CN111102465A - High-pressure hydrogen storage cylinder with plastic liner wound with prepreg tape and manufacturing method thereof - Google Patents

High-pressure hydrogen storage cylinder with plastic liner wound with prepreg tape and manufacturing method thereof Download PDF

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Publication number
CN111102465A
CN111102465A CN201811247060.8A CN201811247060A CN111102465A CN 111102465 A CN111102465 A CN 111102465A CN 201811247060 A CN201811247060 A CN 201811247060A CN 111102465 A CN111102465 A CN 111102465A
Authority
CN
China
Prior art keywords
prepreg tape
winding
resin
hydrogen storage
carbon fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811247060.8A
Other languages
Chinese (zh)
Inventor
孙盛康
黄翔宇
黄胜德
辛美音
张红卫
沈海娟
李静
蔡莺莺
邓文彬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Petrochemical Co Ltd filed Critical China Petroleum and Chemical Corp
Priority to CN201811247060.8A priority Critical patent/CN111102465A/en
Publication of CN111102465A publication Critical patent/CN111102465A/en
Pending legal-status Critical Current

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/02Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
    • F17C1/08Integral reinforcements, e.g. ribs
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2209/00Vessel construction, in particular methods of manufacturing
    • F17C2209/21Shaping processes
    • F17C2209/2154Winding
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage

Abstract

The invention provides a high-pressure hydrogen storage cylinder with a plastic liner wound by a prepreg tape and a manufacturing method thereof. The gas cylinder sequentially comprises an inner container, a carbon fiber prepreg tape winding layer, an isolating membrane and a glass fiber winding layer from inside to outside in a composition structure. The manufacturing method comprises the following steps: a) manufacturing an inner container; b) treating the surface of the inner container; c) winding a carbon fiber prepreg tape; d) coating with an isolating film; e) wet winding of glass fibers and f) curing. The high-pressure hydrogen storage cylinder manufactured by the method provided by the invention has the following advantages: 1) the winding efficiency is improved, and the winding track is stable; 2) the quality fluctuation of the finished gas cylinder is small; 3) the resin used for wet winding of the glass fiber on the outer layer is isolated from the carbon fiber prepreg tape on the inner layer, so that the mutual influence of the resin and the carbon fiber prepreg tape is avoided; 4) by laying the isolation film in the middle, the leakage rate of hydrogen is further reduced.

Description

High-pressure hydrogen storage cylinder with plastic liner wound with prepreg tape and manufacturing method thereof
Technical Field
The invention relates to the field of mobile storage of high-pressure hydrogen, in particular to an IV high-pressure hydrogen storage cylinder for a vehicle and a manufacturing method thereof.
Background
Due to the fact that problems of automobile emission, automobile energy consumption and the like are paid more and more attention, new energy automobiles are the development direction of the automobile industry in the future. With the development of technology, new fuel cell vehicles, fcv (fuel cell vehicles), have been gradually accepted by the market due to their advantages of long endurance, rapid hydrogenation, etc. FCVs convert the chemical energy of a fuel, the primary fuel type being hydrogen, into electrical energy to provide the energy required for driving. At present, a 70MPa high-pressure hydrogen storage cylinder is the main hydrogen storage mode of FCV, the hydrogen can be quickly hydrogenated within 2-5 min, the hydrogen can be heated once and can be driven by more than 600Km, and the service life of the cylinder is more than 15 years.
Because the aluminum inner container can not meet the requirements of fatigue strength and hydrogen storage density per unit mass, an IV bottle is universally used internationally, namely, the plastic material is used as the inner container of the gas bottle. However, the plastic liner has a certain hydrogen leakage rate as the biggest problem. It is known that the hydrogen leakage rate is related to the nature of the barrier material itself, the thickness of the barrier layer, the pressure differential, and other factors. Because the pressure of the hydrogen is greatly reduced after the hydrogen permeates the inner container of the gas cylinder, one or more layers of isolating layers can be added when the outer layer is wound with fibers so as to improve the isolating rate of the gas cylinder to the hydrogen.
Disclosure of Invention
In order to solve the technical problems, the invention provides the high-pressure hydrogen storage cylinder with the prepreg tape wound with the plastic liner and the manufacturing method thereof, wherein the high-pressure hydrogen storage cylinder has high production efficiency, good hydrogen blocking effect and high hydrogen storage density per unit mass.
The following is a specific technical scheme of the invention:
the invention provides a method for manufacturing a high-pressure hydrogen storage cylinder with a plastic liner wound by a prepreg tape, which comprises the following steps:
a) manufacturing the inner container: the inner container is manufactured by adopting high-density polyethylene (HDPE) or modified nylon 6 (modified PA6) in a blow molding mode; the inner container has stable quality in batch production by using a blow molding process; HDPE or modified PA6 can be used for obtaining better impact resistance under the low-temperature condition, and modified PA6 has higher barrier property to hydrogen compared with HDPE;
b) surface treatment of the inner container: plasma treatment is adopted, and resin is uniformly coated on the treated surface, wherein the resin system is a latent epoxy resin system, and the thickness of the coating is 0.1-0.2 mm; the plasma treatment can ensure that the surface of the liner has better adhesive property with resin;
c) winding the carbon fiber prepreg tape: winding carbon fiber prepreg tape resin serving as a raw material on the surface of the inner container in a dry method; the central value of the resin content of the prepreg tape is 20-30%, and the Tg range of the resin of the prepreg tape is 85-120 ℃;
d) and (3) coating by using an isolating film: tightly adhering an isolating film to the surface of the prepreg tape, and winding 1-4 layers; the main body of the isolating membrane is PVA or EVOH, or a high-barrier membrane prepared by extruding and compounding high-barrier resin;
e) and (3) wet winding of glass fiber: winding the common glass fiber on the isolating membrane in a wet winding mode;
f) and (3) curing: and (3) putting the gas cylinder wound with the prepreg tape and the glass fiber into a curing furnace, and curing while rotating, wherein the curing temperature is 80-120 ℃, and the curing time is 2-6 hours.
Preferably, the carbon fiber prepreg tape in step c) is a hot melt tow prepreg tape of a modified epoxy resin system.
Preferably, the high barrier film prepared by extrusion compounding with the high barrier resin in the step d) is a nylon/EVOH high barrier film.
The invention also provides the high-pressure hydrogen storage cylinder with the plastic liner wound by the prepreg tape manufactured by the method, and the composition structure of the high-pressure hydrogen storage cylinder sequentially comprises the liner, a carbon fiber prepreg tape winding layer, an isolating membrane and a glass fiber winding layer from inside to outside. The main performance of the gas cylinder is provided by the carbon fiber winding layer, and the prepreg tape winding can release higher fiber mechanical property due to controllable resin content, so that the use amount of carbon fiber and resin can be reduced, and the production and use cost is further reduced. Meanwhile, the winding speed of the prepreg tape is high, and the prepreg tape is not easy to slip during winding, so that the production period is shortened, and the product quality is more stable. The glass fiber is mainly used as an outer layer reinforcing material to resist damage such as external impact, shearing and the like, because a smooth surface is required, wet winding is generally adopted, the performance of the used resin is low, and in order to prevent external low-performance resin from entering a prepreg winding layer during curing, an isolation layer is necessarily arranged between the two layers. And the prepreg tape has smooth continuous surface of the inner composite material resin layer due to the blocking of the isolating membrane in the curing process, so that the blocking effect on hydrogen is increased.
In summary, the invention has the following advantages:
1. the IV-type plastic liner is used, the fatigue strength of the gas cylinder is improved, and meanwhile, the barrier property of the whole gas cylinder to hydrogen is improved by adding the isolating film on the winding layer.
2. The carbon fiber prepreg tape winding process is introduced, so that the winding speed is improved, the stability of the resin content of the carbon fiber winding layer is ensured, the occurrence probability of slide wires is reduced, and the selection range of winding wire types is expanded.
3. By adding the isolating membrane in the winding layer, two types of resin systems with different performances are completely and independently cured, and the stable quality of the carbon fiber winding layer is ensured. And due to the wrapping of the isolating membrane, the problem of surface glue shortage does not occur when the carbon fiber prepreg tape is cured.
4. Through carrying out plasma treatment and coating resin to plastics inner bag surface for carbon fiber prepreg tape winding layer and inner bag can the in close connection, avoid filling the gassing circulation because of in the use and cause the delaminating between the two.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention. Example 1
The invention provides a method for manufacturing a high-pressure hydrogen storage cylinder with a plastic liner wound by a prepreg tape, which comprises the following steps:
a) manufacturing the inner container: to be provided withThe modified PA6-1 is used as a raw material, and the inner container is manufactured in a blow molding mode, wherein the volume of the inner container is 60-70L;
b) surface treatment of the inner container: carrying out omnibearing plasma treatment on the liner, wherein the specific treatment mode is that the liner is slowly rotated, a plasma processor is started to be aligned to the surface of the liner and slowly and reciprocally moves along the horizontal direction, after the surface of the liner is completely treated, resin is immediately coated, the resin system is a latent epoxy resin reaction system, the thickness of the resin is controlled to be 0.1-0.2 mm, and bristles are arranged on the surface of the resin to improve the adhesive force of fibers;
c) winding the carbon fiber prepreg tape: alternately performing loop winding and spiral winding on the carbon fiber prepreg tape according to a preset line shape; the prepreg tape is a medium-temperature ATP prepreg tape processed by Guangzhou Sao carbon fiber technology Co., Ltd, and the central value of the resin content is 25%; the initial winding tension is 50N, and then the tension is reduced by 1N after every 5 layers of winding until the preset linear winding is completed;
d) and (3) coating by using an isolating film: coating 4 layers of isolating films on the surface of the prepreg tape; because the surface of the prepreg tape has certain viscosity, the first layer of isolating film is closely attached to the prepreg tape; the used isolating film is a high-temperature high-barrier isolating film and comprises components such as EVOH/PA/EVA and the like; the isolation film can be manually coated, or a special program can be set for automatic coating by using a prepreg tape winding head, and certain tension is applied in both modes; the embodiment adopts automatic coating; after the isolation film is coated, a small amount of resin is coated at the tail end for fixing;
e) and (3) wet winding of glass fiber: winding common glass fiber on an isolating film in a wet winding mode, wherein the resin can be CH5140 epoxy resin of Bakeli company of Germany, and the resin content is 35%;
f) and (3) curing: and (3) putting the gas cylinder wound with the prepreg tape and the glass fiber into a curing furnace, curing while rotating, wherein the curing process is 80 ℃/2 hours +110 ℃/3 hours, and obtaining the finished product of the high-pressure hydrogen storage gas cylinder wound with the prepreg tape and the plastic liner after curing. The high-pressure hydrogen storage cylinder has a composition structure comprising an inner container, a carbon fiber prepreg tape winding layer, an isolating membrane and a glass fiber winding layer from inside to outside in sequence. Examples 2 to 3
The method and steps adopted in the embodiments 2-3 are the same as those of the embodiment 1, but the values of part of experimental parameters are different from those of the embodiment 1, and specifically, as shown in table 1, after the curing is completed, the finished product of the high-pressure hydrogen storage cylinder with the prepreg tape wound on the plastic liner is obtained. The high-pressure hydrogen storage cylinder has a composition structure comprising an inner container, a carbon fiber prepreg tape winding layer, an isolating membrane and a glass fiber winding layer from inside to outside in sequence.
Examples 4 to 6
In the embodiments 4 to 6, High Density Polyethylene (HDPE) is used as a raw material, the method and the steps are the same as those in the embodiment 1, and the values of some experimental parameters are different from those in the embodiment 1, specifically as shown in table 1, after the curing is completed, the finished product of the high-pressure hydrogen storage cylinder with the prepreg tape wound around the plastic liner is obtained. The high-pressure hydrogen storage cylinder has a composition structure comprising an inner container, a carbon fiber prepreg tape winding layer, an isolating membrane and a glass fiber winding layer from inside to outside in sequence.
TABLE 1

Claims (4)

1. A method for manufacturing a high-pressure hydrogen storage cylinder with a plastic liner wound by a prepreg tape is characterized by comprising the following steps:
a) manufacturing the inner container: the inner container is manufactured by adopting high-density polyethylene (HDPE) or modified nylon 6 (modified PA6) in a blow molding mode;
b) surface treatment of the inner container: plasma treatment is adopted, and resin is uniformly coated on the treated surface, wherein the resin system is a latent epoxy resin system, and the thickness of the coating is 0.1-0.2 mm;
c) winding the carbon fiber prepreg tape: winding carbon fiber prepreg tape resin serving as a raw material on the surface of the inner container in a dry method; the central value of the resin content of the prepreg tape is 20-30%, and the Tg range of the resin of the prepreg tape is 85-120 ℃;
d) and (3) coating by using an isolating film: tightly adhering an isolating film to the surface of the prepreg tape, and winding 1-4 layers; the main body of the isolating membrane is PVA or EVOH, or a high-barrier membrane prepared by extruding and compounding high-barrier resin;
e) and (3) wet winding of glass fiber: winding the common glass fiber on the isolating membrane in a wet winding mode;
f) and (3) curing: and (3) putting the gas cylinder wound with the prepreg tape and the glass fiber into a curing furnace, and curing while rotating, wherein the curing temperature is 80-120 ℃, and the curing time is 2-6 hours.
2. The method for manufacturing the high-pressure hydrogen storage cylinder with the plastic liner wound by the prepreg according to claim 1, wherein the carbon fiber prepreg in the step c) is a hot-melt filament bundle prepreg of a modified epoxy resin system.
3. The method for manufacturing a high-pressure hydrogen storage cylinder with a prepreg tape wound around a plastic liner according to claim 1, wherein the high-barrier film prepared by extrusion compounding of the high-barrier resin in the step d) is a nylon/EVOH high-barrier film.
4. A high-pressure hydrogen storage cylinder with a plastic liner wound by a prepreg tape manufactured by the manufacturing method of claim 1 is characterized in that the composition structure of the cylinder comprises the liner, a carbon fiber prepreg tape winding layer, an isolating membrane and a glass fiber winding layer from inside to outside in sequence.
CN201811247060.8A 2018-10-25 2018-10-25 High-pressure hydrogen storage cylinder with plastic liner wound with prepreg tape and manufacturing method thereof Pending CN111102465A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811247060.8A CN111102465A (en) 2018-10-25 2018-10-25 High-pressure hydrogen storage cylinder with plastic liner wound with prepreg tape and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811247060.8A CN111102465A (en) 2018-10-25 2018-10-25 High-pressure hydrogen storage cylinder with plastic liner wound with prepreg tape and manufacturing method thereof

Publications (1)

Publication Number Publication Date
CN111102465A true CN111102465A (en) 2020-05-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111645370A (en) * 2020-05-26 2020-09-11 武汉理工大学 Fiber fully-wound hydrogen storage bottle plastic inner container and forming method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111645370A (en) * 2020-05-26 2020-09-11 武汉理工大学 Fiber fully-wound hydrogen storage bottle plastic inner container and forming method thereof
CN111645370B (en) * 2020-05-26 2021-07-27 武汉理工大学 Fiber fully-wound hydrogen storage bottle plastic inner container and forming method thereof

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