IV-type high-pressure hydrogen storage cylinder as well as preparation method and application thereof

Abstract

The invention provides an IV-type high-pressure hydrogen storage cylinder as well as a preparation method and application thereof. The IV-type high-pressure hydrogen storage cylinder structurally comprises an inner container, and a plasma coating is sprayed on the outer surface of the inner container; the carbon fiber winding layer is wound and coated on the outer surface of the inner container sprayed with the plasma coating; the glass fiber winding layer wraps the outer surface, away from the inner container, of the carbon fiber winding layer in a winding mode, and the glass fiber winding layer is made of a composite material of glass fibers and a fire-resistant resin material; the fireproof resin material is modified epoxy resin; wherein the fire-resistant resin material comprises epoxy resin, metal oxide, ammonium phosphate, graphite and a triazine nitrogen-containing heterocyclic organic compound, and the IV-type high-pressure hydrogen storage cylinder prepared from the fire-resistant resin material has excellent fire resistance and impact resistance, is simple in preparation process and has a wide industrial application prospect.

Description

Technical Field

[0001] The present invention relates to the field of mobile storage of high-pressure hydrogen, and in particular to a type IV high-pressure hydrogen storage cylinder and a preparation method and application thereof. Background Art

[0002] The development of hydrogen storage cylinders has a history of more than 50 years. There are four types of hydrogen storage cylinders: all-metal cylinders (Type I), metal liner fiber hoop-wound cylinders (Type II), metal liner fiber fully wrapped cylinders (Type III), non-metal liner fiber fully wrapped cylinders (Type IV). Due to the relatively large weight of Type I and Type II cylinders, it is difficult to meet the unit mass hydrogen storage density requirements. Compared with Type III cylinders, Type IV cylinders generally use a manufacturing method of non-metallic liner such as plastic and fiber winding layer, which makes the cylinder lighter, lower cost, and higher mass hydrogen storage density, making it more suitable for fuel cell vehicle-mounted hydrogen storage. The fiber winding layer in the Type IV cylinder is composed of a carbon fiber winding layer and a glass fiber winding layer. The carbon fiber winding layer is composed of a composite of carbon fiber and epoxy resin matrix, and mainly plays the role of bearing the pressure of the hydrogen storage cylinder. The glass fiber layer is a composite of glass fiber and resin matrix, and mainly plays the role of protecting the carbon fiber winding layer. However, when the hydrogen storage cylinder encounters a high temperature fire environment, the epoxy resin matrix is ​​very likely to soften, causing the mechanical properties of the carbon fiber winding layer to fail and be unable to withstand the internal pressure of the hydrogen storage cylinder, causing the cylinder to rupture and cause serious accidents.

[0003] Faced with the technical problem that the epoxy resin matrix in the carbon fiber winding layer of Type IV gas cylinders is prone to softening in a high temperature environment, thereby causing the hydrogen storage cylinder to rupture, in the prior art, Chinese invention patent CN112377799A discloses that after the carbon fiber winding layer is cured, a layer of refractory resin is brushed on its surface, and then a certain thickness of basalt fiber is wrapped around it for secondary curing, thereby enhancing the fire resistance of the gas cylinder. However, the above-mentioned traditional methods have the following problems: 1) Secondary curing by coating the fire-resistant layer increases the manufacturing cycle and production cost of the gas cylinder; 2) The refractory resin is generally applied manually by brushing, which does not meet the requirements of the standard for automotive compressed hydrogen plastic liner carbon fiber fully wrapped gas cylinders (T / CATSI 02 007—2020) regarding the fully automatic molding process of Type IV hydrogen storage cylinders; 3) Some of the gas cylinders are mainly used for natural gas cylinders, and the fire test verification of the gas cylinders in the standard for automotive compressed hydrogen plastic liner carbon fiber fully wrapped gas cylinders has not been carried out; 4) The fire process of the gas cylinder has a certain impact force, and the fire-resistant layer only considers the fire resistance, but the impact resistance of the gas cylinder is poor.

[0004] Based on this, faced with the problem that the IV-type gas cylinders in the prior art have poor impact resistance or complex manufacturing processes in high temperature environments, there is an urgent need to provide a new IV-type high-pressure hydrogen storage gas cylinder and a preparation method to improve the above problems. Summary of the invention

[0005] The main purpose of the present invention is to provide a type IV high-pressure hydrogen storage cylinder and a preparation method and application thereof, so as to solve the problems of poor impact resistance or complicated manufacturing process of type IV cylinders in the prior art in a high temperature environment.

[0006] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, there is provided a type IV high-pressure hydrogen storage cylinder, the structure of which includes: an inner liner, the outer surface of which is sprayed with a plasma coating; a carbon fiber winding layer, which is wound and coated on the outer surface of the inner liner sprayed with the plasma coating; a glass fiber winding layer, which is wound and coated on the outer surface of the carbon fiber winding layer away from the inner liner, and the material of the glass fiber winding layer is a composite material of glass fiber and a refractory resin material; the refractory resin material is a modified epoxy resin; wherein the refractory resin material includes epoxy resin, metal oxide, ammonium phosphate, graphite and triazine-type nitrogen-containing heterocyclic organic compounds.

[0007] Furthermore, the metal oxide is selected from one or more of titanium dioxide, zinc oxide or ferrosoferric oxide; preferably, the ammonium phosphate salt is selected from one or more of ammonium polyphosphate, phosphate ester or ammonium borate; preferably, the triazine nitrogen-containing heterocyclic organic compound is melamine and / or melamine phosphate; preferably, the graphite is expandable graphite and / or graphene; preferably, the material of the carbon fiber winding layer is a composite material of carbon fiber and epoxy resin; preferably, by weight, the epoxy resin in the refractory resin is 60 to 100 parts, the ammonium phosphate salt is 80 to 100 parts, the graphite is 10 to 20 parts, and the triazine nitrogen-containing heterocyclic organic compound is 50 to 80 parts, and further preferably, the weight ratio of epoxy resin, ammonium phosphate, graphite and triazine nitrogen-containing heterocyclic organic compound is (0.8.~2.0):(1 to 2 ):(0.1~0.4):1; Preferably, the carbon fiber winding layer is formed by winding a composite material strand of carbon fiber and epoxy resin, and the composite material strand of carbon fiber and epoxy resin is formed by impregnating and composited multiple carbon fibers with epoxy resin; further preferably, the diameter of the composite fiber material of carbon fiber and epoxy resin is 0.5~2.0mm, and the thickness of the carbon fiber winding layer is 5~35mm; preferably, the glass fiber winding layer is formed by winding a composite material strand of glass fiber and refractory resin material, and the fiber of the composite material of glass fiber and refractory resin material is a composite fiber formed by impregnating glass fiber in refractory resin material; further preferably, the diameter of the composite fiber of glass fiber and refractory resin material is 0.3~1.0mm, and the thickness of the glass fiber winding layer is 0.5~4.0mm.

[0008] Furthermore, in the glass fiber winding layer, the weight ratio of the refractory resin to the glass fiber is (0.2-0.5):1; preferably, in the carbon fiber winding layer, the weight ratio of the carbon fiber to the epoxy resin is (3-5):1; preferably, the winding method of the glass fiber winding layer is annular winding and / or spiral winding, and further preferably, the number of winding turns of the glass fiber winding layer is 1-10 turns; preferably, the gas source of the plasma equipment is one or more of O2, NH3, and SO2 gases.

[0009] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a method for preparing a type IV high-pressure hydrogen storage cylinder is provided, and the preparation method comprises the following steps: step S1, providing an inner liner; coating the outer surface of the inner liner with a plasma coating; step S2, coating the outer surface of the inner liner coated with the plasma coating to form a carbon fiber winding layer; step S3, further coating the outer surface of the carbon fiber winding layer away from the inner liner to form a glass fiber winding layer, so as to obtain a type IV high-pressure hydrogen storage cylinder.

[0010] Furthermore, step S1 includes: providing an inner liner; using plasma spraying equipment to spray the outer surface of the inner liner to coat the outer surface of the inner liner with a plasma coating; step S2 includes: impregnating carbon fiber with epoxy resin through a resin dipping tank, winding it around the outer surface of the plasma-coated inner liner, and pre-curing it to obtain an inner liner coated with a carbon fiber winding layer; step S3 includes: impregnating glass fiber with a refractory resin solution through a resin dipping tank, winding it around the carbon fiber winding layer, and further curing it to obtain a type IV high-pressure hydrogen storage cylinder; the refractory resin solution includes epoxy resin raw materials, metal oxides, ammonium phosphates, graphite, triazine-type nitrogen-containing heterocyclic organic compounds and solvents.

[0011] Furthermore, the temperature of the glue tank immersion treatment in step S2 and step S3 is 30-70°C; preferably, in step S3, the refractory resin solution contains a modified resin and a solvent, and the weight ratio of the modified resin to the solvent is (3-5):1; preferably, the solvent of step S3 is selected from one or more of xylene, ethanol or isopropanol; preferably, the refractory resin raw materials of step S3 include E44 monomer resin, menthane diamine (MDA), dibutyl phthalate and a silane coupling agent; preferably, the winding tension of the glass fiber winding layer is 10-15N.

[0012] Furthermore, in step S3, the curing treatment temperature is 90-150°C, more preferably 110-120°C, and the curing treatment time is 3-8h; preferably in step S1, the gas source of the plasma equipment is one or more of O2, NH3, and SO2 gases; preferably in the plasma spraying equipment, the plasma flow rate is 20-80L / min, and the spraying power is 1-10KW; preferably, the dyne value of the inner liner surface coated with the plasma coating is 65-85.

[0013] Furthermore, the weight ratio of glass fiber to refractory resin is (2-5):1; preferably, the weight ratio of carbon fiber to epoxy resin is (3-5):1.

[0014] Furthermore, in step S2, the winding tension of the carbon fiber winding layer is 50-80N; preferably, the winding tension of the fiber winding layer decreases from the inside to the outside as the number of winding layers increases, and further preferably, the winding tension difference between two adjacent layers is 0.5-3.0N; preferably, after the carbon fiber winding treatment and before the pre-curing treatment, inflation treatment is required, and further preferably, the pressure of the inflation treatment is 5-20bar; preferably, the temperature of the pre-curing treatment is 40-60°C, and the treatment time is 1-2h.

[0015] According to another aspect of the present invention, there is provided a method for preparing a Type IV high-pressure hydrogen storage cylinder, and its application in the field of mobile storage of high-pressure hydrogen.

[0016] By applying the technical solution of the present invention, the prepared type IV high-pressure hydrogen storage cylinder has excellent fire resistance and impact resistance, and the preparation process is simple, and has broad industrial application prospects. DETAILED DESCRIPTION

[0017] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0018] As described in the background technology part of the present invention, the IV type gas cylinder in the prior art has the problem of poor impact resistance or complicated manufacturing process in a high temperature environment. The present invention provides a IV type high pressure hydrogen storage gas cylinder, the structure of which includes: an inner liner, the outer surface of which is sprayed with a plasma coating; a carbon fiber winding layer, which is coated on the outer surface of the inner liner sprayed with the plasma coating; a glass fiber winding layer, which is coated on the outer surface of the carbon fiber winding layer, and the glass fiber winding layer includes glass fiber and a refractory resin material; wherein the refractory resin material is a modified epoxy resin.

[0019] Based on the problem that the bonding force between the liner (nylon-6 or polyethylene) and the carbon fiber winding layer in the IV type high pressure hydrogen storage cylinder in the prior art is weak, especially in a high temperature environment, it is easy to cause the carbon fiber winding layer to fall off, and the inner liner sprayed with a plasma coating used in the present invention further enhances the bonding strength between the inner liner and the carbon fiber winding layer in the IV type high pressure hydrogen storage cylinder. The plasma treatment can introduce polar groups or active points on the surface of the inner liner, so that a chemical bond or van der Waals force is formed between the inner liner material and the carbon fiber winding layer material, thereby achieving the purpose of enhancing the bonding and improving the mechanical strength and impact resistance of the IV type high pressure hydrogen storage cylinder. Then, a carbon fiber winding layer is coated on the outer surface of the inner liner sprayed with a plasma coating. The role of the carbon fiber winding layer is to further increase the bearing pressure of the IV type high pressure hydrogen storage cylinder, and then a glass fiber winding layer is coated on the outer surface of the carbon fiber winding layer to protect the carbon fiber winding layer. However, in the face of the IV type high pressure hydrogen storage cylinder in the prior art in a high temperature environment, the glass fiber winding layer prepared by conventional methods has poor fire resistance and poor impact resistance. The glass fiber winding layer in the IV type high pressure hydrogen storage cylinder of the present invention comprises glass fiber and fire resistant resin material to improve its fire resistance and impact resistance.

[0020] In particular, the refractory resin material in the present invention is a refractory resin, which includes epoxy resin, metal oxide, ammonium phosphate and triazine nitrogen-containing heterocyclic organic compounds. The present invention creatively adopts the above-mentioned refractory resin. As one of the largest varieties of thermosetting resins, epoxy resin has excellent thermosetting properties, stable thermochemical properties and strong fire resistance. Among them, the ammonium phosphate in the refractory resin dehydrates the epoxy resin at high temperature to form a dense carbon layer, which can isolate oxygen and heat sources to achieve good fireproof performance; the triazine nitrogen-containing heterocyclic organic compound can be carbonized at high temperature and release a large amount of gas, so that the carbon layer in the refractory resin changes from a single-layer structure to a mesh structure, increasing the distance between the fire source and the glass fiber winding layer, thereby enhancing the fire resistance of the gas cylinder; graphite can increase the density between the refractory resin carbon layers, thereby increasing the strength of the glass fiber winding layer, and then improving the fire resistance and impact strength of the gas cylinder; the metal oxide, as a granular form, plays a skeleton role in the mesh refractory resin carbon layer, thereby increasing the strength of the mesh refractory resin carbon layer. Therefore, on the one hand, the mesh refractory resin carbon layer has good mechanical properties, which can prevent the glass fiber winding layer from falling off due to the impact of flames. In addition, the glass fiber winding layer has a certain effect of isolating heat sources, and the excellent fireproof properties of ammonium phosphate itself can prevent the temperature of the gas cylinder from rising rapidly during the fire process. On the other hand, the refractory resin and the glass fiber winding layer are integrated into one design, which reduces the manufacturing process of the refractory layer, thereby further reducing the process and improving production efficiency.

[0021] In a preferred embodiment, the metal oxide is selected from one or more of titanium dioxide, zinc oxide or ferroferric oxide, so that it can further play a skeleton role in the reticular refractory resin and improve the strength of the reticular refractory resin; preferably, the ammonium phosphate salt is selected from one or more of ammonium polyphosphate, phosphate ester or ammonium borate, so as to further improve the fireproof performance; preferably, the triazine nitrogen-containing heterocyclic organic compound is selected from melamine and / or melamine phosphate, so as to further enable it to carbonize and release a large amount of gas at high temperature, and the refractory resin can hinder the heat transfer between the fire source and the carbon fiber winding layer in the IV type high-pressure hydrogen storage cylinder, thereby enhancing the fire resistance of the cylinder; preferably, the graphite is expandable graphite and / or graphene, which better increases the density between the refractory resins, thereby improving the strength of the glass fiber winding layer, and then improving the fire resistance and impact strength of the cylinder. Preferably, the material of the carbon fiber winding layer is a composite material of carbon fiber and epoxy resin, so as to further improve the mechanical strength of the carbon fiber winding layer.

[0022] In a preferred embodiment, the refractory resin contains 60 to 100 parts of epoxy resin, 80 to 100 parts of ammonium phosphate, 10 to 20 parts of graphite, and 50 to 80 parts of triazine-type nitrogen-containing heterocyclic organic compounds. It is further preferred that the weight ratio of epoxy resin, ammonium phosphate, graphite and triazine-type nitrogen-containing heterocyclic organic compounds is (0.8. to 2.0):(1 to 2):(0.1 to 0.4):1. The refractory resin has excellent fire resistance and impact strength.

[0023] In order to further improve the mechanical strength and stability of the carbon fiber winding layer, the carbon fiber winding layer is formed by winding a composite material strand rope of carbon fiber and epoxy resin, and the composite material strand rope of carbon fiber and epoxy resin is twisted by multiple fibers of the composite material of carbon fiber and epoxy resin, and the fibers of the composite material of carbon fiber and epoxy resin are composite fibers formed by impregnating carbon fiber in epoxy resin material; it is further preferred that the diameter of the composite fiber material of carbon fiber and epoxy resin is 0.5-2.0 mm, and the thickness of the carbon fiber winding layer is 5-35 mm.

[0024] In a preferred embodiment, the glass fiber winding layer is formed by winding a composite material strand of glass fiber and refractory resin material, and the composite material strand of glass fiber and refractory resin material is twisted by multiple fibers of the composite material of glass fiber and refractory resin material, and the fibers of the composite material of glass fiber and refractory resin material are composite fibers formed by impregnating glass fiber in refractory resin material; further preferably, the diameter of the composite fiber of glass fiber and refractory resin material is 0.3-1.0 mm, and the thickness of the glass fiber winding layer is 0.5-4.0 mm, thereby improving the mechanical strength of the glass fiber and further improving the impact strength of the gas cylinder.

[0025] In order to further improve the fire resistance and impact strength of Type IV high-pressure hydrogen storage cylinders, it is preferred that the weight ratio of refractory resin to glass fiber in the glass fiber winding layer is (0.2-0.5):1, and the weight ratio of carbon fiber to epoxy resin in the carbon fiber winding layer is (3-5):1.

[0026] In a preferred embodiment, the glass fiber winding layer is wound in a circumferential manner and / or in a spiral manner, and the number of windings of the glass fiber winding layer is preferably 1 to 10, thereby improving the mechanical strength of the glass fiber and the carbon fiber, and the preparation process is simple and suitable for large-scale production. In order to further improve the adhesion of the liner, it is further preferred that the gas source of the plasma equipment is one or more of O2, NH3, and SO2 gases.

[0027] Another aspect of the present invention also provides a method for preparing a Type IV high-pressure hydrogen storage cylinder, the preparation method comprising the following steps: providing an inner liner; coating the outer surface of the inner liner with a plasma coating; coating the outer surface of the inner liner coated with the plasma coating with a carbon fiber winding layer; further coating the outer surface of the carbon fiber winding layer away from the coated inner liner with a glass fiber winding layer to obtain a Type IV high-pressure hydrogen storage cylinder; the refractory resin solution comprises an epoxy resin raw material, a metal oxide, an ammonium phosphate salt, graphite, a triazine-type nitrogen-containing heterocyclic organic compound and a solvent.

[0028] A person skilled in the art may first take an inner liner, then coat the outer surface of the inner liner with a plasma coating, and then coat the outer surface of the inner liner coated with the plasma coating with a carbon fiber winding layer. Finally, a glass fiber winding layer is further coated on the outer surface of the carbon fiber winding layer away from the coated inner liner to obtain a type IV high-pressure hydrogen storage cylinder; wherein the refractory resin solution includes epoxy resin raw materials, metal oxides, ammonium phosphate salts, graphite, triazine-type nitrogen-containing heterocyclic organic compounds, and solvents. The type IV high-pressure hydrogen storage cylinder obtained by the preparation method of the present invention has excellent fire resistance and impact strength.

[0029] In a preferred embodiment, step S1 includes: providing an inner liner; spraying the outer surface of the inner liner with a plasma spraying device to coat the outer surface of the inner liner with a plasma coating; and / or step S2 includes: impregnating carbon fiber in epoxy resin to obtain composite fibers of a composite material of carbon fiber and epoxy resin, then taking a plurality of composite fibers and twisting them into strands, winding them around the outer surface of the inner liner coated with plasma coating, and pre-curing them to obtain an inner liner coated with a carbon fiber winding layer; and / or step S3 includes: impregnating glass fiber in a refractory resin to obtain composite fibers of a composite material of glass fiber and refractory resin, then taking a plurality of composite fibers and twisting them into strands, winding them around the outer surface of the carbon fiber winding layer away from the inner liner, and further curing them to obtain a type IV high-pressure hydrogen storage cylinder, wherein the refractory resin solution includes epoxy resin raw material, metal oxide, ammonium phosphate, graphite, triazine nitrogen-containing heterocyclic organic compounds and solvents.

[0030] The technicians in this field first use plasma spraying equipment to spray the surface of the inner liner to coat the outer surface of the inner liner with a plasma coating, and then impregnate the carbon fiber in epoxy resin to obtain a composite fiber of a composite material of carbon fiber and epoxy resin, and then take a plurality of composite fibers and twist them into strands, which are wound around the outer surface of the inner liner coated with plasma coating, and pre-cured to obtain an inner liner coated with a carbon fiber winding layer. Finally, take glass fiber and impregnate it in a refractory resin to obtain a composite fiber of a composite material of glass fiber and refractory resin, and then take a plurality of composite fibers and twist them into strands, which are wound around the outer surface of the carbon fiber winding layer away from the inner liner, and further cured to obtain a Type IV high-pressure hydrogen storage cylinder. The Type IV high-pressure hydrogen storage cylinder obtained by the preparation method of the present invention has excellent fire resistance and impact strength.

[0031] In a preferred embodiment, the impregnation temperature is 30-70°C, thereby further promoting the full immersion of the carbon fiber and glass fiber in the impregnation solution, improving their bonding strength, and further improving their mechanical properties. It is further preferred that the winding tension of the glass fiber winding layer is 10-15N.

[0032] In order to further improve the fire resistance and impact strength of the glass fiber winding layer, the solvent is preferably selected from one or more of xylene, ethanol or isopropanol; further preferably, in the refractory resin solution, the weight ratio of the refractory resin to the solvent is (3-5):1, and the epoxy resin raw materials preferably include E44 monomer resin, menthane diamine (MDA), dibutyl phthalate and a silane coupling agent, and the epoxy resin described above is obtained by curing the above-mentioned epoxy resin raw materials.

[0033] In a preferred embodiment, the preparation method of epoxy resin is as follows: take 100-150 parts of E44 monomer resin, 50-80 parts of menthane diamine (MDA), 10-20 parts of dibutyl phthalate and 1-5 parts of silane coupling agent and mix them at a stirring rate of 300-500 rpm and a stirring time of 10-20 min.

[0034] In order to further improve the mechanical properties and fire resistance of the glass fiber winding layer, in step S3, the curing temperature is 90-150°C, preferably 110-120°C, and the curing time is 3-8 hours; thereby further removing impurities such as air in the glass fiber winding layer to optimize the performance. Preferably, the curing process is carried out in a curing furnace, thereby further improving the fire resistance and impact resistance of the gas cylinder.

[0035] In order to further improve the bonding strength between the inner liner and the carbon fiber winding layer in the IV type high-pressure hydrogen storage cylinder, it is preferred that in step S1, the gas source of the plasma equipment is one or more of O2, NH3, and SO2 gases, and it is further preferred that in the plasma spraying equipment, the plasma flow rate is 20-80L / min, and the spraying power is 1-10KW; the dyne value of the inner liner surface coated with the plasma coating is 65-85.

[0036] In a preferred embodiment, the inner liner is injection molded using nylon-6 as raw material, the mold temperature during the injection molding process is 40-80°C, the barrel temperature is 200-300°C, the nozzle temperature is 250-320°C, the plasticizing pressure is 150-300bar, the injection pressure is 200-500bar, the injection time is 10-20s, and the cooling time is 100-200s.

[0037] In a preferred embodiment, the preparation steps of the refractory resin include: taking raw materials E44 monomer resin, menthane diamine, dibutyl phthalate, silane coupling agent, ammonium polyphosphate, melamine, titanium dioxide, expandable graphite, xylene, and ethanol, mixing, and rapidly stirring for 1 to 2 hours at a stirring rate of 300 to 500 r / min, and then using ultrasound for oscillation for 10 to 20 minutes, thereby obtaining a refractory resin with excellent performance.

[0038] In order to further improve the mechanical properties and fire resistance of the glass fiber winding layer and increase the bearing pressure of the Type IV high-pressure hydrogen storage cylinder, the weight ratio of glass fiber to fire-resistant resin is preferably (2-5):1; the weight ratio of carbon fiber to epoxy resin is (3-5):1.

[0039] In a preferred embodiment, in step S2, the winding tension of the carbon fiber winding layer is 50-80N, preferably the winding tension of the carbon fiber winding layer decreases from the inside to the outside as the number of winding layers increases, and further preferably the winding tension difference between two adjacent layers is 0.5-3.0N, so that the bearing pressure of the IV type high-pressure hydrogen storage cylinder can be further increased. Preferably, the temperature of the carbon fiber winding treatment is 35-45°C, so that the carbon fiber winding treatment is more sufficient, preferably after the carbon fiber winding treatment and before the pre-curing treatment, it is also necessary to perform an inflation treatment, and further preferably the inflation treatment pressure is 5-20bar, in order to further remove the air in the carbon fiber winding layer, preferably the pre-curing treatment temperature is 40-60°C, and the treatment time is 1-2h.

[0040] In a preferred embodiment, a protective cover is prepared by molding a polyurethane material, and epoxy structural adhesive is applied to the surfaces of the ends of the gas cylinder after polishing. The protective cover is then adhered to the ends of the gas cylinder and cured at room temperature for 1 to 2 hours.

[0041] In a preferred embodiment, the epoxy resin comprises: 100 parts of E44 monomer resin, 50-80 parts of menthane diamine (MDA), 10-20 parts of dibutyl phthalate, and 1-5 parts of silane coupling agent. The epoxy resin has excellent thermosetting properties and strong thermal stability.

[0042] Another aspect of the present invention further provides a type IV high-pressure hydrogen storage cylinder, or a type IV high-pressure hydrogen storage cylinder obtained by the above-mentioned method for preparing the type IV high-pressure hydrogen storage cylinder, and its application in the field of mobile storage of high-pressure hydrogen.

[0043] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0044] Example 1

[0045] 1) Liner: Nylon-6 is used as the raw material for injection molding. The mold temperature during the injection molding process is 45°C, the barrel temperature is 240°C, the nozzle temperature is 260°C, the plasticizing pressure is 250bar, the injection pressure is 400bar, the injection time is 10s, and the cooling time is 110s.

[0046] 2) Inner liner treatment: The plasma gas source is O2 plasma flow rate 60L / min, the spraying power is 3KW, and the dyne value of the inner liner surface after spraying is 70.

[0047] 3) Carbon fiber winding layer: T700 carbon fiber + E51 epoxy resin is used to prepare the carbon fiber winding layer. The inner volume is 57L, and 8 strands of carbon fiber are used for winding. The resin glue tank temperature is 35°C. The initial winding tension is 75N, and it decreases by 1N for each layer. After the tension decreases to 45N, it will no longer decrease. A total of 40 layers are wound. The inner winding process is inflated with an inflation pressure of 8bar. After the carbon fiber winding is completed, it is pre-cured at a temperature of 60°C and a pre-curing time of 1h. Among them, the weight ratio of refractory resin to carbon fiber is 25:75.

[0048] 4) Glass fiber winding layer: Take 100 parts of E44 monomer resin, 60 parts of menthane diamine (MDA), 10 parts of dibutyl phthalate, 2 parts of silane coupling agent, 80 parts of ammonium polyphosphate, 60 parts of melamine, 10 parts of titanium dioxide powder, 15 parts of expandable graphite, and the solvent is: 100 parts of xylene and 50 parts of ethanol. Mix the above raw materials with the solvent and stir rapidly for 1 hour at a stirring rate of 300 r / min, then oscillate with ultrasound for 10 minutes at an ultrasonic frequency of 28 kHz to obtain a refractory resin solution.

[0049] The glass fiber is impregnated with a refractory resin solution through a dipping tank, wound around a carbon fiber winding layer, and further cured to obtain a Type IV high-pressure hydrogen storage cylinder. The weight ratio of refractory resin to glass fiber is 1:3, the temperature of the dipping tank is 50°C, and the glass fiber winding tension is 12N. After winding, curing is performed at a curing temperature of 120°C and a curing time of 3h. In the refractory resin solution, the weight ratio of solvent to refractory resin is 1:3.

[0050] Finally, a protective cover was used. The protective cover was molded with polyurethane material. After the ends of the gas cylinder were polished, epoxy structural adhesive (E44 resin: polyamide curing agent = 1:1 mixture) was applied on the surface. Then the protective cover was pasted to the ends of the gas cylinder and cured at room temperature for 2 hours.

[0051] Among them, the diameter of the composite fiber of carbon fiber and epoxy resin in the IV type high-pressure hydrogen storage cylinder is 0.7mm, and the thickness of the carbon fiber winding layer is 21mm. The diameter of the composite fiber strand of glass fiber and refractory resin is 0.6mm, and the thickness of the glass fiber winding layer is 2mm. The winding method of the glass fiber winding layer is spiral winding 1 layer + hoop winding 2 layers, and the winding method of the carbon fiber winding layer is spiral winding 10 layers and hoop winding 20 layers.

[0052] Example 2

[0053] The only difference from Example 1 is that the metal oxide is zinc oxide.

[0054] Example 3

[0055] The only difference from Example 1 is that the metal oxide is ferrosoferric oxide.

[0056] Example 4

[0057] The only difference from Example 1 is that the ammonium phosphate salt is a phosphate ester.

[0058] Example 5

[0059] The difference from Example 1 is only that: ammonium phosphate is ammonium borate.

[0060] Example 6

[0061] The only difference from Example 1 is that the triazine nitrogen-containing heterocyclic organic compound is melamine phosphate.

[0062] Example 7

[0063] The only difference from Example 1 is that the graphite is graphene.

[0064] Example 8

[0065] The only difference from Example 1 is that the weight ratio of epoxy resin, ammonium phosphate, graphite and triazine nitrogen-containing heterocyclic organic compound is 0.8:1:0.1:1.

[0066] Example 9

[0067] The only difference from Example 1 is that the weight ratio of epoxy resin, ammonium phosphate, graphite and triazine nitrogen-containing heterocyclic organic compound is 2.0:2:0.4:1.

[0068] Example 10

[0069] The only difference from Example 1 is that the weight ratio of epoxy resin, ammonium phosphate, graphite and triazine nitrogen-containing heterocyclic organic compound is 0.8:2:0.4:1.

[0070] Embodiment 11

[0071] The only difference from Example 1 is that the weight ratio of epoxy resin, ammonium phosphate, graphite and triazine nitrogen-containing heterocyclic organic compound is 2.0:1:0.1:1.

[0072] Comparative Example 1

[0073] A conventional method is adopted to prepare a type IV high-pressure hydrogen storage cylinder, wherein the refractory resin material is epoxy resin.

[0074] Comparative Example 2

[0075] The only difference from Example 1 is that no metal oxide is contained.

[0076] Comparative Example 3

[0077] The only difference from Example 1 is that no ammonium phosphate is contained.

[0078] Comparative Example 4

[0079] The only difference from Example 1 is that no graphite is contained.

[0080] Comparative Example 5

[0081] The only difference from Example 1 is that it does not contain triazine nitrogen-containing heterocyclic organic compounds.

[0082] Performance Testing:

[0083] Fire test: It is carried out according to the standard of automotive compressed hydrogen plastic liner carbon fiber fully wrapped gas cylinders, requiring that during the fire process, the gas in the gas cylinder is released in time through the pressure relief device, and the gas cylinder does not explode.

[0084] The IV type high pressure hydrogen storage cylinders prepared in the above examples and comparative examples were tested, and the results are shown in Table 1 below.

[0085] Table 1

[0086]

[0087] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0088] It can be found from the test results of the above embodiments and comparative examples that when the IV type high pressure hydrogen storage cylinder of the present invention is used, especially when the structure of the IV type high pressure hydrogen storage cylinder includes a refractory resin, wherein the refractory resin material includes epoxy resin, metal oxide, ammonium phosphate, graphite and triazine type nitrogen heterocyclic organic compound, the IV type high pressure hydrogen storage cylinder has excellent fire resistance, excellent impact resistance in a high temperature environment, and a simple manufacturing process, and has broad application prospects. However, when the IV type high pressure hydrogen storage cylinder structure does not contain a refractory resin material, or one or more components of epoxy resin, metal oxide, ammonium phosphate, graphite and triazine type nitrogen heterocyclic organic compound are not added to the refractory resin material, the prepared IV type high pressure hydrogen storage cylinder has poor fire resistance or impact resistance.

[0089] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A type IV high pressure hydrogen storage cylinder, characterized in that: The structure of the IV type high pressure hydrogen storage cylinder includes: An inner liner, the outer surface of which is sprayed with a plasma coating; A carbon fiber winding layer is wound and coated on the outer surface of the inner liner sprayed with the plasma coating; A glass fiber winding layer is wound and coated on the outer surface of the carbon fiber winding layer away from the inner liner, and the material of the glass fiber winding layer is a composite material of glass fiber and a refractory resin material; the refractory resin material is a modified epoxy resin; Wherein, the fire-resistant resin material includes epoxy resin, metal oxide, ammonium phosphate, graphite and triazine nitrogen-containing heterocyclic organic compound.

2. The IV type high pressure hydrogen storage cylinder according to claim 1, characterized in that: The metal oxide is selected from one or more of titanium dioxide, zinc oxide or ferrosoferric oxide; Preferably, the ammonium phosphate salt is selected from one or more of ammonium polyphosphate, phosphate ester or ammonium borate; Preferably, the triazine nitrogen-containing heterocyclic organic compound is melamine and / or melamine phosphate; Preferably, the graphite is expandable graphite and / or graphene; Preferably, the material of the carbon fiber winding layer is a composite material of carbon fiber and epoxy resin; Preferably, in parts by weight, the epoxy resin in the refractory resin is 60 to 100 parts, the ammonium phosphate is 80 to 100 parts, the graphite is 10 to 20 parts, and the triazine nitrogen-containing heterocyclic organic compound is 50 to 80 parts. More preferably, the weight ratio of the epoxy resin, the ammonium phosphate, the graphite and the triazine nitrogen-containing heterocyclic organic compound is (0.

8. to 2.0):(1 to 2):(0.1 to 0.4):1; Preferably, the carbon fiber winding layer is formed by winding a composite material strand of carbon fiber and epoxy resin, and the composite material strand of carbon fiber and epoxy resin is formed by impregnating and compounding a plurality of carbon fibers with epoxy resin; further preferably, the diameter of the composite fiber material of carbon fiber and epoxy resin is 0.5-2.0 mm, and the thickness of the carbon fiber winding layer is 5-35 mm; Preferably, the glass fiber winding layer is formed by winding a composite material strand rope of the glass fiber and the refractory resin material, and the fibers of the composite material of the glass fiber and the refractory resin material are composite fibers formed by impregnating the glass fiber in the refractory resin material; further preferably, the diameter of the composite fiber of the glass fiber and the refractory resin material is 0.3-1.0 mm, and the thickness of the glass fiber winding layer is 0.5-4.0 mm.

3. The IV type high pressure hydrogen storage cylinder according to claim 1 or 2, characterized in that: In the glass fiber winding layer, the weight ratio of the refractory resin to the glass fiber is (0.2-0.5):1; Preferably, in the carbon fiber winding layer, the weight ratio of the carbon fiber to the epoxy resin is (3-5):1; Preferably, the winding mode of the glass fiber winding layer is hoop winding and / or spiral winding. Further preferably, the number of winding turns of the glass fiber winding layer is 1 to 10 turns. Preferably, the gas source of the plasma equipment is one or more of O2, NH3, and SO2 gases.

4. A method for preparing a type IV high-pressure hydrogen storage cylinder according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: Step S1, providing an inner liner; coating the outer surface of the inner liner with a plasma coating; Step S2, forming a carbon fiber winding layer on the outer surface of the inner liner coated with the plasma coating; Step S3, further coating the outer surface of the carbon fiber winding layer away from the inner liner to form a glass fiber winding layer to obtain the IV type high-pressure hydrogen storage cylinder.

5. The method for preparing a type IV high-pressure hydrogen storage cylinder according to claim 4, characterized in that: The step S1 comprises: providing an inner liner; spraying the outer surface of the inner liner with a plasma spraying device to coat the outer surface of the inner liner with the plasma coating; The step S2 comprises: impregnating the carbon fiber with epoxy resin through a resin dipping tank, winding the carbon fiber around the outer surface of the plasma-coated liner, and performing a pre-curing treatment to obtain an liner coated with a carbon fiber winding layer; The step S3 comprises: impregnating the glass fiber into a refractory resin solution through a dipping tank, winding the glass fiber around the carbon fiber winding layer, and further curing the glass fiber to obtain the type IV high-pressure hydrogen storage cylinder; the refractory resin solution comprises epoxy resin raw material, metal oxide, ammonium phosphate, graphite, triazine nitrogen-containing heterocyclic organic compound and solvent.

6. The method for preparing a type IV high pressure hydrogen storage cylinder according to claim 5, characterized in that: The temperature of the glue tank dipping treatment in step S2 and step S3 is 30-70° C.; Preferably, in the step S3, the refractory resin solution comprises a modified resin and a solvent, and the weight ratio of the modified resin to the solvent is (3-5):1; Preferably, the solvent in step S3 is selected from one or more of xylene, ethanol or isopropanol; Preferably, the refractory resin raw material in step S3 includes E44 monomer resin, menthane diamine (MDA), dibutyl phthalate and a silane coupling agent; Preferably, the winding tension of the glass fiber winding layer is 10-15N.

7. The method for preparing a type IV high pressure hydrogen storage cylinder according to claim 5, characterized in that: In the step S3, the curing temperature is 90 to 150° C., more preferably 110 to 120° C., and the curing time is 3 to 8 hours; Preferably, in step S1, the gas source of the plasma equipment is one or more of O2, NH3, and SO2 gases; Preferably, in the plasma spraying equipment, the plasma flow rate is 20 to 80 L / min, and the spraying power is 1 to 10 KW; Preferably, the dyne value of the inner liner surface coated with the plasma coating is 65-85.

8. The method for preparing a type IV high pressure hydrogen storage cylinder according to claim 4 or 5, characterized in that: The weight ratio of the glass fiber to the refractory resin is (2-5):1; Preferably, the weight ratio of the carbon fiber to the epoxy resin is (3-5):

1.

9. The method for preparing a type IV high pressure hydrogen storage cylinder according to claim 5, characterized in that: In the step S2, the winding tension of the carbon fiber winding layer is 50-80N; Preferably, the winding tension of the carbon fiber winding layer decreases from the inside to the outside as the number of winding layers increases. Further preferably, the winding tension difference between two adjacent layers is 0.5 to 3.0 N. Preferably, after the carbon fiber winding process and before the pre-curing process, an inflation process is required. Further preferably, the pressure of the inflation process is 5 to 20 bar. Preferably, the pre-curing treatment temperature is 40-60° C., and the treatment time is 1-2 hours.

10. Use of a Type IV high-pressure hydrogen storage cylinder according to any one of claims 1 to 3, or a Type IV high-pressure hydrogen storage cylinder obtained by the method for preparing a Type IV high-pressure hydrogen storage cylinder according to any one of claims 4 to 9, in the field of mobile storage of high-pressure hydrogen.

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