A method of manufacturing a cryogenic high pressure hydrogen storage cylinder and liner

Abstract

The application provides a preparation method of a low-temperature high-pressure hydrogen storage bottle and an inner liner, relates to the technical field of hydrogen storage, and is used for guaranteeing the overall performance of the low-temperature high-pressure hydrogen storage bottle. The low-temperature high-pressure hydrogen storage bottle comprises the inner liner, and the inner liner comprises the following components in percentage by mass: Li: 0.54-1.60%, Si: 0.27-0.88%, Fe: 0.27-0.77%, Cu: 0.13-0.44%, Mn: 0.09-0.99%, Mg: 0.72-1.32%, Cr: 0.03-0.39%, Zn: 0-0.33%, Ti: 0-0.17%, negative thermal expansion material: 27.00-72.00%, and the balance is aluminum and inevitable impurity elements. Therefore, the shrinkage phenomenon of the inner liner can be reduced on the overall level when the temperature is reduced, the debonding and delamination between the inner liner and the winding layer are avoided, and then the overall performance of the low-temperature high-pressure hydrogen storage bottle is maintained.

Description

TECHNICAL FIELD

[0001] The application relates to the hydrogen storage technical field, in particular to a low-temperature high-pressure hydrogen storage bottle and a preparation method of an inner liner. BACKGROUND

[0002] Hydrogen energy is a kind of secondary energy with rich sources, green and low carbon, and has the advantages of high combustion value, zero pollution and rich reserves. In order to meet the needs of large-scale storage and application, hydrogen needs to be densified, that is, as much fuel as possible is stored in a limited space.

[0003] Low-temperature high-pressure hydrogen storage is a method combining low-temperature hydrogen storage and high-pressure hydrogen storage, which uses an adiabatic pressure-resistant gas cylinder to store hydrogen in a supercritical state under low-temperature and high-pressure combined conditions. Compared with other hydrogen storage methods, low-temperature high-pressure hydrogen storage has significant advantages in mass hydrogen storage density, volume hydrogen storage density, hydrogen storage cost, safety and evaporation loss. The hydrogen storage bottle in the related art is a pressure vessel using aluminum alloy as an inner liner material and wound by a fiber composite material, which is usually used to store high-pressure gas at room temperature. However, in the process of low-temperature high-pressure hydrogen storage, there is a temperature cycle process from high temperature (room temperature) to low temperature (hydrogen storage temperature). Due to the different thermal expansion coefficients, the aluminum alloy inner liner and the composite material layer will produce debonding and delamination. This debonding and delamination phenomenon makes the inner liner unstable and appears a collapsed bulge under the action of external pressure. When the container is pressurized again, the bulge is pressed back, and this process is repeated, which causes the metal inner liner to be damaged under fatigue, thereby affecting the overall performance of the hydrogen storage bottle. SUMMARY

[0004] In order to solve the above technical problems, the application provides a preparation method of a low-temperature high-pressure hydrogen storage bottle and an inner liner, which is used to ensure the overall performance of the low-temperature high-pressure hydrogen storage bottle.

[0005] To achieve the above purpose, the embodiments of the application adopt the following technical solutions:

[0006] In a first aspect, the embodiments of the application provide a low-temperature high-pressure hydrogen storage bottle. The low-temperature high-pressure hydrogen storage bottle comprises an inner liner. The inner liner comprises the following components in mass percentage: Li: 0.54-1.60%, Si: 0.27-0.88%, Fe: 0.27-0.77%, Cu: 0.13-0.44%, Mn: 0.09-0.99%, Mg: 0.72-1.32%, Cr: 0.03-0.39%, Zn: 0-0.33%, Ti: 0-0.17%, negative thermal expansion material: 27.00-72.00%, and the balance is aluminum and unavoidable impurity elements.

[0007] According to the low-temperature high-pressure hydrogen storage bottle provided in the embodiments of the present application, the inner liner is made of aluminum alloy and a material with a negative thermal expansion coefficient. When the temperature decreases, the aluminum alloy material produces a shrinkage effect and the material with a negative thermal expansion coefficient produces an expansion effect, so that the shrinkage of the inner liner when the temperature decreases can be reduced on the whole, and the debonding and delamination between the inner liner and the winding layer can be avoided, thereby being beneficial to maintaining the overall performance of the low-temperature high-pressure hydrogen storage bottle.

[0008] In some embodiments, the inner liner comprises the following components in percentage by mass: Li: 0.60-1.50%, Si: 0.30-0.80%, Fe: 0.30-0.70%, Cu: 0.15-0.40%, Mn: 0.10-0.90%, Mg: 0.80-1.20%, Cr: 0.04-0.35%, Zn: 0-0.30%, Ti: 0-0.15%, zirconium tungstate: 50%, and the balance being aluminum and inevitable impurity elements.

[0009] In some embodiments, the inner liner comprises the following components: Li: 0.60-1.50%, Si: 0.30-0.80%, Fe: 0.30-0.70%, Cu: 0.15-0.40%, Mn: 0.10-0.90%, Mg: 0.80-1.20%, Cr: 0.04-0.35%, Zn: 0-0.30%, Ti: 0-0.15%, scandium tungstate: 55%, and the balance being aluminum and inevitable impurity elements.

[0010] In some embodiments, the low-temperature high-pressure hydrogen storage bottle further comprises a winding layer. The winding layer is a fiber resin composite material, and the winding layer is arranged on the outer side of the inner liner.

[0011] In some embodiments, the fiber in the fiber resin composite material comprises carbon fiber or basalt fiber. The resin in the fiber resin composite material comprises epoxy resin or modified epoxy resin.

[0012] In a second aspect, the present application provides a preparation method of the above-mentioned inner liner, which comprises: smelting: melting and heat preservation of raw materials in a smelting furnace, and effectively removing impurities and gas in the melt through gas removal and slag removal refining means; casting: pouring after smelting to obtain a cast ingot; heat treatment: placing the cast ingot in a soaking furnace for homogenization treatment; face milling: transporting the cast ingot obtained after homogenization treatment to a milling machine to cut off the head and tail for face milling; hot rolling: hot rolling the cast ingot after face milling in a hot rolling workshop; annealing: placing the plate after hot rolling at room temperature in an annealing furnace.

[0013] In some embodiments, during smelting, the temperature in the smelting furnace is 740-760℃, and the heat preservation time is 30-40 min.

[0014] In some embodiments, the temperature of the heat treatment is 550-580 DEG C, and the holding time is 6-10 hours.

[0015] In some embodiments, during the hot rolling, the starting rolling temperature is 500-520 DEG C, the finishing rolling temperature is 280-300 DEG C, and the thickness of the inner lining plate material obtained by the hot rolling is 20-40 mm.

[0016] In some embodiments, the temperature of the annealing is 80-100 DEG C, and the holding time is 4 hours.

[0017] The technical effects brought by any one of the designs in the second aspect can refer to the technical effects brought by different designs in the first aspect, which will not be repeated here. BRIEF DESCRIPTION OF DRAWINGS

[0018] The accompanying drawings, which are incorporated herein and constitute part of the specification, illustrate embodiments consistent with the application and, together with the description, serve to explain the principles of the application.

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the application or the technical solutions in the related art, the accompanying drawings needed to be used in the embodiments or the related art description will be briefly introduced. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0020] Figure 1 A schematic diagram of the low-temperature high-pressure hydrogen storage bottle provided by some embodiments of the application.

[0021] Reference signs:

[0022] 100, low-temperature high-pressure hydrogen storage bottle;

[0023] 1, bottom; 2, cylinder; 3, head; 4, bottle mouth; 5, winding layer. DETAILED DESCRIPTION

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the application or the technical solutions in the related art, the accompanying drawings needed to be used in the embodiments or the related art description will be briefly introduced. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0025] In the description of the application, it should be understood that the terms "upper", "lower", "front", "back", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the application.

[0026] In the description of the embodiments of the present application, it should be noted that unless specifically defined and limited otherwise, the terms "mounting", "connected", "connection" should be interpreted broadly, for example, "connection" can be removable connection, or can be non-removable connection, can be direct connection, or indirect connection through intermediate medium. Among them, "fixed connection" refers to the connection of each other and the relative position relationship after the connection does not change. In addition, the orientation language mentioned in the embodiments of the present application, such as "inner", "outer" and the like, is only the direction of the drawing, therefore, the orientation language used is to better, more clearly illustrate and understand the embodiments of the present application, and is not intended to indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, therefore, it cannot be understood as a limitation on the embodiments of the present application.

[0027] In the description of the embodiments of the present application, the terms "including", "containing" or any other variant thereof are intended to cover non-exclusive inclusion, so that the process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or includes elements inherent to such process, method, article or device. Without more limitation, the element defined by the sentence "including a…" does not exclude the presence of another identical element in the process, method, article or device including the element. Without more limitation, the element defined by the sentence "including a…" does not exclude the presence of another identical element in the process, method, article or device including the element.

[0028] Please refer to Figure 1 , Figure 1 The schematic diagram of the low-temperature high-pressure hydrogen storage bottle provided by some embodiments of the present application. The embodiments of the present application provide a low-temperature high-pressure hydrogen storage bottle 100, which comprises a winding layer 5 and an inner liner. The winding layer 5 is a fiber resin composite material. The winding layer 5 is arranged outside the inner liner.

[0029] The inner liner of one embodiment of the present application is described below.

[0030] The present application provides an inner liner applied to a hydrogen storage bottle. The inner liner can include the following components in percentage by mass: Li: 0.54-1.60%, Si: 0.27-0.88%, Fe: 0.27-0.77%, Cu: 0.13-0.44, Mn: 0.09-0.99%, Mg: 0.72-1.32%, Cr: 0.03-0.39%, Zn: 0-0.33%, Ti: 0-0.17%, negative thermal expansion material: 27.00-72.00%, and the balance being aluminum and unavoidable impurity elements.

[0031] Exemplarily, the inner liner can include the following components in percentage by mass: Li: 0.80%, Si: 0.28%, Fe: 0.28%, Cu: 0.14%, Mn: 0.10%, Mg: 0.75%, Cr: 0.06%, Zn: 0.10%, Ti: 0.10%, negative thermal expansion material: 28.00%, and the balance being aluminum and inevitable impurity elements.

[0032] Exemplarily, the inner liner can include the following components in percentage by mass: Li: 0.70%, Si: 0.50%, Fe: 0.40%, Cu: 0.25%, Mn: 0.50%, Mg: 0.90%, Cr: 0.20%, Zn: 0.20%, Ti: 0.12%, negative thermal expansion material: 40.00%, and the balance being aluminum and inevitable impurity elements.

[0033] The low-temperature high-pressure hydrogen storage bottle according to the embodiments of the present application can reduce the shrinkage of the inner liner when the temperature decreases, avoid the debonding and delamination between the inner liner and the winding layer 5, and thus help maintain the overall performance of the low-temperature high-pressure hydrogen storage bottle 100.

[0034] The preparation method of the inner liner is described below.

[0035] The present application provides a preparation method of an inner liner, which comprises the following steps:

[0036] Smelting: the prepared raw materials are added into a smelting furnace to be melted at 740-760°C, and the slag and gas in the melt are effectively removed through degassing and slag removal refining means;

[0037] Casting: after smelting, casting is performed to obtain a cast ingot;

[0038] Heat treatment: the cast ingot is placed in a soaking furnace, heated to 550-580°C, and soaked for 6-10 hours for homogenization treatment, so as to reduce the residual stress in the material and improve the mechanical properties of the material;

[0039] Face milling: the cast ingot obtained after homogenization treatment is transported to a milling machine to mill the head and tail;

[0040] Hot rolling: the cast ingot after face milling is subjected to hot rolling in a hot rolling workshop to obtain an inner liner plate with a thickness of 20-40 mm, wherein the starting rolling temperature is 500-520°C and the final rolling temperature is 280-300°C;

[0041] Annealing: after the hot-rolled plate is cooled to room temperature, it is placed in an annealing furnace, the annealing temperature is 80-100°C, the holding time is 4h, and an aluminum alloy negative thermal expansion material plate is formed.

[0042] When the aluminum alloy negative thermal expansion material plate is obtained, the inner liner is manufactured, and the manufacturing steps are as follows: first, the aluminum alloy negative thermal expansion material plate is spun by a spinning device to form a pipe with a closed bottom and an open end. Then, the spinning machine is used to spin and form the head 3 and the bottle mouth 4. Finally, the spinning and forming piece is heat treated to obtain the inner liner blank of the low-temperature high-pressure hydrogen storage bottle 100.

[0043] It should be noted that the inner liner can include the bottom 1, the cylinder 2, the head 3 and the bottle mouth 4.

[0044] In some embodiments, the fibers in the fiber resin composite material include carbon fibers or basalt fibers. The resin in the fiber resin composite material includes epoxy resin or modified epoxy resin.

[0045] When the inner liner blank is obtained, the winding layer 5 is fixed on the inner liner, and the manufacturing steps are as follows: first, the aluminum alloy negative thermal expansion material inner liner is fixed. Then, the carbon fiber tows are combined with the resin in the glue dipping device, and the inner liner is wound under tension control. The winding method alternately uses hoop winding and spiral winding. The hoop winding angle is 90°, and is only performed on the cylinder 2; the spiral winding angle is 5-50°, and is performed on the cylinder 2, the bottom 1 and the head 3, and the angle is gradually increased during winding, such as 5° for the first layer, 15° for the second layer, and 25° for the third layer. Finally, the gas cylinder obtained after winding is sent into a curing oven and heated to 90-110°C, and the resin is cured for 2-3h to obtain the low-temperature high-pressure hydrogen storage bottle 100.

[0046] The inner liner of another embodiment of the present application is described below.

[0047] In some embodiments, the inner liner can include the following components in mass percentage: Li: 0.60-1.50%, Si: 0.30-0.80%, Fe: 0.30-0.70%, Cu: 0.15-0.40%, Mn: 0.10-0.90%, Mg: 0.80-1.20%, Cr: 0.04-0.35%, Zn: 0-0.30%, Ti: 0-0.15%, zirconium tungstate: 50%, and the balance is aluminum and unavoidable impurity elements. Such setting is conducive to maintaining the overall performance of the low-temperature high-pressure hydrogen storage bottle 100.

[0048] Exemplarily, the inner liner can include the following components in percentage by mass: Li: 0.70%, Si: 0.70%, Fe: 0.60%, Cu: 0.30%, Mn: 0.80%, Mg: 1.10%, Cr: 0.25%, Zn: 0.20%, Ti: 0.10%, zirconium tungstate: 50%, and the balance being aluminum and inevitable impurity elements.

[0049] The manufacturing steps of the low-temperature high-pressure hydrogen storage cylinder 100 using the above inner liner are as follows: the aluminum alloy zirconium tungstate plate is subjected to spinning by a spinning device to form a pipe material with a closed bottom at one end and an open end at the other end, the spinning device is then used to form the end cap 3 and the cylinder mouth 4, and finally the spinning formed part is subjected to heat treatment to obtain the inner liner blank. The winding layer 5 is made of carbon fiber epoxy resin composite material. After the aluminum alloy zirconium tungstate inner liner is fixed, the carbon fiber tows are combined with the resin in a resin impregnation device, and the inner liner is wound under tension control. The winding method alternately uses hoop winding and spiral winding. The hoop winding angle is 90°, and is only performed on the cylinder 2; the spiral winding angle is 5-50°, and is performed on the cylinder 2, the closed bottom 1 and the end cap 3. The angle is gradually increased during the winding process, the first layer is 5°, the second layer is 15°, and the third layer is 25°. Finally, the cylinder obtained after winding is sent into a curing oven and heated to 90-110°C for 2-3 hours to cure the resin, thereby obtaining the low-temperature high-pressure hydrogen storage cylinder 100.

[0050] The inner liner of another embodiment of the present application is described below.

[0051] In some embodiments, the inner liner includes the following components in percentage by mass: Li: 0.60-1.50%, Si: 0.30-0.80%, Fe: 0.30-0.70%, Cu: 0.15-0.40%, Mn: 0.10-0.90%, Mg: 0.80-1.20%, Cr: 0.04-0.35%, Zn: 0-0.30%, Ti: 0-0.15%, scandium tungstate: 55%, and the balance being aluminum and inevitable impurity elements. Such a setting is conducive to maintaining the overall performance of the low-temperature high-pressure hydrogen storage cylinder 100.

[0052] Exemplarily, the inner liner can include the following components in percentage by mass: Li: 0.8%, Si: 0.60%, Fe: 0.50%, Cu: 0.20%, Mn: 0.70%, Mg: 1.05%, Cr: 0.20%, Zn: 0.15%, Ti: 0.12%, scandium tungstate: 55%, and the balance being aluminum and inevitable impurity elements.

[0053] It should be noted that the method for manufacturing the low-temperature high-pressure hydrogen storage cylinder 100 using the inner liner is similar to the above, and will not be described here.

[0054] In the description of the present specification, specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in an appropriate manner.

[0055] The above description is merely a specific implementation of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A cryogenic high pressure hydrogen storage cylinder, characterized by, The low-temperature high-pressure hydrogen storage bottle comprises an inner liner; the inner liner comprises the following components in mass percentage: Li: 0.60-1.50%, Si: 0.30-0.80%, Fe: 0.30-0.70%, Cu: 0.15-0.40%, Mn: 0.10-0.90%, Mg: 0.80-1.20%, Cr: 0.04-0.35%, Zn: 0-0.30%, Ti: 0-0.15%, zirconium tungstate: 50%, and the balance being aluminum and inevitable impurity elements; or, The inner liner comprises the following components in mass percentage: Li: 0.60-1.50%, Si: 0.30-0.80%, Fe: 0.30-0.70%, Cu: 0.15-0.40%, Mn: 0.10-0.90%, Mg: 0.80-1.20%, Cr: 0.04-0.35%, Zn: 0-0.30%, Ti: 0-0.15%, scandium tungstate: 55%, and the balance being aluminum and inevitable impurity elements. The low-temperature high-pressure hydrogen storage bottle further comprises a winding layer, which is a fiber resin composite material and is arranged outside the inner liner.

2. The cryogenic high-pressure hydrogen storage bottle of claim 1, wherein, The fiber in the fiber resin composite material comprises carbon fiber or basalt fiber; and the resin in the fiber resin composite material comprises epoxy resin or modified epoxy resin.

3. The method of producing a liner for a cryogenic high-pressure hydrogen storage cylinder according to any one of claims 1 to 2, characterized in that, The preparation method comprises: melting: raw materials are added into a melting furnace for melting, heat preservation, and effective removal of impurities and gas in the melt through gas removal and slag removal refining means; casting: after melting, pouring is performed to obtain a cast ingot; heat treatment: the cast ingot is placed in a soaking furnace for homogenization treatment; face milling: the cast ingot obtained after homogenization treatment is transported to a milling machine to mill the head and tail; hot rolling: the cast ingot after face milling is subjected to hot rolling in a hot rolling workshop; annealing: after the hot-rolled plate is cooled to room temperature, it is placed in an annealing furnace.

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