A hydrogen embrittlement resistant hydrogen storage tank liner, method of manufacture and use thereof

Abstract

The application provides a hydrogen embrittlement resistant hydrogen storage tank liner and a manufacturing method and application thereof, and belongs to the technical field of hydrogen energy. The hydrogen embrittlement resistant hydrogen storage tank liner comprises, from inside to outside, a hydrogen storage structure, a carbon fiber layer and an aluminum alloy liner. The hydrogen storage structure is a gaseous hydrogen storage structure, a solid hydrogen storage structure or a gas-solid hydrogen storage structure, and is used for hydrogen storage. Thermoplastic carbon fibers are wound on the outside of the hydrogen storage structure to form the carbon fiber layer, and the carbon fiber layer is attached to the aluminum alloy liner to form a hydrogen embrittlement resistant layer, which is used for preventing hydrogen embrittlement and improving hydrogen storage pressure. The application can realize lightweight while increasing the pressure bearing capacity of the hydrogen storage structure, can be applied to solid hydrogen storage structures and gas-solid hydrogen storage structures, has a wider application range and a better application prospect, and the hydrogen embrittlement resistant layer formed by attaching the carbon fiber layer to the aluminum alloy liner can avoid direct contact between the aluminum alloy liner and hydrogen, thereby greatly avoiding hydrogen embrittlement of the aluminum alloy, and effectively improving hydrogen storage efficiency, safety and service life.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen energy technology, and more specifically, relates to an anti-hydrogen embrittlement hydrogen storage tank liner, its manufacturing method, and its application. Background Technology

[0002] Currently, most Chinese companies possess technology for vehicle-mounted hydrogen storage tanks with a pressure of 35 MPa, primarily using Type III tanks. Development of 70 MPa hydrogen storage tanks remains immature. Due to the limited strength of aluminum alloy liners, increasing their working pressure necessitates increasing the wall thickness, significantly increasing their mass and drastically reducing hydrogen storage efficiency per unit mass. Furthermore, under high pressure, direct contact between the aluminum alloy liner and hydrogen gas can cause hydrogen embrittlement, severely impacting their service life.

[0003] In terms of existing technology, there are two solutions to overcome the hydrogen embrittlement problem of aluminum inner liners in hydrogen storage tanks: The first is to laminate a layer of polyethylene film onto the inner wall of the metal liner. Using blow molding (compressed air), the polyethylene film is tightly adhered to the inner wall, isolating hydrogen gas and effectively preventing hydrogen embrittlement. However, the polyethylene film cannot withstand high temperatures and can only be used for high-pressure gaseous hydrogen storage. If hydrogen storage metal is used, a large amount of heat will be released during hydrogen storage, which polyethylene material cannot withstand due to its low temperature resistance. Furthermore, the bonding in this process is not very strong. The second solution is to design an anti-hydrogen embrittlement layer formed by combining an inner layer of hydrogen storage metal and an outer layer of aluminum alloy. However, at high hydrogen storage pressures, the anti-hydrogen embrittlement function of this structure will decrease sharply, seriously affecting the safety and service life of the hydrogen storage tank.

[0004] Therefore, hydrogen storage tanks combining high-pressure gaseous and solid-state hydrogen storage cannot effectively solve the hydrogen embrittlement problem of aluminum liners and still require improvement. In terms of current manufacturing processes, composite material hydrogen storage tanks mostly use welding and other connection methods to combine with aluminum alloy liners. This method reduces the strength of the liners to some extent, and further improvements are needed to achieve high-pressure hydrogen storage. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a hydrogen storage tank liner with hydrogen embrittlement prevention, its manufacturing method and application, aiming to solve the problem of poor pressure bearing capacity and hydrogen embrittlement prevention capacity of existing hydrogen storage tank liners.

[0006] To achieve the above objectives, according to one aspect of the present invention, a hydrogen storage tank liner for preventing hydrogen embrittlement is provided, comprising a hydrogen storage structure, a carbon fiber layer, and an aluminum alloy liner arranged sequentially from the inside to the outside. The hydrogen storage structure is a gaseous hydrogen storage structure, a solid hydrogen storage structure, or a gas-solid hydrogen storage structure, used for hydrogen storage. Thermoplastic carbon fiber is wound around the outside of the hydrogen storage structure to form a carbon fiber layer, and is bonded to the aluminum alloy liner to form a hydrogen embrittlement-preventing layer, used to prevent hydrogen embrittlement and increase the hydrogen storage pressure.

[0007] As a further preferred embodiment, the hydrogen storage structure is a gas-solid hydrogen storage structure, comprising two ventilated filter hemispherical shells, several phase change heat pipes, and several solid hydrogen storage rings. The ventilated filter hemispherical shells have a ventilation channel in the middle for supplying hydrogen from the aluminum alloy inner liner. The two ventilated filter hemispherical shells have filter holes on their planes, and the planes of the two ventilated filter hemispherical shells are arranged opposite each other, respectively connected to the phase change heat pipes, for filtering the hydrogen output from the phase change heat pipes and sending it into the aluminum alloy inner liner. Each of the phase change heat pipes is arranged parallel to the two ventilated filter hemispherical shells along the axial direction. Simultaneously, the solid hydrogen storage rings are circularly sleeved on the outside of the phase change heat pipes and connected to the phase change heat pipes via connecting pipes, thereby achieving gas-solid composite hydrogen storage.

[0008] As a further preferred embodiment, the phase change heat pipe and the connecting pipe are made of a composite solid-solid phase change material with aluminum powder as the phase change material and high-alumina bauxite and white mud as the matrix material.

[0009] As a further preferred embodiment, the solid hydrogen storage ring is made of a hydrogen storage material and a metal matrix, wherein the hydrogen storage material is an AB5 type hydrogen storage alloy and the metal matrix is ​​an aluminum alloy or copper.

[0010] According to another aspect of the present invention, a method for manufacturing an inner liner of a hydrogen storage tank to prevent hydrogen embrittlement is provided, the method comprising the following steps:

[0011] S1 is used to prepare hydrogen storage structures;

[0012] S2 wraps thermoplastic carbon fibers around the periphery of the hydrogen storage structure to form a carbon fiber layer, and then performs air plasma surface treatment on it to improve its chemical activity.

[0013] S3 prepares a cylindrical aluminum alloy inner liner and performs an oxidation treatment on its interior to increase its adhesiveness. The composite structure of hydrogen storage structure and carbon fiber layer obtained in step S2 is then inserted into the aluminum alloy inner liner to make them fit together. The inner liner of the hydrogen embrittlement-resistant hydrogen storage tank is obtained by spin forming.

[0014] As a further preferred embodiment, when the hydrogen storage structure is a gas-solid hydrogen storage structure, step S1 includes the following sub-steps:

[0015] S11 uses aluminum powder as the phase change material and high-alumina bauxite and white mud as the matrix material to perform unidirectional film pressing and then aging treatment to make a phase change heat pipe.

[0016] S12 is made of aluminum alloy through a stamping process to form a metal matrix ring;

[0017] S13 melts and anneals the hydrogen storage alloy and uses it to prepare hydrogen storage alloy sheets. Then, the hydrogen storage alloy sheets are covered on the outside of the metal matrix ring by electrochemical action to obtain a solid hydrogen storage ring.

[0018] S14 sintersects powdered copper into a hemispherical air-filtering shell.

[0019] S15 connects the phase change heat pipe, the solid hydrogen storage ring, and the ventilated filter hemispherical shell to form a gas-solid hydrogen storage structure.

[0020] As a further preferred embodiment, in step S15, the phase change heat pipe, the solid hydrogen storage ring, and the ventilated filter hemispherical shell are connected by friction welding.

[0021] According to another aspect of the present invention, a hydrogen embrittlement-resistant hydrogen storage tank is provided, comprising a protective layer, an outer fiber layer and an inner liner arranged sequentially from the outside to the inside, wherein the inner liner is the aforementioned hydrogen embrittlement-resistant hydrogen storage tank inner liner.

[0022] In summary, the technical solutions conceived by this invention have the following beneficial effects compared with the prior art:

[0023] 1. This invention forms a carbon fiber layer by winding thermoplastic carbon fiber around the outside of the hydrogen storage structure, which can increase the pressure resistance of the hydrogen storage structure while achieving weight reduction. Compared with polyethylene bag film, the carbon fiber layer can withstand high temperature and can be applied to solid hydrogen storage structures and gas-solid hydrogen storage structures, with a wider range of applications and better application prospects. Furthermore, the anti-hydrogen embrittlement layer formed by bonding the carbon fiber layer with the aluminum alloy inner liner can prevent the aluminum alloy inner liner from directly contacting hydrogen, thereby greatly avoiding hydrogen embrittlement of the aluminum alloy. Compared with the anti-hydrogen embrittlement layer formed by bonding the hydrogen storage metal with the aluminum alloy inner liner, it can prevent hydrogen embrittlement under higher pressure, effectively improving hydrogen storage efficiency, safety and service life.

[0024] 2. At the same time, the present invention optimizes the hydrogen storage structure, providing a basis for the carbon fiber winding of the anti-hydrogen embrittlement layer, which can better prevent the aluminum alloy from undergoing hydrogen embrittlement under high pressure. Furthermore, the hydrogen storage structure adopts a solid-solid phase change heat exchange material, which greatly improves the heat exchange efficiency and realizes the recycling of energy, effectively improving the hydrogen storage efficiency while achieving a lightweight design.

[0025] 3. In addition, the present invention optimizes the materials of the phase change heat pipe and the solid hydrogen storage ring, so that the hydrogen storage structure has high latent heat of phase change and hydrogen absorption capacity, and has good cycle life. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the structure of the inner liner of the hydrogen storage tank for preventing hydrogen embrittlement provided in an embodiment of the present invention;

[0027] Figure 2 This is a schematic diagram of the hydrogen storage structure provided in an embodiment of the present invention;

[0028] Figure 3This is a flowchart illustrating the preparation process of the hydrogen embrittlement-resistant hydrogen storage tank liner provided in this embodiment of the invention.

[0029] In all the accompanying drawings, the same reference numerals are used to denote the same elements or structures, wherein:

[0030] 1-Phase change heat pipe, 2-Solid hydrogen storage ring, 3-Ventilation filter hemispherical shell, 4-Carbon fiber layer, 5-Aluminum alloy inner liner. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0032] like Figure 1 As shown, according to one aspect of the present invention, a hydrogen storage tank liner with hydrogen embrittlement prevention is provided, comprising a hydrogen storage structure, a carbon fiber layer 4, and an aluminum alloy liner 5 arranged sequentially from the inside to the outside. The hydrogen storage structure is a gaseous hydrogen storage structure, a solid hydrogen storage structure, or a gas-solid hydrogen storage structure, used for hydrogen storage. Thermoplastic carbon fiber is wound around the outside of the hydrogen storage structure to form a carbon fiber layer 4, and is bonded to the aluminum alloy liner 5 to form a hydrogen embrittlement prevention layer, so that the aluminum alloy liner 5 avoids direct contact with hydrogen gas, which can greatly prevent hydrogen embrittlement of the aluminum alloy. It achieves weight reduction while increasing the hydrogen storage pressure, can prevent hydrogen embrittlement at higher pressures, increases hydrogen storage efficiency, and greatly improves safety and service life under the same hydrogen storage pressure. Compared with the blown film formed by polyethylene in the prior art, the carbon fiber layer 4 formed by thermoplastic carbon fiber winding can not only better combine with the aluminum alloy to form a hydrogen embrittlement prevention layer, but also can be applied to high-temperature environments and is suitable for structures using hydrogen storage metals, with a wider range of application scenarios.

[0033] Furthermore, the hydrogen storage structure is a gas-solid hydrogen storage structure, which effectively improves hydrogen storage efficiency compared with a single hydrogen storage mode. It includes two ventilated and filtered hemispherical shells 3, several phase change heat pipes 1, and several solid hydrogen storage rings 2. The ventilated and filtered hemispherical shells 3 have a ventilation channel in the middle for supplying hydrogen from the aluminum alloy inner liner, while also enabling a lightweight design. Ventilation and filtration holes are opened on the plane of the ventilated and filtered hemispherical shells 3, and the two planes of the ventilated and filtered hemispherical shells 3 are arranged opposite each other and connected to the phase change heat pipes 1 respectively, for filtering the hydrogen output from the phase change heat pipes 1 and sending it into the aluminum alloy inner liner. Each phase change heat pipe 1 is arranged parallel to the two ventilated and filtered hemispherical shells 3 along the axial direction, while the solid hydrogen storage rings 2 are arranged in a circular shape around the outside of the phase change heat pipes 1 and connected to the phase change heat pipes 1 through connecting pipes, thereby realizing gas-solid composite hydrogen storage.

[0034] Furthermore, the phase change heat pipe 1 and the connecting pipe adopt a composite solid-solid phase change material with aluminum powder as the phase change material and high-alumina bauxite and white mud as the matrix material, which has advantages such as high latent heat of phase change, large heat storage density, stable performance and high thermal conductivity; the solid hydrogen storage ring 2 is made of hydrogen storage material and metal matrix. The hydrogen storage material is AB5 type hydrogen storage alloy, which has high hydrogen absorption capacity and cycle durability, and has good cycle life; the metal matrix is ​​aluminum alloy or copper, which has good electrical conductivity and can be better combined with hydrogen storage alloy.

[0035] According to another aspect of the present invention, a method for manufacturing an inner liner of a hydrogen storage tank to prevent hydrogen embrittlement is provided, the method comprising the following steps:

[0036] S1 is used to prepare hydrogen storage structures;

[0037] S2 wraps thermoplastic carbon fiber around the hydrogen storage structure to form carbon fiber layer 4, and performs air plasma surface treatment on it to remove the weak boundary layer on its surface, introduce hydroxyl and carboxyl groups, improve its chemical activity, and facilitate subsequent bonding with aluminum alloy liner.

[0038] S3 prepares a cylindrical aluminum alloy inner liner and performs an oxidation treatment on its interior to increase its adhesiveness. The composite structure of hydrogen storage structure and carbon fiber layer obtained in step S2 is then inserted into the aluminum alloy inner liner to make them fit together. After multiple spinning and molding processes, the hydrogen embrittlement-resistant hydrogen storage tank inner liner is obtained.

[0039] Furthermore, when the hydrogen storage structure is a gas-solid hydrogen storage structure, step S1 includes the following sub-steps:

[0040] S11 uses a composite solid-solid phase change material with high-alumina bauxite and white mud as the matrix material. The composite solid-solid phase change material is placed in a mold and unidirectionally pressed by applying pressure from the top. Then, it is aged to make a phase change heat pipe 1. Its main body is made into a hollow cylindrical shape, which is conducive to participating in heat exchange and improving efficiency.

[0041] S12 is made of aluminum alloy through a stamping process to form a metal matrix ring;

[0042] S13 is subjected to melting and annealing heat treatment of hydrogen storage alloy, and hydrogen storage alloy sheet is prepared by medium frequency induction fast quenching and spinning. The prepared hydrogen storage alloy sheet is subjected to low pressure heat treatment, and then the alloy powder obtained by sieving 200 mesh alloy powder is used to cover the outside of the metal matrix ring by electrochemical action to obtain solid hydrogen storage ring 2.

[0043] S14 sintersects powdered copper into a hemispherical air-filtering hemispherical shell 3;

[0044] S15 connects the phase change heat pipe 1, the solid hydrogen storage ring 2, and the ventilated filter hemispherical shell 3 by friction welding to form a gas-solid hydrogen storage structure.

[0045] According to another aspect of the present invention, a hydrogen embrittlement-resistant hydrogen storage tank is provided, which includes a protective layer, an outer fiber layer and an inner liner arranged sequentially from the outside to the inside. The inner liner adopts the aforementioned hydrogen embrittlement-resistant hydrogen storage tank inner liner, which has good hydrogen embrittlement resistance while achieving high hydrogen storage pressure and high hydrogen storage efficiency.

[0046] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A hydrogen embrittlement resistant inner vessel for a hydrogen storage tank, characterized by, The hydrogen embrittlement resistant hydrogen storage tank liner comprises, from outside to inside, a hydrogen storage structure, a carbon fiber layer (4) and an aluminum alloy liner (5), the hydrogen storage structure is a gas-solid hydrogen storage structure and is used for hydrogen storage, and the hydrogen storage structure comprises two air filtering half-shell shells (3) and a plurality of phase change heat pipes (1) and a plurality of solid-state hydrogen storage rings (2), the air filtering half-shell shells (3) are provided with air passages in the middle, and the air passages are used for conveying hydrogen in the aluminum alloy liner to the outside; the air filtering half-shell shells (3) are provided with filtering holes in the planes, the planes of the two air filtering half-shell shells (3) are oppositely arranged and connected with the phase change heat pipes (1) respectively, and the air filtering half-shell shells (3) are used for filtering hydrogen output by the phase change heat pipes (1) and conveying the hydrogen into the aluminum alloy liner; the phase change heat pipes (1) are arranged in parallel along the axial direction between the two air filtering half-shell shells (3), and the solid-state hydrogen storage rings (2) are annularly sleeved outside the phase change heat pipes (1) and connected with the phase change heat pipes (1) through connecting pipes, so as to realize gas-solid composite hydrogen storage; the thermoplastic carbon fiber is wound outside the hydrogen storage structure to form the carbon fiber layer (4), and the carbon fiber layer (4) is combined with the aluminum alloy liner (5) to form a hydrogen embrittlement resistant layer, so as to prevent hydrogen embrittlement and improve hydrogen storage pressure.

2. The hydrogen embrittlement resistant inner vessel for a hydrogen storage tank of claim 1, wherein The phase change heat pipes (1) and the connecting pipes adopt a composite solid-solid phase change material taking aluminum powder as a phase change material and taking high alumina and white mud as a base material.

3. The hydrogen embrittlement resistant inner vessel of the hydrogen storage tank according to claim 1, wherein The solid-state hydrogen storage rings (2) are made of a hydrogen storage material and a metal matrix, the hydrogen storage material is an AB5 type hydrogen storage alloy, and the metal matrix is aluminum alloy or copper.

4. The method of claim 1 to 3, wherein the method is characterized by, The method comprises the following steps: S1, preparing a hydrogen storage structure, comprising the following sub-steps: S11, performing unidirectional film press forming on a composite solid-solid phase change material taking aluminum powder as a phase change material and taking high alumina and white mud as a base material, and then performing aging treatment to prepare phase change heat pipes (1); S12, preparing a metal matrix annular ring through stamping forming process of aluminum alloy; S13, performing melting and annealing heat treatment on a hydrogen storage alloy, preparing hydrogen storage alloy sheets by using the hydrogen storage alloy, covering the hydrogen storage alloy sheets outside the metal matrix annular ring by using electrochemical action, and then preparing solid-state hydrogen storage rings (2); S14, sintering powdery copper into half-spherical air filtering half-shell shells (3); S15, connecting the phase change heat pipes (1), the solid-state hydrogen storage rings (2) and the air filtering half-shell shells (3) to form a gas-solid hydrogen storage structure; S2, winding thermoplastic carbon fiber outside the hydrogen storage structure to form a carbon fiber layer, and performing air plasma surface treatment on the carbon fiber layer to improve chemical activity of the carbon fiber layer; S3, preparing a cylindrical aluminum alloy liner, performing oxidation treatment on the inside of the aluminum alloy liner to increase adhesion, combining the composite structure of the hydrogen storage structure and the carbon fiber layer obtained in step S2 with the aluminum alloy liner, and performing spinning forming to prepare the hydrogen embrittlement resistant hydrogen storage tank liner.

5. The method of claim 4, wherein the step of forming the inner vessel is performed by a method comprising: In step S15, the phase change heat pipes (1), the solid-state hydrogen storage rings (2) and the air filtering half-shell shells (3) are connected by using friction welding. ​ 6. A hydrogen embrittlement resistant hydrogen storage tank characterized by comprising: The hydrogen embrittlement resistant hydrogen storage tank comprises, from outside to inside, a protective layer, a peripheral fiber layer and a liner, and the liner is the hydrogen embrittlement resistant hydrogen storage tank liner according to any one of claims 1 to 3.

Images