High-pressure hydrogen storage container inner wall hydrogen barrier structure

Abstract

The utility model discloses a kind of high-pressure hydrogen storage container inner wall hydrogen barrier structure, including high-pressure hydrogen storage container, the high-pressure hydrogen storage container inner wall surface is sandblasted or inner grinding treatment, form the base of roughness Ra0.8-1.6 μm, nano-porous FeF2 transition layer, CrF3 main anticorrosion layer and TaF5 / NiF2 lubricating layer are sequentially arranged on the base.The utility model is without corrosion crack after 72 hours hydrogen permeation test, corrosion rate is reduced to 0.01mm / a below;Substrate tensile strength retention rate is ≥95%;Fluoride film layer life is more than 3 times higher than traditional plating layer.

Description

Technical Field

[0001] This utility model belongs to the field of high-pressure hydrogen storage container manufacturing technology, and in particular relates to a hydrogen-blocking structure on the inner wall of a high-pressure hydrogen storage container. Background Technology

[0002] Existing high-pressure hydrogen storage containers (such as those made of 30CrMo or 4130X alloy steel) are prone to hydrogen embrittlement corrosion of their inner walls due to hydrogen molecule permeation. Conventional anti-corrosion methods (such as high-nickel-based materials, plating, or coatings) have the following drawbacks:

[0003] 1. High-nickel-based materials: They have good resistance to hydrogen embrittlement, but their tensile strength is insufficient (e.g., Inconel 718 is only about 850 MPa), which cannot meet the requirements of high-pressure hydrogen storage.

[0004] 2. Traditional plating / coating: low adhesion, poor durability, and easy to peel off in long-term hydrogen environment;

[0005] 3. Surface treatment technology: Not designed for hydrogen permeation mechanism, resulting in limited anti-corrosion effect.

[0006] Therefore, addressing the shortcomings of the existing technologies has become the focus of efforts for those skilled in the field. Utility Model Content

[0007] The purpose of this invention is to provide a hydrogen barrier structure for the inner wall of a high-pressure hydrogen storage container. By generating a dense fluoride film in situ, it blocks hydrogen from contacting the metal while retaining the high strength of the substrate, thus completely solving the shortcomings of the prior art.

[0008] The objective of this utility model is achieved through the following technical solution:

[0009] A hydrogen barrier structure for the inner wall of a high-pressure hydrogen storage container includes a high-pressure hydrogen storage container. The inner wall surface of the high-pressure hydrogen storage container is treated by sandblasting or internal grinding to form a substrate with a roughness of Ra0.8-1.6μm. A nanoporous FeF2 transition layer, a CrF3 main anti-corrosion layer, and a TaF5 / NiF2 lubricating layer are sequentially disposed on the substrate.

[0010] Preferably, the transition layer is embedded in micro-pits in the substrate by sandblasting.

[0011] Preferably, the thickness of the main anti-corrosion layer is 1-3 μm.

[0012] Preferably, the lubricating layer contains ≥60% TaF5.

[0013] Preferably, the substrate contains microcapsules of a fluoride precursor with a particle size of 5-20 μm and a distribution density of 10-50 capsules / cm³. 2 .

[0014] Preferably, the system also includes an exhaust gas treatment module containing a Ca(OH)2 reaction tank for generating marble (CaF2) and recovering fluorine gas.

[0015] This invention employs a composite membrane design: a fluoride membrane layer combined with an alloy steel substrate, which combines high corrosion resistance (hydrogen permeability reduction ≥90%) and a low coefficient of friction (≤0.1).

[0016] This utility model features an environmentally friendly recycling structure: the exhaust gas treatment module converts fluorine gas into marble, avoiding pollution and enabling resource utilization.

[0017] Compared with the prior art, the beneficial effects of this utility model are as follows:

[0018] Resistance to hydrogen embrittlement corrosion: No corrosion cracks were observed after a 72-hour hydrogen permeation test, and the corrosion rate was reduced to below 0.01 mm / a;

[0019] High strength retention: The tensile strength retention rate of the base material is ≥95% (e.g., ≥1020MPa after treatment of 4130X steel);

[0020] Long lifespan and high reliability: The lifespan of fluoride films is more than 3 times longer than that of traditional coatings. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the structure of the inner wall of the high-pressure hydrogen storage container in this utility model. Detailed Implementation

[0022] Exemplary embodiments of the present disclosure will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

[0023] like Figure 1 As shown, a hydrogen barrier structure for the inner wall of a high-pressure hydrogen storage container includes a high-pressure hydrogen storage container 1. The inner wall surface of the high-pressure hydrogen storage container 1 is treated by sandblasting or internal grinding to form a substrate 2 with a roughness Ra of 0.8-1.6 μm. A nanoporous FeF2 transition layer 3, a CrF3 main anti-corrosion layer 4, and a TaF5 / NiF2 lubricating layer 5 are sequentially disposed on the substrate 2 to form a gradient composite film layer.

[0024] In this embodiment, the transition layer 3 (thickness 0.1-0.5 μm) is embedded into micro-pits in the substrate by sandblasting to enhance adhesion. The dense CrF3 main anti-corrosion layer 4 has a thickness of 1-3 μm and blocks hydrogen permeation. The lubrication layer 5 contains TaF5 ≥ 60% and has a thickness of 0.1-0.5 μm, reducing the coefficient of friction to ≤ 0.05.

[0025] The substrate 2 contains microcapsules of a fluoride precursor with a particle size of 5-20 μm and a distribution density of 10-50 capsules / cm³. 2 The preferred fluoride precursor is WF6, which is released and repaired in situ when the film is worn.

[0026] In this embodiment, the forming process of the gradient composite film layer is as follows:

[0027] First stage: 80% fluorine gas + 20% nitrogen gas, pressure 0.3 MPa, rotation 10 revolutions / minute, forming FeF2 transition layer 3;

[0028] Second stage: Switch to 60% fluorine gas + 40% argon gas, pressure 0.5MPa, rotate 5 revolutions / minute, and deposit CrF3 main anti-corrosion layer 4;

[0029] Third stage: Spray TaF5 suspension, and after drying, form a lubricating layer 5.

[0030] This embodiment also employs weld strengthening treatment, applying additional magnetron sputtering to the welded area to directionally deposit CrF3 particles and compensate for thickness differences.

[0031] This embodiment also includes an exhaust gas treatment module, which contains a Ca(OH)2 reaction tank for generating marble (CaF2) and recovering fluorine gas. Unreacted fluorine gas is absorbed by the Ca(OH)2 solution to generate marble (CaF2) and release CO2. The CO2 reacts with HF to generate hydrogen fluoride gas, which is then reintroduced into the container to participate in film formation, increasing the fluorine utilization rate to over 90%.

[0032] This invention achieves a ≥95% reduction in hydrogen permeability in its high-pressure hydrogen storage container (no corrosion detected after 72 hours); a friction coefficient ≤0.05; and a membrane adhesion strength ≥45MPa (no peeling observed during pull-out testing). Lifespan is extended: dynamic repair increases membrane lifespan by 3 times (simulating 10 years of hydrogen environment erosion). Fluorine gas recycling rate reaches 90%, marble purity ≥98%, and byproducts can be used as raw materials for fluorochemicals.

[0033] The innovation of this utility model lies in:

[0034] Gradient composite structure: multi-layer film layer synergistic design, taking into account adhesion, corrosion protection and lubrication;

[0035] Dynamic self-healing: Microcapsule technology solves the problem of localized wear and breaks through the lifespan limitations of static films;

[0036] Process-structure synergy: The combination of staged gas injection and magnetron sputtering ensures uniform film formation in complex areas;

[0037] Resource utilization: Zero emissions are achieved through exhaust gas recycling, and by-products are utilized for high-value applications.

[0038] Similarly, it should be understood that, in order to simplify this disclosure and aid in understanding one or more of the various aspects of the invention, in the above description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof. However, this method of disclosure should not be construed as reflecting an intention that the claimed invention requires more features than expressly recited in each claim. Rather, as reflected in the following claims, the inventive aspect lies in fewer than all features of a single foregoing disclosed embodiment. Therefore, the claims following the detailed description are hereby expressly incorporated into that detailed description, wherein each claim itself is a separate embodiment of the invention.

[0039] Those skilled in the art will understand that modules in the device of the embodiments can be adaptively changed and placed in one or more devices different from that embodiment. Modules, units, or components in the embodiments can be combined into a single module, unit, or component, and further, they can be divided into multiple sub-modules, sub-units, or sub-components. Except where at least some of such features and / or processes or units are mutually exclusive, any combination can be used to combine all features disclosed in this specification (including the accompanying claims, abstract, and drawings) and all processes or units of any method or device so disclosed. Unless expressly stated otherwise, each feature disclosed in this specification (including the accompanying claims, abstract, and drawings) may be replaced by an alternative feature that serves the same, equivalent, or similar purpose.

[0040] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are meant to be within the scope of this invention and form different embodiments.

[0041] It should be noted that the above embodiments are illustrative of the present invention and not restrictive, and that those skilled in the art can devise alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses should not be construed as limiting the claims. The word "comprising" does not exclude the presence of elements or steps not listed in the claims. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The present invention can be implemented by means of hardware comprising several different elements and by means of a suitably programmed computer. In the unit claims enumerating several means, several of these means may be embodied by the same item of hardware. The use of the words first, second, and third, etc., does not indicate any order. These words can be interpreted as names.

[0042] The above description is only a preferred embodiment of the present utility model and is not intended to limit the present utility model. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present utility model should be included within the protection scope of the present utility model.

Claims

1. A hydrogen-barrier structure for the inner wall of a high-pressure hydrogen storage container, comprising a high-pressure hydrogen storage container, characterized in that: The inner wall surface of the high-pressure hydrogen storage container is treated by sandblasting or internal grinding to form a substrate with a roughness of Ra0.8-1.6μm. A nanoporous FeF2 transition layer, a CrF3 main anti-corrosion layer and a TaF5 / NiF2 lubricating layer are sequentially disposed on the substrate.

2. The hydrogen barrier structure on the inner wall of the high-pressure hydrogen storage container according to claim 1, characterized in that: The transition layer is embedded in micro-pits in the substrate by sandblasting.

3. The hydrogen barrier structure on the inner wall of the high-pressure hydrogen storage container according to claim 2, characterized in that: The thickness of the main anti-corrosion layer is 1-3 μm.

4. The hydrogen barrier structure on the inner wall of the high-pressure hydrogen storage container according to claim 3, characterized in that: The lubricating layer contains ≥60% TaF5.

5. The hydrogen barrier structure on the inner wall of the high-pressure hydrogen storage container according to claim 4, characterized in that: The substrate is pre-embedded with microcapsules containing a fluoride precursor, with a particle size of 5-20 μm and a distribution density of 10-50 capsules / cm³. 2 .

6. The hydrogen barrier structure on the inner wall of the high-pressure hydrogen storage container according to any one of claims 1-5, characterized in that: It also includes an exhaust gas treatment module containing a Ca(OH)2 reaction tank for generating marble (CaF2) and recovering fluorine gas.

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