JP2011231900A - High pressure tank and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high pressure tank which suppresses retention of hydrogen gas between a resin liner and an FRP layer, and which is filled with hydrogen gas to assume a pressurized state, and a method of manufacturing the same.SOLUTION: The high pressure tank includes: a resin liner 12; an intermediate layer 20 that contains a minute ball 24 formed to the resin liner 12; and a FRP layer 22 formed by winding fiber permeating a resin around the intermediate layer 20.

Description

  The present invention relates to a high-pressure tank and a method for manufacturing a high-pressure tank.

  A high-pressure container such as a high-pressure tank uses an FRP (Fiber Reinforced Plastic) member that is lighter and tougher than iron or the like, and an FRP layer made of an FRP member is formed on the liner surface. Here, the FRP member includes, for example, a fiber and a resin and is reinforced with plastic.

  As a method for forming the FRP layer, for example, a filament winding method (hereinafter also referred to as “FW method”) is known. In this filament winding method, a fiber impregnated with a resin is wound around a cylindrical substrate, This is a method of forming an FRP layer. After forming the FRP layer, usually a thermosetting treatment is performed.

  In Patent Document 1, in a high-pressure gas tank in which reinforcing fibers wound around the outer periphery of a tank liner are solidified with a resin, powder having high thermal conductivity is mixed into at least a part of the resin, It has been proposed to increase heat conductivity and dissipate heat generated when hydrogen gas is filled into a high-pressure gas tank. Here, copper powder is illustrated as a powder with high thermal conductivity.

JP 2004-183753 A

  In a high-pressure tank filled with hydrogen gas under pressure, since the inside of the high-pressure tank is pressurized, the space between the liner near the base and the FRP layer and the space between the base and the FRP layer are sealed. ing. On the other hand, when a resin liner is used as the liner for the high-pressure tank, the pressurized hydrogen gas in the high-pressure tank gradually permeates through the resin liner, though a small amount. There is a case where it stays between the FRP layer. When the high-pressure tank is depressurized in such a state, gaps are generated between the resin liner in the vicinity of the base part and the FRP layer and between the base part and the FRP layer, and stay between the resin liner and the FRP layer. The high-concentration hydrogen gas that has been discharged is released from the gap between the base and the FRP layer at once (see FIGS. 7 and 8).

  The present invention has been made in view of the above problems, and in a pressurized high-pressure tank filled with hydrogen gas, the high-pressure tank and the high-pressure tank for suppressing the retention of hydrogen gas between the resin liner and the FRP layer are provided. A manufacturing method is provided.

  In order to achieve the above object, the high-pressure tank and the manufacturing method of the high-pressure tank of the present invention have the following characteristics.

  (1) A high-pressure tank having a resin liner, an intermediate layer including microspheres formed on the resin liner, and an FRP layer formed by winding a fiber impregnated with resin around the intermediate layer.

  In a high-pressure tank filled with hydrogen gas, a small amount of hydrogen gas that has passed through the resin liner moves to the base of the high-pressure tank through an intermediate layer containing microspheres formed on the resin liner that serves as a gas discharge path. And is stably discharged out of the high-pressure tank. Thereby, in the pressurized high-pressure tank, stagnation of hydrogen gas between the resin liner and the FRP layer is suppressed.

  (2) In the high-pressure tank according to (1), the microsphere is a micro hollow sphere.

  Since the micro hollow sphere has high strength, the intermediate layer formed between the resin liner and the FRP layer can continue to function as a gas discharge path without being crushed even under high pressure.

  (3) In the high-pressure tank described in (2) above, the micro hollow sphere is a micro balloon.

  Since the microballoon has high strength among micro hollow spheres, the intermediate layer formed between the resin liner and the FRP layer can continue to function as a gas discharge path without being crushed even under high pressure. it can.

  (4) A method for manufacturing a high-pressure tank, comprising: a step of applying a resin containing microspheres to a resin liner to form an intermediate layer; and a step of winding an impregnated fiber around the intermediate layer to form an FRP layer. It is.

  Before forming the FRP layer, a resin containing microspheres is applied to the resin liner to form an intermediate layer that functions as a gas discharge path, so that a small amount of hydrogen gas can permeate from the resin liner in the high-pressure tank during pressurization. Even so, the permeated hydrogen gas moves to the base of the high-pressure tank through the intermediate layer, and is stably released out of the high-pressure tank. Thereby, it is suppressed that hydrogen gas retains between a resin liner and a FRP layer.

  (5) In the method for manufacturing a high-pressure tank described in (4) above, the resin applied to the liner and the resin impregnated in the fiber are uncured thermosetting resins.

  By using the uncured thermosetting resin, it is possible to improve the adhesion between the heat-cured resin liner, the intermediate layer, and the FRP layer.

  (6) In the method for manufacturing a high-pressure tank according to (4) or (5), the microsphere is a microhollow sphere.

  Since the micro hollow sphere has higher strength than the micro solid sphere, the intermediate layer formed between the resin liner and the FRP layer does not collapse even under high pressure in the obtained high pressure tank. It can continue to function as a discharge route.

  (7) In the method for manufacturing a high-pressure tank according to (6), the micro hollow sphere is a micro balloon.

  Since the microballoon has high strength among micro hollow spheres, the intermediate layer formed between the resin liner and the FRP layer does not collapse in the high-pressure tank obtained, even under high pressure, and the gas is discharged. Can continue to function as a route.

  According to the present invention, the retention of hydrogen gas between the resin liner and the FRP layer is suppressed in a pressurized high pressure tank filled with hydrogen gas.

It is sectional drawing which shows an example of a structure of the high voltage | pressure cylinder in this invention. FIG. 2 is an enlarged cross-sectional view of a portion X surrounded by a dashed line in FIG. 1. FIG. 3 is an enlarged cross-sectional view of a Y portion surrounded by a dashed line in FIG. 2. It is a schematic perspective view which shows an example of the formation process of the intermediate | middle layer in this invention. It is a schematic perspective view which shows an example of the formation process of the FRP layer in this invention. It is a flowchart explaining an example of the manufacturing method of the high pressure tank in embodiment of this invention. It is sectional drawing of the nozzle | cap | die vicinity which shows an example of the state of the high pressure tank at the time of the pressurization after conventional hydrogen filling, and leaving as it is. It is sectional drawing of the nozzle | cap | die part vicinity which shows an example of the state of the high pressure tank at the time of the conventional pressure reduction.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  As shown in FIG. 7, for example, in a conventional high-pressure tank, when the hydrogen gas is filled, the inside of the high-pressure tank is pressurized, so that there is a gap between the resin liner 12 near the base portion 16 and the FRP layer 22. In addition, the space between the base portion 16 and the FRP layer 22 is sealed. On the other hand, the pressurized hydrogen gas in the high-pressure tank gradually permeates through the resin liner 12 (as indicated by the arrows in FIG. 7), and the hydrogen gas that has permeated through the resin liner 12 There is a case where it stays at 80 between the FRP layer 22. When the high-pressure tank is depressurized in such a state, gaps are generated between the resin liner 12 and the FRP layer 22 in the vicinity of the base part 16 and between the base part 16 and the FRP layer 22, as shown in FIG. The high-concentration hydrogen gas 90 staying between the resin liner 12 and the FRP layer 22 at the time of pressurization is released from the gap 82 between the base part 16 and the FRP layer 22 at a time.

  Therefore, an example of the high-pressure tank and the high-pressure tank manufacturing method of the present invention that suppresses the stagnation of hydrogen gas between the resin liner and the FRP layer in the pressurized high-pressure tank filled with hydrogen gas will be described below. In addition, what is shown below is an example, Comprising: It is not limited to this.

  An example of the structure of the high-pressure tank in the present embodiment is shown in FIG. As shown in FIG. 1, in the high-pressure tank 10, a cap portion 16 is provided on both sides of a hollow resin liner 12, and an outer layer 14 is provided on the outer periphery of the resin liner 12.

  Further, a cross section near the base portion 16 will be described with reference to FIG. 2 in which an X portion surrounded by a dashed line in FIG. 1 is enlarged. As shown in FIG. 2, the outer layer 14 is provided so as to cover the vicinity of the tip of the base part 16, and the resin liner 12 is disposed so as to contact the protruding part of the base part 16.

  Furthermore, an example of the configuration of the outer layer 14 in the present embodiment will be described with reference to FIG. 3 in which the Y portion surrounded by the one-dot broken line in FIG. 2 is enlarged. As shown in FIG. 3, the resin liner 12 is provided with an intermediate layer 20 including microspheres 24, and the intermediate layer 20 is provided with an FRP layer 22 formed by winding fibers impregnated with resin, and the outer layer 14. Consists of an intermediate layer 20 and an FRP layer 22.

  The material of the resin liner 12 is not particularly limited, and examples thereof include nylon resin, polyethylene resin, polypropylene resin, and other hard resins.

  Further, the intermediate layer 20 in the present embodiment is composed of a microsphere 24 and a resin 26 for ensuring adhesion between the resin liner 12 and the FRP layer 22.

  The microsphere 24 may be a micro solid sphere or a micro hollow sphere, but is preferably a micro hollow sphere. Since the micro hollow sphere is lighter and stronger than the micro solid sphere, the micro hollow sphere is not crushed even under high pressure, and as a result, the intermediate layer 20 formed between the resin liner 12 and the FRP layer 22 is obtained. Can continue to function as a gas exhaust path.

  Examples of the fine hollow sphere include a microsphere, a microballoon, a hollow bubble, and a syntactic foam material. In this embodiment, a microballoon is preferable. Examples of the microballoon include glass microballoon, silica microballoon, shirasu microballoon, carbon microballoon, phenol microballoon, vinyl chloride microballoon, alumina microballoon, zirconia microballoon, and the like in this embodiment. Glass microballoons are preferred.

  The diameter of the glass microballoon used in the present embodiment is preferably 50 μm to 300 μm. When the diameter of the glass microballoon is less than 50 μm, the strength of the intermediate layer 20 is high, but the hydrogen gas that permeates the resin liner 12 when pressurized in the high-pressure tank moves to the base portion 16 along the intermediate layer 20. It becomes difficult to be discharged out of the high-pressure tank. On the other hand, when the diameter of the glass microballoon exceeds 300 μm, the hydrogen gas that permeates through the resin liner 12 during pressurization of the high-pressure tank easily moves to the base portion 16 along the intermediate layer 20, but the intermediate layer 20 The strength of the will decrease. In the present embodiment, a high-strength glass microballoon having a diameter in the above range is more preferable.

  A thermosetting resin is preferably used as the resin 26 used for the mid layer 20. A thermosetting resin consists of a mixture of resin and a hardening | curing agent shown below.

  The resin may be any resin as long as it is thermosetting by reaction with a curing agent. For example, phenol resin, urea resin, unsaturated polyester resin, vinyl ester resin, polyimide resin, bismaleimide resin, polyurethane resin, Examples include diallyl phthalate resin and epoxy resin. The main agent is preferably an epoxy resin, which may be linear or branched.

  The curing agent may be any curing agent as long as the thermosetting resin can be obtained by reaction. For example, primary, secondary, and tertiary amines such as aliphatic amines, aromatic amines, and modified amines. Specifically, amines such as piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol Examples include a curing agent, a polyamide resin, a mercaptan curing agent, and a thiol curing agent such as triazine thiol.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and glycidyl ester type epoxy resin. The curing rate of the thermosetting resin can be controlled by appropriately selecting and blending the above-described epoxy resin and curing agent.

  In the present embodiment, considering the strength and hydrogen gas permeability, the intermediate layer 20 is more preferably thick enough to have the above-described microballoons arranged side by side, but is not limited thereto.

  The FRP layer 22 in the present embodiment is formed by winding a fiber impregnated with a resin around the intermediate layer 20. As resin, the thermosetting resin mentioned above is preferable. On the other hand, as the fibers, for example, inorganic fibers such as metal fibers, glass fibers, carbon fibers, and alumina fibers, synthetic organic fibers such as aramid fibers, and natural organic fibers such as cotton are used. These fibers may be used alone or in combination (as mixed fiber). As a fiber in this embodiment, a carbon fiber is preferable.

  Next, an example of the manufacturing method of the high-pressure tank of this invention is demonstrated using FIGS. 4-6. As shown in FIG. 6, the manufacturing method of the high-pressure tank according to the present embodiment includes a step (S100) of applying a resin containing microspheres to a hollow liner to form an intermediate layer, and a fiber impregnated with the resin in the middle. And (F102) forming an FRP layer by winding the layer. Furthermore, when the above-described thermosetting resin is used as the resin, the FRP layer is wound and formed, and then heated in a heating furnace to cure the resin (S104). Moreover, a base part is provided in the location which was the opening part of the resin liner, and a high pressure tank is formed.

  An example of the intermediate layer forming step (S100 in FIG. 6) is shown in FIG. As shown in FIG. 4, microspheres such as glass microballoons and low-viscosity thermosetting are performed by temporarily fixing the rotating shaft 30 to the opening for the base portion 16 of the hollow resin liner 12 and rotating the rotating shaft 30. A resin liquid 50 made of a functional resin is applied. In FIG. 4, spray coating is performed using the resin coater 40, but the present invention is not limited to this, and for example, a coating method such as brush coating, roll coating, or roll coater may be selected as appropriate. As a low-viscosity thermosetting resin used for the resin liquid 50, for example, a mixture of the above-described curing agent and epoxy resin, preferably a low-viscosity one, and an uncured one is preferable. Furthermore, in consideration of winding the resin-impregnated fiber in the next step, a thermosetting resin having a relatively low curing rate is more preferable. Further, the ratio of the microspheres and the thermosetting resin in the resin liquid 50 is appropriately selected in consideration of the strength of the intermediate layer and the hydrogen gas permeability.

  An example of the FRP layer forming step (S102 in FIG. 6) is shown in FIG. As shown in FIG. 5, the resin-impregnated fiber 60 is applied to the outer periphery of the intermediate layer 18 in a state where the applied resin is uncured while rotating the rotating shaft 30 through a fiber bundle guide (airo) 70 by the FW method. Use a to wind. Here, the resin impregnated in the resin-impregnated fiber 60 is preferably a thermosetting resin, and more preferably a mixture of the above-described curing agent and epoxy resin.

  The present invention is effective for any application as long as it uses a high-pressure tank, but can be used particularly for a high-pressure tank for supplying fuel gas to a fuel cell for vehicles.

  DESCRIPTION OF SYMBOLS 10 High pressure tank, 12 Resin liner, 14 Outer layer, 16 Base part, 18 Intermediate layer in which applied resin is uncured, 20 Intermediate layer, 22 FRP layer, 24 Microsphere, 26 Resin, 30 Rotating shaft, 40 Resin Coating machine, 50 resin liquid, 60 resin-impregnated fiber, 70 fiber bundle guide (airo).

Claims (7)

A resin liner;
An intermediate layer containing microspheres formed on a resin liner;
An FRP layer formed by winding a fiber impregnated with a resin around an intermediate layer;
A high-pressure tank characterized by comprising: The high-pressure tank according to claim 1,
The high pressure tank, wherein the microsphere is a micro hollow sphere. The high-pressure tank according to claim 2,
The high pressure tank, wherein the micro hollow sphere is a micro balloon. Applying a resin containing microspheres to a resin liner to form an intermediate layer;
Winding a fiber impregnated with resin around an intermediate layer to form an FRP layer;
A method for producing a high-pressure tank, comprising: In the manufacturing method of the high-pressure tank according to claim 4,
The method for manufacturing a high-pressure tank, wherein the resin applied to the liner and the resin impregnated in the fiber are uncured thermosetting resins. In the manufacturing method of the high-pressure tank according to claim 4 or claim 5,
The method for producing a high-pressure tank, wherein the microsphere is a micro hollow sphere. In the manufacturing method of the high-pressure tank according to claim 6,
The method for producing a high-pressure tank, wherein the hollow microsphere is a microballoon.

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