface of the liner, and because the shrinkage exerts certain prestress on the liner, even if the cylindrical carbon nanotube fiber braided fabric is sleeved on the outer surface of the liner.
In some embodiments, the curing process comprises: and sequentially arranging demoulding cloth and a vacuum bag on the surface of one side, far away from the inner container, of the cylindrical carbon nanotube fiber braided fabric, sealing the vacuum bag by adopting a sealant, packaging the cylindrical carbon nanotube fiber braided fabric and the demoulding cloth in the vacuum bag, and then heating and curing the cylindrical carbon nanotube fiber braided fabric in a vacuum environment to obtain the container. The embodiment of the invention adopts a vacuum heating and curing mode, the surface of the cylindrical carbon nanotube fiber braided fabric is sequentially provided with the demolding cloth and the vacuum bag, the vacuum bag is sealed by sealant and the like, so that the cylindrical carbon nanotube fiber braided fabric and the demolding cloth are packaged in the vacuum bag, then the cylindrical carbon nanotube fiber braided fabric is heated and cured under the vacuum condition to be combined with the inner container, and the vacuum bag and the demolding cloth are removed after cooling, thus obtaining the container. The curing mode effectively prevents the cylindrical carbon nanotube fiber braided fabric from generating bubbles and the like in the curing process to influence the strength of the container, the outer surface of the inner container is uniform in thickness, and the compressive strength and the impact resistance of the inner container can be effectively enhanced by combining the stable cylindrical carbon nanotube fiber braided fabric.
In some embodiments, in order to further improve the curing effect, the cylindrical carbon nanotube fiber fabric can be heated and cured by vacuum after a proper amount of resin is injected into the vacuum bag during vacuum heating and curing, so that the cylindrical carbon nanotube fiber fabric can be further protected, the external impact resistance of the cylindrical carbon nanotube fiber fabric can be improved, external impact can be effectively borne, the cylindrical carbon nanotube fiber fabric can be prevented from being damaged by external impact force, the transmission of internal stress generated by the cylindrical carbon nanotube fiber fabric to the inner container can be improved, and the pressure resistance of the container can be enhanced.
In some embodiments, a demolding cloth and a vacuum bag are sequentially arranged on the surface of one side of the cylindrical carbon nanotube fiber braided fabric, which is far away from the inner container, the vacuum bag is sealed by a sealant, so that the cylindrical carbon nanotube fiber braided fabric and the demolding cloth are packaged in the vacuum bag, and then the inner container is respectively kept warm for 2-4 hours at the rotating speed of 5-10 r/min under the temperature conditions of 40-80 ℃, 80-100 ℃, 100-120 ℃ and 120-140 ℃. In the curing process of the embodiment of the invention, the inner container rotates at a low speed of 5-10 r/min, so that the inner container is heated uniformly, the curing process of the cylindrical carbon nanotube fiber braided fabric coated in each direction is consistent, and the resin in the cylindrical carbon nanotube fiber braided fabric is prevented from layering to generate gaps. If the rotating speed is too slow, the curing processes of the resins coated in all directions are inconsistent, so that the resins are layered and gaps are generated; if the rotation speed is too high, the local resin is not ready to be cured, resulting in poor curing uniformity of the cylindrical carbon nanotube fiber braid. In addition, the resin in the cylindrical carbon nanotube fiber braided fabric is gradually softened and fully contacted with the fibers by heating in a gradient temperature rise mode, and the resin is gradually solidified to form a uniform fiber braided layer; if the temperature difference of the adjacent stages is large, an excessively high exothermic peak is caused, huge internal stress is generated to cause the defects of the interior and the appearance of the cylindrical carbon nanotube fiber braided fabric, and the balanced bearing of the internal stress of the cylindrical carbon nanotube fiber braided fabric is influenced.
In some embodiments, the surface of the cylindrical carbon nanotube fiber braided fabric on the side away from the inner container is sequentially provided with demolding cloth, vacuum bag polytetrafluoroethylene demolding cloth, an isolation film and a vacuum bag, the demolding cloth, the vacuum bag and the vacuum bag are sealed by a sealing adhesive tape, the vacuum pumping is performed, the curing is completed while rotating under the heating condition, and the heat preservation is performed for 2-4 hours respectively under the conditions that the rotating speed is 5-10 r/min, the temperature is 40-80 ℃, 80-100 ℃, 100-120 ℃ and 120-140 ℃. And after the solidification is finished, cooling the temperature to room temperature, removing the vacuum system, and demolding to obtain the cylindrical carbon nanotube fiber braided fabric reinforced container.
In some embodiments, before the curing step, the method further comprises the steps of: and spirally winding a fiber belt pre-impregnated with second resin on the surface of one side of the cylindrical carbon nanotube fiber braided fabric far away from the inner container. In some specific embodiments, the included angle between the fiber belt and the central axis of the liner is 10-45 degrees, the fibers are wound at a low angle, the circumferential winding of the cylinder part can be 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%; meanwhile, the transition edges of the cylinder part and the bottom of the inner container can be strengthened by the angle, so that all parts of the inner container are enhanced. Optionally, the fiber tape is selected from one of carbon nanotube fiber, carbon fiber, glass fiber, and kevlar fiber. The high-strength fiber is spirally wound on the liner sleeved with the cylindrical carbon nanotube fiber braided fabric, so that the mechanical property of the liner can be further improved, and the bottom or transition area of the liner is strengthened on the basis of enhancing the circumferential strength of the cylindrical carbon nanotube fiber braided fabric, so that the liner is more favorable for being used as a high-pressure storage container.
In some embodiments, the second resin is selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin. The resins adopted by the embodiment of the invention have good thermosetting property, so that the fiber band can be stably bonded on the surface of the cylindrical carbon nanotube fiber braided fabric, 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 cylindrical carbon nanotube fiber braid has a thickness of 4 to 15 mm. The cylindrical carbon nanotube fiber braided fabric with the thickness of 4-15 mm effectively ensures the load of the cylindrical carbon nanotube fiber braided fabric on the internal stress of the inner container 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 cylindrical carbon nanotube fiber braided fabric is too thin, the cylindrical carbon nanotube fiber braided fabric cannot effectively bear and dredge the internal stress of the tank body; the larger the thickness of the cylindrical wall of the cylindrical carbon nanotube fiber braided fabric is, the larger the reinforcement is provided, so that the liner can be in a compression stress state, and the fatigue performance of the container is improved. However, if the thickness is too large, the total weight of the container is increased, the container cannot be lightened, the subsequent increase of other fiber winding is not facilitated, and if the thickness is too large, uneven stress in a fiber layer is caused, so that the reinforcing performance is reduced. Therefore, if the thickness of the cylindrical carbon nanotube fiber fabric is too thick, not only the manufacturing cost is increased, but also the fiber layer wrapped outside the inner container can apply too much pressure to the inner container, which is also not beneficial to the high-pressure storage of the tank body.
In some embodiments, the step of obtaining a cylindrical carbon nanotube fiber braid comprises: and weaving the carbon nanotube fibers into the cylindrical carbon nanotube fiber woven fabric after the carbon nanotube fibers are subjected to first resin soaking treatment. According to the embodiment of the invention, the carbon nanotube fibers soaked with the resin are woven into the cylindrical carbon nanotube fiber woven fabric in a cross weaving mode or the like, so that the resin can penetrate into each part of the woven cylinder more deeply and uniformly, the resin which is fully penetrated by the woven cylinder in the subsequent curing process can be firmly bonded on the outer surface of the inner container, a uniform and stable carbon nanotube fiber woven layer is formed, and the compressive strength of the inner container is improved.
In some embodiments, the carbon nanotube fibers are carbon nanotube fibers produced by drawing carbon nanotube filaments directly from a carbon nanotube array. In some specific embodiments, the carbon nanotube fiber is prepared by twisting a carbon nanotube array film with the width of 7.5 cm-12 cm under the condition that the twist is 100-15000 tpm, and the carbon nanotube fiber prepared under the condition has better mechanical property, is favorable for being woven into a cylinder shape, has better toughness and can exert better reinforcing effect on the inner container. In other embodiments, the resin-impregnated cylindrical carbon nanotube fiber braid is prepared by impregnating a woven carbon nanotube fabric tube with a resin. In other embodiments, the resin impregnated cylindrical carbon nanotube fiber braid is prepared by coating the inner and outer surfaces of a carbon nanotube braid with a resin. In some embodiments, the carbon nanotubes in the carbon nanotube array have a length of 200-500 microns and a diameter of 6-10 nanometers.
In some embodiments, the first resin is selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin. The resins adopted by the embodiment of the invention have good thermosetting property, so that the cylindrical carbon nanotube fiber braided fabric 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 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, a bonding layer is further included between the inner container and the cylindrical carbon nanotube fiber braided fabric, the bonding layer can further enhance the combination stability of the cylindrical carbon nanotube fiber braided fabric and the inner container, the storage stability of the tank body is improved, and the inner container and the cylindrical carbon nanotube fiber braided fabric 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, and the above technical effect can be achieved by the bonding layer with the thickness.
Accordingly, as shown in fig. 1, the embodiment of the invention also provides a container, and the container is prepared by the method.
The high-pressure hydrogen storage bottle provided by the embodiment of the invention is prepared by the method and comprises the inner container and the cylindrical carbon nanotube fiber braided fabric sleeved on the outer surface of the inner container, on one hand, the cylindrical carbon nanotube fiber braided fabric has good elasticity, elasticity and smoothness and is a cylindrical whole and can be tightly attached to the radian of the inner container tank body, so that the toughness of the inner container tank body is improved, the impact bearing capacity of the tank body is enhanced, the fiber slippage can be prevented, and the bearing capacity of internal stress in the inner container tank body is further enhanced; on the other hand, the cylindrical carbon nanotube fiber braided fabric has good elasticity, can provide a reaction force for the inner container, and further improves the high pressure resistance of the container. The container provided by the embodiment of the invention has excellent high-pressure resistance, is particularly suitable for storing hydrogen, and has good storage stability and high compressive strength.
In some embodiments, a bonding layer is further included between the inner container and the cylindrical carbon nanotube fiber braid. 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 bonding layer has a thickness of 0.5 to 1.0 mm.
In some embodiments, the cylindrical carbon nanotube fiber fabric has a wall thickness of 4 to 15 mm. In some embodiments, the resin-impregnated cylindrical carbon nanotube fiber braid is formed by cross-weaving resin-impregnated carbon nanotube fibers.
In some embodiments, the carbon nanotube fiber is prepared by twisting a carbon nanotube array film having a width of 7.5cm to 12cm at a twist of 100 to 15000 tpm.
In some embodiments, the resin is selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin.
In some embodiments, the inner container is selected from a seamless columnar aluminum alloy structure with the thickness of 3-6 mm.
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 that the details of the above-described operation and operation of the present invention will be readily understood by those skilled in the art, and the manner of attaining an understanding of the invention and the method of making the same, the above-described embodiments are illustrated by way of example in the following.
Example 1
A container comprising the following preparation steps:
s1, spraying a polyurethane layer on the inner container;
s2, pulling a 0.5cm carbon nanotube film in the carbon nanotube array, and twisting the carbon nanotube film into carbon nanofibers by 100 tpm; doubling 50 carbon nanotube fibers into carbon nanotube fiber bundles, and impregnating by hot-melt epoxy resin to obtain carbon nanotube fiber prepreg yarns; and (3) the carbon nanotube fiber prepreg yarns are crossed and woven into cylindrical woven cloth by a weaving machine to obtain a cylindrical woven tube of the carbon nanotube fiber, wherein the diameter of the cylindrical woven tube is 118mm, and the thickness of the cylindrical woven tube is 20 mm. And nesting the carbon nano tube fiber cylindrical weaving cylinder in a polytetrafluoroethylene hollow sleeve, wherein the inner diameter of the polytetrafluoroethylene sleeve is consistent with the outer diameter of the inner container, and the thickness of the polytetrafluoroethylene sleeve is 0.4 mm.
S3, nesting the polytetrafluoroethylene sleeve nested with the cylindrical carbon nanotube fiber braided fabric on the inner container, and taking out the polytetrafluoroethylene sleeve to obtain the inner container nested with the cylindrical carbon nanotube fiber braided fabric.
S4, sequentially laying a polytetrafluoroethylene demolding cylinder, an isolating membrane and a vacuum bag on the surface of the inner container nested with the cylindrical carbon nanotube fiber braided fabric, sealing through a sealing adhesive tape, vacuumizing, completing solidification while rotating around an axial direction under a heating condition, wherein the rotating speed is 5-10 r/min, the solidification temperatures are 40, 80, 120 and 140 ℃, the temperature is respectively kept for 2 hours, then naturally cooling, removing a vacuum system, and demolding to obtain the cylindrical carbon nanotube fiber braided fabric reinforced container.
Example 2
S1, spraying a polyurethane layer on the inner container;
s2, pulling a 0.5cm carbon nanotube film in the carbon nanotube array, and twisting the carbon nanotube film into carbon nanofibers by 100 tpm; doubling 50 carbon nanotube fibers into carbon nanotube fiber bundles, and impregnating by hot-melt epoxy resin to obtain carbon nanotube fiber prepreg yarns; the carbon nanotube fiber prepreg yarns were cross-woven into a cylindrical woven fabric by a knitting machine to obtain a cylindrical woven tube of carbon nanotube fibers having a diameter of 118 mm. And nesting the carbon nano tube fiber cylindrical weaving cylinder in a polytetrafluoroethylene hollow sleeve, wherein the inner diameter of the polytetrafluoroethylene sleeve is consistent with the outer diameter of the inner container, and the thickness of the polytetrafluoroethylene sleeve is 0.4 mm.
S3, nesting the polytetrafluoroethylene sleeve nested with the cylindrical carbon nanotube fiber braided fabric on the inner container, and taking out the polytetrafluoroethylene sleeve to obtain the inner container nested with the cylindrical carbon nanotube fiber braided fabric.
And S4, spirally winding a carbon nanotube fiber belt on the surface of the inner container nested with the cylindrical carbon nanotube fiber fabric, wherein the angle is 16.7 degrees, and the thickness of the carbon nanotube fiber resin layer is 20 millimeters, so that the inner container wound with the carbon nanotube fiber is obtained.
S5, sequentially laying a polytetrafluoroethylene demolding cylinder, an isolating membrane and a vacuum bag on the surface of the inner container wound with the carbon nanotube fibers, sealing through a sealing adhesive tape, vacuumizing, curing while rotating around an axial direction under a heating condition, wherein the rotating speed is 5-10 r/min, the curing temperatures are 40, 80, 120 and 140 ℃, heat preservation is respectively carried out for 2 hours, then, natural cooling is carried out, a vacuum system is removed, and demolding is carried out to obtain the cylindrical carbon nanotube fiber braided fabric reinforced container.
Comparative example 1
A container, comprising the steps of:
① spraying polyurethane layer on the inner container;
② carries out the preparation of carbon fiber resin layer at the surface of carbon nanotube fiber resin layer, adopts the carbon fiber tape 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 of carbon nanotube fiber resin layer is 20 millimeters.
③ and winding with adhesive tape, heating and curing the wound container in a curing furnace at 5r/min around the axis, maintaining at 40, 80, 120, and 140 deg.C for 2 hr, naturally cooling, and removing adhesive tape to obtain the final product.
Comparative example 2
A container, comprising the steps of:
s1, spraying a polyurethane layer on the inner container;
s2, directly weaving carbon nanotube fiber cylinder woven cloth on the inner container by using the inner container as a core mold and a horizontal weaving machine, wherein the carbon nanotube fiber is pre-impregnated with epoxy resin, so that the carbon nanotube fiber cylinder woven cloth is wound on the inner container cylinder part and has the thickness of 20 mm;
s3, sequentially laying polytetrafluoroethylene demolding cloth, an isolation film and a vacuum bag on the surface of the inner container nested with the carbon nanotube fiber woven cloth, sealing through a sealing adhesive tape, vacuumizing, curing while rotating around an axial direction under a heating condition, wherein the rotating speed is 5-10 r/min, the curing temperatures are 40, 80, 120 and 140 ℃, heat preservation is respectively carried out for 2 hours, then, natural cooling is carried out, a vacuum system is removed, and demolding is carried out to obtain the carbon nanotube fiber woven cloth reinforced container.
Comparative example 3
A container, comprising the steps of:
s1, spraying a polyurethane layer on the inner container;
s2, the carbon nanotube fiber tape pre-impregnated with epoxy resin was wound around the cylindrical portion of the pressure vessel in the circumferential direction with respect to the axis of the pressure vessel, and 15N tension was applied to the carbon nanotube fiber during winding. The carbon nanotube fiber band contains 3 carbon nanotube fiber bundles, and the carbon nanotube fiber bundles contain 6000 carbon nanotube fiber doubling.
S3, sequentially laying polytetrafluoroethylene release cloth, an isolation film and a vacuum bag on the surface of the liner wound with the carbon nanotube fiber tape with the thickness of 20 mm, sealing by a sealing adhesive tape, vacuumizing, curing while rotating around an axial direction under a heating condition, wherein the rotating speed is 5-10 r/min, the curing temperatures are 40, 80, 120 and 140 ℃, heat preservation is respectively carried out for 2 hours, then naturally cooling, removing a vacuum system, and demoulding to obtain the carbon nanotube fiber tape reinforced container.
Further, in order to verify the improvement of the container prepared in the embodiment of the present invention, the container provided in the embodiment 1 of the present invention and the containers provided in the comparative examples 1 to 3 were subjected to an internal pressure failure test to investigate the pressure resistance, and the test results are shown in the following table 1:
TABLE 1
From the above test results, it can be seen that the containers provided in examples 1 and 2 of the present invention have higher burst pressure, which is the compressive strength of the reaction, than the containers of comparative examples 1 to 3, and therefore the larger the burst pressure, the better. According to the embodiment of the invention, the cylindrical carbon nanotube fiber braided fabric with the diameter slightly smaller than the outer diameter of the inner container is nested, so that a prestress can be provided for the cylindrical part of the inner container, and the cylindrical part can be better reinforced. The pre-stress provided by direct braiding or winding in the comparative example is limited and it is clear that the burst pressure is lower than in example 1.
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 (10)
1. A method of making a high pressure hydrogen storage cylinder comprising the steps of:
obtaining a cylindrical carbon nanotube fiber braided fabric, wherein the cylindrical carbon nanotube fiber braided fabric is of an integrated structure and has no seam in the longitudinal direction;
and (3) obtaining a liner, sleeving the cylindrical carbon nanotube fiber braided fabric on the outer surface of the liner, and curing to obtain the high-pressure hydrogen storage bottle with the outer surface wound with the carbon nanotube fiber.
2. The method of manufacturing a high-pressure hydrogen storage cylinder according to claim 1,
in the same radial direction, the circumferential length of the cylindrical carbon nanotube fiber braided fabric is 97-99.5% of that of the inner container; and/or the presence of a gas in the gas,
the thickness of the cylindrical carbon nanotube fiber braided fabric is 4-15 mm.
3. The method of producing a high-pressure hydrogen storage cylinder as claimed in claim 1 or 2,
the curing treatment step includes: and sequentially arranging demoulding cloth and a vacuum bag on the surface of one side of the cylindrical carbon nanotube fiber braided fabric, which is far away from the inner container, sealing the vacuum bag to enable the cylindrical carbon nanotube fiber braided fabric and the demoulding cloth to be packaged in the vacuum bag, and then heating and curing the cylindrical carbon nanotube fiber braided fabric in a vacuum environment to obtain the high-pressure hydrogen storage bottle coated with the carbon nanotube fibers.
4. The method of manufacturing a high-pressure hydrogen storage cylinder according to claim 3,
the conditions for heating and curing the cylindrical carbon nanotube fiber braid in a vacuum environment include: the inner container is respectively kept warm for 2-4 hours at the rotating speed of 5-10 r/min under the temperature conditions of 40-80 ℃, 80-100 ℃, 100-120 ℃ and 120-140 ℃.
5. The method of manufacturing a high-pressure hydrogen storage cylinder according to claim 4,
the carbon nanotube fiber is prepared by directly pulling out carbon nanotube fiber from a carbon nanotube array; and/or the presence of a gas in the gas,
the step of obtaining a cylindrical carbon nanotube fiber braid comprises: weaving the carbon nanotube fibers into the cylindrical carbon nanotube fiber woven fabric after the carbon nanotube fibers are subjected to first resin soaking treatment; and/or the presence of a gas in the gas,
and a bonding layer is also arranged between the inner container and the cylindrical carbon nanotube fiber braided fabric.
6. The method of manufacturing a high-pressure hydrogen storage cylinder according to claim 5,
the length of the carbon nano tube in the carbon nano tube array is 200-500 microns, and the diameter is 6-10 nanometers; and/or the presence of a gas in the gas,
the material of the bonding layer is selected from: at least one of polyurethane, acrylic acid, epoxy resin and chlorinated rubber; and/or the presence of a gas in the gas,
the thickness of the bonding layer is 0.5-1.0 mm.
7. The method of producing a high-pressure hydrogen storage cylinder as claimed in claim 5 or 6,
before the step of curing treatment, the method further comprises the steps of: and spirally winding a fiber belt soaked with second resin on the surface of one side of the cylindrical carbon nanotube fiber braided fabric far away from the inner container.
8. The method of manufacturing a high-pressure hydrogen storage cylinder according to claim 7,
the included angle between the fiber belt and the central axis of the inner container is 10-45 degrees; and/or the presence of a gas in the gas,
the fiber band is selected from at least one of carbon nanotube fiber, carbon fiber, glass fiber and Kevlar fiber.
9. The method of manufacturing a high-pressure hydrogen storage cylinder according to claim 8,
the first resin and the second resin are each independently selected from: at least one of epoxy resin, unsaturated polyester resin, polyamide resin and vinyl resin.
10. A high-pressure hydrogen storage cylinder manufactured by the method for manufacturing a high-pressure hydrogen storage cylinder according to any one of claims 1 to 9.
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| CN112743878A (en) * | 2020-12-16 | 2021-05-04 | 北京新能源汽车技术创新中心有限公司 | Fiber composite material high-pressure hydrogen storage cylinder and preparation method thereof |
| CN112963723A (en) * | 2021-03-10 | 2021-06-15 | 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 |
| CN113446509A (en) * | 2021-07-06 | 2021-09-28 | 江阴市富仁高科股份有限公司 | Design method of high-pressure hydrogen storage tank with plastic inner container |
| WO2022099541A1 (en) * | 2020-11-12 | 2022-05-19 | 深圳烯湾科技有限公司 | Gas cylinder and manufacturing method therefor |
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| WO2022099541A1 (en) * | 2020-11-12 | 2022-05-19 | 深圳烯湾科技有限公司 | Gas cylinder and manufacturing method therefor |
| CN112743878A (en) * | 2020-12-16 | 2021-05-04 | 北京新能源汽车技术创新中心有限公司 | Fiber composite material high-pressure hydrogen storage cylinder and preparation method thereof |
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