WO2023085683A1

WO2023085683A1 - High-pressure storage container and manufacturing method thereof

Info

Publication number: WO2023085683A1
Application number: PCT/KR2022/017085
Authority: WO
Inventors: 한송이; 임미소
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2021-11-15
Filing date: 2022-11-03
Publication date: 2023-05-19
Also published as: KR20230070730A

Abstract

Disclosed are a high-pressure storage container and a manufacturing method thereof. The high-pressure storage container according to an embodiment of the present invention comprises: a tubular liner which provides a storage space for storing high-pressure hydrogen and is open at one end in the longitudinal direction; a boss which allows the storage space to communicate with the outside and is coupled to the one end of the liner in the longitudinal direction; and a hydrogen blocking layer which is formed on at least one of the outer surface or inner surface of the liner to prevent the high-pressure hydrogen inside the storage space from passing through the liner to the outside.

Description

High-pressure storage vessel and manufacturing method thereof

The present invention relates to a high-pressure storage vessel and a method for manufacturing the same, and more particularly, to a high-pressure storage vessel for storing a fluid such as hydrogen under a high pressure and a method for manufacturing the same.

In recent years, as the importance of the environment has been emphasized, the eco-friendly vehicle market is growing rapidly, and electric vehicles and hydrogen electric vehicles are competing with each other with their strengths and weaknesses. In this situation, automobile manufacturers are trying to share the platform of electric vehicles and hydrogen electric vehicles in order to improve productivity and respond flexibly to the market.

In order to share the platform of electric vehicles and hydrogen electric vehicles, the hydrogen storage tank of the hydrogen electric vehicle needs to have a shape that can be mounted in a rectangular space for mounting the battery of the electric vehicle. Accordingly, there is an increasing demand for development of a tubular or bent tubular hydrogen storage tank.

In order to manufacture a hydrogen storage tank in a tubular or bent tubular shape, the liner must be long or include a curved section. When the liner is long or includes a curved section, a problem in that durability easily deteriorates due to repeated pressure occurs. In particular, when the liner is made of a curved pipe, the liner is molded into a corrugated pipe shape, and a reinforcing part is formed in addition to the liner. this happens

(Patent Document 1) Korean Patent Registration No. 10-2242337

The present invention is to solve the problems of the prior art, and an object of the present invention is to provide a high-pressure storage container having a pipe-shaped high-pressure storage container in which a liner has hydrogen tightness and durability, and a manufacturing method thereof.

According to one aspect of the present invention, providing a storage space in which high-pressure hydrogen is stored and a tubular liner with one end open in the longitudinal direction; a boss coupled to one end of the liner in the longitudinal direction and communicating the storage space with the outside; and a hydrogen barrier layer formed on at least one of an outer surface and an inner surface of the liner to prevent high-pressure hydrogen in the storage space from passing through the liner to the outside.

In the high-pressure storage container according to an embodiment of the present invention, the hydrogen barrier layer may have a thickness of 0.3 to 10 μm.

In the high-pressure storage container according to an embodiment of the present invention, the hydrogen barrier layer may have a hydrogen permeability of 5.0×10 ⁻¹³ mol·m/(m²·S·Pa) (@15°C) or less.

In the high pressure storage container according to an embodiment of the present invention, the hydrogen barrier layer may be formed by coating a coating composition including a thermoplastic resin, a UV curable resin, a silane coupling agent, a hydrolysis resistant agent, and a photoinitiator.

In the high-pressure storage container according to an embodiment of the present invention, the thermoplastic resin is made of at least one of a urethane-based resin and a polyester-based resin, the UV curable resin is an acrylate-based resin, and the silane coupling agent is It is composed of at least one of epoxy, vinyl, and methacyl, the hydrolysis agent is an aromatic carbodiimide series, and the photoinitiator is benzophenone, thioctic It may consist of at least one of Thioxanthone and Ketone.

In the high-pressure storage container according to an embodiment of the present invention, the coating composition includes 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, and 0.1 to 60 wt% of the hydrolysis agent. 2wt% and the photoinitiator may be composed of 0.1 ~ 2wt%.

The high-pressure storage vessel according to an embodiment of the present invention may further include a shell disposed while covering an outer surface of the liner.

According to another aspect of the present invention, providing a storage space in which high-pressure hydrogen is stored and forming a tubular liner with one end open in the longitudinal direction; forming a hydrogen barrier layer on at least one of an outer surface and an inner surface of the liner to prevent high-pressure hydrogen in the storage space from passing through the liner to the outside; and coupling a boss to one end of the liner in the longitudinal direction so that the outside and the storage space communicate with each other.

In the high-pressure storage container manufacturing method according to an embodiment of the present invention, the hydrogen barrier layer may be coated on the outer surface of the liner to a thickness of 0.3 to 10 μm.

In the high-pressure storage container manufacturing method according to an embodiment of the present invention, the hydrogen barrier layer may be formed by coating a coating composition including a thermoplastic resin, a UV curable resin, a silane coupling agent, a hydrolysis resistant agent, and a photoinitiator.

In the high-pressure storage container manufacturing method according to an embodiment of the present invention, the thermoplastic resin is made of at least one of a urethane-based resin and a polyester-based resin, the UV curable resin is an acrylate-based resin, and the silane couple The ringing agent is composed of at least one of epoxy, vinyl, and methacyl, the hydrolysis agent is an aromatic carbodiimides series, and the photoinitiator is benzophenone, It may consist of at least one of Thioxanthone and Ketone.

In the high-pressure storage container manufacturing method according to an embodiment of the present invention, the coating composition includes 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, and the hydrolysis-resistant agent 0.1 ~ 2wt% and may be composed of 0.1 ~ 2wt% of the photoinitiator.

In the method for manufacturing the high-pressure storage vessel according to an embodiment of the present invention, in the step of forming the hydrogen barrier layer, the coating composition may be diluted in a solvent, coated, and then cured to form the hydrogen barrier layer.

In the high-pressure storage container manufacturing method according to an embodiment of the present invention, the coating composition may be coated on the outer surface of the liner through a spray method, and then UV cured after hot air drying.

According to an embodiment of the present invention, since a hydrogen barrier layer for blocking hydrogen permeation is provided in a pipe-shaped liner, a high-pressure storage container having improved hydrogen airtightness and excellent durability against repeated pressure can be provided.

1 is a view showing a high-pressure storage vessel according to an embodiment of the present invention.

2 is a cross-sectional view of part A of FIG. 1 .

FIG. 3 is a view showing a case where the position of the hydrogen barrier layer in FIG. 2 is changed to the inner surface of the liner.

4 is a view showing a modified example of a high-pressure storage vessel according to an embodiment of the present invention.

5 is a flowchart of a method for manufacturing a high-pressure storage vessel according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. This invention may be embodied in many different forms and is not limited to the embodiments set forth herein. In order to clearly describe the present invention, parts irrelevant to the description are omitted in the drawings, and the same reference numerals are attached to the same or similar components throughout the specification.

In this specification, terms such as "include" or "have" are intended to describe the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

In this specification, spatially relative terms such as "front", "rear", "side", "upper" or "lower" may be used to describe correlations with components shown in the drawings. These are relative terms based on what is shown in the drawings, and the positional relationship may be interpreted in the opposite way according to the orientation. In addition, the fact that certain components are “connected” to other components includes cases where they are not only directly connected to each other but also indirectly connected to each other unless there are special circumstances.

1 is a view showing a high-pressure storage vessel according to an embodiment of the present invention. 2 is a cross-sectional view of part A of FIG. 1 .

The high-pressure storage vessel 1 according to an embodiment of the present invention is for storing a fluid such as hydrogen in a high-pressure state. The high-pressure storage vessel 1 according to an embodiment of the present invention may have an atypical shape such as a tubular tube or a bent tube compared to a conventional cylindrical high-pressure storage vessel.

Referring to FIGS. 1 and 2 , a high-pressure storage vessel 1 according to an embodiment of the present invention includes a liner 100, a boss 200, a hydrogen barrier layer 300, and a shell 400. According to one embodiment of the present invention, even when the liner 100 has a relatively long pipe shape compared to its diameter, the hydrogen barrier layer 300 can ensure the hydrogen tightness of the liner 100, Durability can be maintained even under repeated pressure.

The liner 100 provides a storage space in which high-pressure hydrogen is stored. The liner 100 may have a pipe shape with one end opened in the longitudinal direction. In addition, the liner 100 may be made of a resin material, a polymer material, or the like. For example, the liner 100 may be made of high-density polyethylene material (HDPE), amide-based material (PA6, PA66, PA11, PA12), polyurethane-based material (TPU), or the like.

The boss 200 communicates the outside with the storage space and is coupled to one end of the liner 100 in the longitudinal direction. The boss 200 is a part to which a valve for injecting fluid into the high-pressure storage container 1 is coupled. The boss 200 may be made of a metal material. For example, the boss 200 may be made of aluminum.

The hydrogen barrier layer 300 is formed on at least one of the outer and inner surfaces of the liner 100 to prevent high-pressure hydrogen in the storage space from passing through the liner 100 to the outside. In one embodiment of the present invention, the hydrogen barrier layer 300 may be formed by coating the outer surface of the liner 100 . In other words, the hydrogen barrier layer 300 may be disposed between the liner 100 and the shell 400 .

The hydrogen blocking layer 300 may have a thickness of 0.3 to 10 μm. In addition, the hydrogen barrier layer 300 may have a hydrogen permeability of 5.0×10 ⁻¹³ mol·m/(m²·S·Pa) (@15°C) or less.

As described above, the hydrogen barrier layer 300 may be formed through coating. More specifically, the hydrogen barrier layer 300 may be formed by coating a coating composition including a thermoplastic resin, a UV curable resin, a silane coupling agent, a hydrolysis resistant agent, and a photoinitiator. The thermoplastic resin is made of at least one of a urethane-based resin and a polyester-based resin, the UV curable resin is an acrylate-based resin, and the silane coupling agent is an epoxy, vinyl, and methacrylic resin. ), wherein the hydrolysis agent is an aromatic carbodiimide series, and the photoinitiator is any one or more of benzophenone, thioxanthone, and ketone series. can be made with

The coating composition may be composed of 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, 0.1 to 2 wt% of the hydrolysis agent, and 0.1 to 2 wt% of the photoinitiator. . The hydrogen barrier layer 300 may be formed by curing after the coating composition is diluted in a solvent and coated. At this time, as the solvent, an alcohol-based composition, a ketone-based composition, or the like may be used. For example, the hydrogen barrier layer 300 may be formed by coating the outer surface of the liner 100 with the coating composition through a spray method, drying with hot air, and UV curing.

Table 1 below shows composition ratios of coating compositions applied to the high-pressure storage vessel 1 according to an embodiment of the present invention and comparative examples.

	열가소성 수지thermoplastic profit	UV경화성 수지UV curable profit	실란 커플링제Silane coupling agent	내가수 분해제my number disintegrant	광개시제photoinitiator	수소 투과도hydrogen permeability
실시예 1Example 1	45wt%45wt%	45wt%45wt%	8wt%8wt%	1wt%1wt%	1wt%1wt%	1.2810^-13 1.2810 ^-13
실시예 2Example 2	30wt%30wt%	60wt%60wt%	8wt%8wt%	1wt%1wt%	1wt%1wt%	1.0410^-13 1.0410 ^-13
실시예 3Example 3	60wt%60wt%	30wt%30wt%	8wt%8wt%	1wt%1wt%	1wt%1wt%	1.5810^-13 1.5810 ^-13
비교예 1Comparative Example 1	70wt%70wt%	20wt%20wt%	8wt%8wt%	1wt%1wt%	1wt%1wt%	4.6510^-12 4.6510 ^-12
비교예 2Comparative Example 2	20wt%20wt%	70wt%70wt%	8wt%8wt%	1wt%1wt%	1wt%1wt%	4.6510^-10 4.6510 ^-10
비교예 3Comparative Example 3	40wt%40wt%	55wt%55wt%	3wt%3wt%	1wt%1wt%	1wt%1wt%	4.6510^-11 4.65 ^10-11

In the examples and comparative examples shown in Table 1, the thermoplastic resin is thermoplastic polyurethane (TPU), the UV curable resin is urethane acrylate, the silane coupling agent is 3Glycidoxypropyl trimethoxysilane (a glycidyl group, that is, an epoxy group), I Aromatic carbodiimides were used as the hydrolysis agent, and hydroxycyclohexyl phenyl ketone (alpha hydroxy ketone) was used as the photoinitiator. In addition, the coating composition was coated on a PET substrate to a thickness of 0.3 μm to make samples, and the hydrogen permeability of each sample was measured using an evaluation device (TOYOSEIKI, BT-1) at an evaluation temperature of 15 ° C and an evaluation pressure of 1 bar. Examples 1, 2 and 3 show hydrogen permeability of 5.0 × 10 ^-13 mol·m/(m²·S·Pa) (@15°C) or less. However, Comparative Examples 1 to 3 were found to have hydrogen permeability exceeding 5.0×10 ^-13 mol·m/(m²·S·Pa) (@15°C). The amine group included in the UV curable resin, urethane acrylate, is sufficiently cross-linked with epoxy silane, and the vinyl group of the UV curable resin, urethane acrylate, is cross-linked to show high cross-linking density. It is believed to be due to On the other hand, when the content of the TPU resin is less than 30wt%, the molecular weight of the entire matrix is not sufficient, making it difficult to form a uniform film.

In addition, when the content of urethane acrylate, which is a UV curable resin, is less than 30wt%, the crosslinking of the composition is not sufficient, and when the content exceeds 60wt%, the molecular weight is not large enough, so brittleness is increased and the coating film cracks ( cracks) may occur.

In addition, when the content of the silane coupling agent is less than 5wt%, sufficient cross-linking is not formed, and when the content is 10wt% or more, unreacted silane coupling agent remains and causes a decrease in hydrogen permeability.

Even in the case of the hydrolysis-resistant agent and the photoinitiator, when the content thereof is 2 wt% or more, it acts as an impurity and lowers the hydrogen permeability.

Considering these results, the coating composition includes 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, 0.1 to 2 wt% of the hydrolysis agent, and 0.1 to 2 wt% of the photoinitiator. % is found to be optimal.

The shell 400 surrounds the outer surface of the liner 100 and is disposed. The shell 400 may be disposed to surround an outer surface of the liner 100 and at least a portion of a portion of the boss 200 exposed to the outside of the liner 100 . The shell 400 provides pressure resistance to the high-pressure storage vessel 1 . In the high-pressure storage vessel 1 according to an embodiment of the present invention, the liner 100 forms a storage space therein, and the shell 400 provides pressure resistance capable of withstanding the pressure of the high-pressure hydrogen stored in the storage space. can

The shell 400 may be formed on the outer surface of the liner 100 through a method such as brazing or winding. The shell 400 may be made of a composite material. For example, the shell 400 may be made of carbon fiber composites, thermosetting resins, and thermoplastic resins.

FIG. 3 is a view showing a case where the position of the hydrogen barrier layer in FIG. 2 is deformed to the inner surface of the liner.

Referring to FIG. 3 , in one embodiment of the present invention, the hydrogen barrier layer 300 may be formed on the inner surface of the liner 100 instead of the outer surface of the liner 100 . In other words, even when the hydrogen barrier layer 300 is formed on the inner surface of the liner 100, the hydrogen airtightness of the liner 100 can be secured.

Referring to FIG. 4 , a modified example of the high-pressure storage vessel 1 according to an embodiment of the present invention is formed in a curved tube shape. That is, the liner 100 has a curved pipe shape and the shell 400 also has a corresponding shape. Meanwhile, the above descriptions of the liner 100, the boss 200, the hydrogen barrier layer 300, and the shell 400 are the same in the modified example of the high-pressure storage vessel 1 according to an embodiment of the present invention.

A method for manufacturing a high-pressure storage vessel according to an embodiment of the present invention is for manufacturing a high-pressure storage vessel according to an embodiment of the present invention as described above. In the case of the method for manufacturing a high-pressure storage vessel according to an embodiment of the present invention, hydrogen airtightness can be improved by forming the hydrogen barrier layer 300 on the liner 100 .

Referring to FIG. 5 , the method for manufacturing a high-pressure storage vessel according to an embodiment of the present invention provides a storage space in which high-pressure hydrogen is stored and forms a tubular liner 100 with one open end in the longitudinal direction (S100), Forming a hydrogen barrier layer 300 on at least one of the outer and inner surfaces of the liner 100 to block the high-pressure hydrogen in the storage space from passing through the liner 100 to the outside (S200), A step of coupling the boss 200 to one end of the longitudinal direction of the liner 100 so that the space communicates (S300) and a step of disposing the shell 400 so as to surround the outer surface of the liner 100 (S400).

In the step of molding the liner 100 (S100), the liner 100 may be manufactured by extrusion. At this time, the liner 100 may be continuously molded into a pipe shape.

In the step of forming the hydrogen blocking layer 300 (S200), the hydrogen blocking layer 300 may be coated on the outer surface of the liner 100 to a thickness of 0.3 to 10 μm. More specifically, the hydrogen barrier layer 300 may be formed by coating a coating composition including a thermoplastic resin, a UV curable resin, a silane coupling agent, a hydrolysis resistant agent, and a photoinitiator.

As described above, the thermoplastic resin is made of at least one of a urethane-based resin and a polyester-based resin, the UV curable resin is an acrylate-based resin, and the silane coupling agent is an epoxy or vinyl and methacyl, wherein the hydrolysis agent is an aromatic carbodiimide series, and the photoinitiator is benzophenone, thioxanthone, and ketone. It may consist of any one or more of the systems. In addition, the coating composition may be composed of 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, 0.1 to 2 wt% of the hydrolysis agent, and 0.1 to 2 wt% of the photoinitiator. can

The hydrogen barrier layer 300 may be formed by curing after the coating composition is diluted in a solvent and coated. At this time, as the solvent, an alcohol-based composition, a ketone-based composition, or the like may be used. In addition, the hydrogen barrier layer 300 may be formed by UV curing after the coating composition is coated on the outer surface of the liner 100 through a spray method, followed by hot air drying. For example, the hydrogen barrier layer 300 may be formed by diluting the coating composition with a solid content of 25 to 35 wt % in a methyl ethyl ketone (MEK) solvent, coating it by a spray method, and then drying and UV curing.

In the step of coupling the boss 200 (S300), the boss 200 is coupled to the longitudinal end of the liner 100. The boss 200 is a part to which a valve for injecting fluid into the high-pressure storage container 1 is coupled, and may be made of a metal material. For example, the boss 200 may be made of aluminum.

In the step of disposing the shell 400 (S400), the shell 400 may be formed on the outer surface of the liner 100 through a method such as brazing or winding. The shell 400 may be made of a composite material. For example, the shell 400 may be made of carbon fiber composites, thermosetting resins, and thermoplastic resins.

Although one embodiment of the present invention has been described, the spirit of the present invention is not limited by the embodiments presented herein, and those skilled in the art who understand the spirit of the present invention, within the scope of the same spirit, the addition of components, Other embodiments may be easily suggested by changes, deletions, additions, and the like. However, it will be said that this is also within the scope of the present invention.

Claims

a tubular liner having one open end in a longitudinal direction and providing a storage space in which high-pressure hydrogen is stored;

a boss coupled to one end of the liner in the longitudinal direction and communicating the storage space with the outside; and

and a hydrogen barrier layer formed on at least one of outer and inner surfaces of the liner to prevent high-pressure hydrogen in the storage space from passing through the liner to the outside.
According to claim 1,

The hydrogen barrier layer is a high pressure storage container having a thickness of 0.3 ~ 10㎛.
According to claim 1,

The hydrogen barrier layer is a high-pressure storage container having a hydrogen permeability of 5.0 × 10 -13 mol · m / (m 2 · S · Pa) (@ 15 ℃) or less.
According to claim 1,

The hydrogen barrier layer is formed by coating a coating composition containing a thermoplastic resin, a UV curable resin, a silane coupling agent, a hydrolysis resistant agent and a photoinitiator.
According to claim 4,

The thermoplastic resin is made of at least one of a urethane-based resin and a polyester-based resin, the UV curable resin is an acrylate-based resin, and the silane coupling agent is an epoxy, vinyl, and methacrylic resin. ), wherein the hydrolysis agent is an aromatic carbodiimide series, and the photoinitiator is any one or more of benzophenone, thioxanthone, and ketone series. A high-pressure storage vessel made of.
According to claim 4,

The coating composition is a high-pressure storage container composed of 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, 0.1 to 2 wt% of the hydrolysis agent, and 0.1 to 2 wt% of the photoinitiator. .
According to claim 1,

The high-pressure storage vessel further comprising a shell disposed while surrounding the outer surface of the liner.
forming a tubular liner having an open longitudinal end and providing a storage space in which high-pressure hydrogen is stored;

forming a hydrogen barrier layer on at least one of an outer surface and an inner surface of the liner to prevent high-pressure hydrogen in the storage space from passing through the liner to the outside; and

and coupling a boss to one end of the liner in the longitudinal direction so that the outside and the storage space communicate with each other.
According to claim 8,

The hydrogen barrier layer is coated on the outer surface of the liner to a thickness of 0.3 to 10 μm.
According to claim 8,

The hydrogen barrier layer is formed by coating a coating composition containing a thermoplastic resin, a UV curable resin, a silane coupling agent, a hydrolysis resistant agent and a photoinitiator.
According to claim 10,

The thermoplastic resin is made of at least one of a urethane-based resin and a polyester-based resin, the UV curable resin is an acrylate-based resin, and the silane coupling agent is an epoxy, vinyl, and methacrylic resin. ), wherein the hydrolysis agent is an aromatic carbodiimide series, and the photoinitiator is any one or more of benzophenone, thioxanthone, and ketone series. Method for manufacturing a high-pressure storage vessel consisting of.
According to claim 10,

The coating composition is a high-pressure storage container composed of 30 to 60 wt% of the thermoplastic resin, 30 to 60 wt% of the UV curable resin, 5 to 10 wt% of the silane coupling agent, 0.1 to 2 wt% of the hydrolysis agent, and 0.1 to 2 wt% of the photoinitiator. manufacturing method.
According to claim 10,

In the step of forming the hydrogen barrier layer, the coating composition is diluted in a solvent, coated, and then cured to form the hydrogen barrier layer.
According to claim 13,

The coating composition is coated on the outer surface of the liner through a spray method and then UV cured after hot air drying.