CN100430641C - High pressure hydrogen storage bottle made of PBO fiber and carbon fiber mixed composite material and preparation method - Google Patents

High pressure hydrogen storage bottle made of PBO fiber and carbon fiber mixed composite material and preparation method Download PDF

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Publication number
CN100430641C
CN100430641C CNB2006101509885A CN200610150988A CN100430641C CN 100430641 C CN100430641 C CN 100430641C CN B2006101509885 A CNB2006101509885 A CN B2006101509885A CN 200610150988 A CN200610150988 A CN 200610150988A CN 100430641 C CN100430641 C CN 100430641C
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winding
layer
thickness
screw
hoop
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CN1948818A (en
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张春华
黄玉东
曹海琳
宋元军
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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Abstract

The invention relates to a hydrogen cylinder and its preparation method, in which, on the outside surface of the aluminum alloy lining is bonded an adhesive layer and the outside surface of the adhesive layer is bonded to the inside surface of the inner structure layer of carbon fibre composite; the inside surface of the outer structure layer of PBO fibre composite is wound on the outside surface of the inner structure layer and on the outside surface of the outer structure layer is wound an outer protective covering of coating an adhesive layer on the outside surface of the lining, overlying a spiral and toroidal wound inner structure layer, an outer structure layer and an outer protective covering; curing and then getting the present inventive hydrogen cylinder.

Description

The preparation method of pbo fiber and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder
Technical field
The present invention relates to the preparation method of composite material high-pressure hydrogen storage cylinder.
Background technique
Along with the extensive use of hydrogen energy source, particularly the hydrogen internal combustion engine automobile and with hydrogen be power fuel cell car technology day be tending towards the large-scale commercial applications application, more and more higher to the requirement of hydrogen storage vessel combination property.At present hydrogen storage vessel is based on steel cylinder, but this container exists body weight, poor stability because hydrogen density is little, so that it stores up hydrogen efficiency is very low, when being pressurized to 15MPa, the times of fatigue of cycle charge discharge about 3000 times, quality hydrogen-storage density≤3%.For the hydrogen storage vessel of mobile purposes, strengthen hydrogen pressure and improve and take the hydrogen amount and might cause hydrogen molecule to overflow or produce the hydrogen embrittlement phenomenon from container wall.And not only require in light weightly for the high-pressure hydrogen storage cylinder that high-technology fields such as clean energy resource fuel cell system use, also require safe to use.Therefore, according to the character of gas cylinder storage medium hydrogen, adopt seamless aluminium alloy lining that whole spinning process makes to solve the tightness, hydrogen embrittlement of gas cylinder and the problem of the low fatigue failure that causes because of weld cracking as the liner of hydrogen storage cylinder.
Summary of the invention
The present invention is in order to solve existing steel cylinder body weight, poor stability, because hydrogen density is little, so its storage hydrogen efficiency is very low, and when being pressurized to 15MPa, quality hydrogen-storage density≤3%.For mobile purposes, strengthen hydrogen pressure and improve and take the hydrogen amount and might cause hydrogen molecule to overflow or produce the hydrogen embrittlement phenomenon from container wall; Adopt the container tensile strength of single fibrous composite poor, stretch modulus is lower, the problem of anti-fracture strain and poor impact toughness, the invention provides the preparation method of a kind of pbo fiber and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder, concrete technological scheme is as follows:
Hybrid composite high-pressure hydrogen storage cylinder of the present invention comprises inside liner, adhesives layer and fibrous composite layer, it also comprises the glass fiber compound material external protection coating, the fibrous composite layer is made of carbon fiber composite inner structure layer and pbo fiber composite material external structure layer, inside liner adopts aluminum alloy, the outer surface and the adhesives layer of aluminium alloy lining layer are bonding, the internal surface of the outer surface of adhesives layer and carbon fiber composite inner structure layer is bonding, the internal surface of pbo fiber composite material external structure layer is wrapped on the outer surface of carbon fiber composite inner structure layer, and the outer surface of pbo fiber composite material external structure layer twines the glass fiber compound material external protection coating.
The preparation method of pbo fiber of the present invention and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder adopts the following step:
Step 1, even brushing one deck elastic interface adhesives layer 2 on the outer surface of aluminium alloy lining layer 1 at first;
Step 2, adopt fiber wet method winding process to carry out the making of carbon fiber composite inner structure layer 3 at the outer surface of adhesives layer 2, twine according to hocket carbon fiber composite screw and hoop of screw and hoop successively, the winding angle that screw twines is 15.5 °～19.5 °, each winding layer thickness is 0.6mm～0.7mm, and the thickness of carbon fiber inner structure layer 3 is 4.8mm～8.4mm;
Step 3, on the outer surface of the carbon fiber composite inner structure layer 3 of step 2, adopting the hocket winding of pbo fiber composite material external structure layer 4 of screw and hoop, the winding angle that screw twines is 16.0 °～19.5 °, each winding layer thickness is 0.4mm～0.5mm,, the winding thickness of pbo fiber external structure layer 4 is 2.0mm～4.0mm;
Step 4, twine two～three layers and hoop at the outer surface screw of the pbo fiber composite structural laminate 4 of step 3 and twine two～triplex glass fibrous composite external protection coating 5, the screw winding angle is 25 °～45 °, each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating 5 is 2mm～3mm;
Step 5, the bottle behind the above-mentioned stack winding shaping is put into curing oven be cured, the initial solidification temperature is 60 ℃～70 ℃, insulation 2h～3h, be warming up to 110 ℃～120 ℃, insulation 2h～4h, be warming up to 145 ℃～155 ℃ insulation 3h～5h at last, bottle naturally cools to room temperature with stove and comes out of the stove, and promptly makes pbo fiber of the present invention and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder.
The thickness of above-mentioned aluminium alloy lining layer 1 is that the thickness of 3mm～6mm, elastic adhesive layer 2 is 0.5mm～0.7mm.
The present invention has remedied the failure damage that the pressurized container made by single carbon fiber composite causes because of its low shock resistance and low strain level, remedied the failure damage that the pressurized container made by the composite material of single pbo fiber causes because of compression performance a little less than it and low interface shearing stress again, two kinds of materials of pbo fiber and carbon fiber are learnt from other's strong points to offset one's weaknesses, reached two kinds of purposes that fiber composite structure is optimized.Adopt aluminium alloy lining layer 1 integral spinning forming can satisfy the tightness of hydrogen under the circulation high pressure, have outstanding anti-hydrogen corrosivity, can not produce the hydrogen embrittlement crackle, avoid the fatigue failure that causes because of weld seam.What glass fiber compound material external protection coating 5 can be protected pbo fiber composite material external structure layer 4 avoids mechanical deterioration and light ageing.High-pressure hydrogen storage cylinder of the present invention has long service life (times of fatigue of this high-pressure hydrogen storage cylinder cycle charge discharge is greater than 8000 times), higher safety reliability (bursting pressure is greater than 83MPa, and working pressure can reach 35MPa).
Description of drawings
Fig. 1 is a longitudinal profile structural representation of the present invention.
Embodiment
Embodiment one: describe present embodiment in conjunction with Fig. 1.Present embodiment is made up of aluminium alloy lining layer 1, elastic adhesive transition layer 2, carbon fiber composite inner structure layer 3, pbo fiber composite material external structure layer 4 and glass fiber compound material external protection coating 5, bonding between aluminium alloy lining layer 1 and the carbon fiber composite inner structure layer 2 by elastic adhesive transition layer 2, the internal surface of pbo fiber composite material external structure layer 4 is wrapped on the outer surface of carbon fiber composite inner structure layer 3, at the outer surface winding glass fiber compound material external protection coating 5 of pbo fiber composite material external structure layer 4.
Embodiment two: the preparation method of present embodiment adopts the following step:
Step 1, even brushing one deck elastic interface adhesives layer 2 on the outer surface of aluminium alloy lining layer 1 at first; Aluminium alloy lining layer 1 material adopts 6061 aluminum alloys, and 6061 aluminum alloys have outstanding anti-hydrogen corrosivity, can not produce the hydrogen embrittlement crackle.The thickness of aluminium alloy lining layer 1 is that the thickness of 3mm～6mm, elastic adhesive layer 2 is 0.5mm～0.7mm.The seamless column structure that aluminium alloy lining layer 1 adopts whole rotary pressure technology to be shaped has been avoided the fatigue failure that causes because of weld seam.
Step 2, adopt fiber wet method winding process to carry out the making of carbon fiber composite inner structure layer 3 at the outer surface of adhesives layer 2, carry out successively that one to two helical layer twines, two layers of hoop twines, one to two helical layer twines, one to two layer of hoop twines, one to three helical layers twine and one deck hoops twine carbon fiber composite, the winding angle that screw twines is 15.5 °～19.5 °, each winding layer thickness is 0.6mm～0.7mm, and the winding thickness of carbon fiber composite inner structure layer 3 is 4.2mm～8.4mm;
Step 3, one to three helical layer twines, one deck hoop twines, two to three helical layers twine and one deck hoop winding shaping pbo fiber composite material external structure layer 4 adopting successively on the outer surface of the carbon fiber composite inner structure layer 3 of step 2, the winding angle that screw twines is 16.0 °～19.5 °, each winding layer thickness is 0.4mm～0.5mm, and the winding thickness of pbo fiber composite material external structure layer 4 is 2.0mm～4.0mm;
Step 4, adopt screw to twine two～three layers and hoop at the outer surface of the pbo fiber composite structural laminate 4 of step 3 to twine two～triplex glass fibrous composite external protection coating 5, the screw winding angle is 25 °～45 °, each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating 5 is 2mm～3mm;
Step 5, the bottle behind the above-mentioned stack winding shaping is put into curing oven be cured, the initial solidification temperature is 60 ℃～70 ℃, insulation 2h～3h, be warming up to 110 ℃～120 ℃, insulation 2h～4h, be warming up to 145 ℃～155 ℃ insulation 3h～5h at last, bottle naturally cools to room temperature with stove and comes out of the stove, and promptly makes pbo fiber of the present invention and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder.
The resin matrix of carbon fiber composite and pbo fiber composite material is epoxy-resin systems.
The elastic adhesive transition layer had both had the function of bonding aluminum liner and carbon fiber composite, also had the effect that the protection aluminum liner is not subjected to the electrochemical corrosion of carbon fiber simultaneously.
The glass fiber compound material that external protection coating 5 adopts can protect pbo fiber composite material external structure layer 4 to avoid mechanical deterioration and environment to its aging effect.
Embodiment three: the difference of present embodiment and embodiment two is that the brushing thickness of the elastic adhesive layer 2 of step 1 is 0.6mm; Carry out the winding of one deck screw, two layers of hoop winding, helical layer winding, the winding of one deck hoop, helical layer winding and the winding of one deck hoops in the step 2 successively, the winding angle that screw twines is 15.5 °, the thickness of each winding layer is 0.6mm, and the thickness of carbon fiber composite inner structure layer 3 is 4.2mm; Adopt the winding of one deck screw, the winding of one deck hoop, the winding of two helical layers and one deck hoop to twine in the step 3 successively, the winding angle that screw twines is 16 °, the thickness of each winding layer is 0.4mm, and the winding thickness of pbo fiber composite material external structure layer 4 is 2mm; Screw twines two layers and two layers of glass fiber compound material of hoop winding in the step 4, and the screw winding angle is 25 °, and each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating 5 is 2mm; The bottle solidifying temperature is 60 ℃ in the step 5, and insulation 3h is warming up to 110 ℃ then, and insulation 4h is warming up to 150 ℃ at last again, insulation 5h.Other step is identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two is that the brushing thickness of the elastic adhesive layer 2 of step 1 is 0.6mm; Carry out successively in the step 2 that one deck screw twines, two layers of hoop twines, two helical layers twine, two layers of hoop twines, two helical layers twine and one deck hoops twine, the winding angle that screw twines is 17 °, the thickness of each winding layer is 0.6mm, and the winding thickness of carbon fiber composite inner structure layer 3 is 6mm; Adopt two helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of two helical layers and one deck hoop, the winding angle that screw twines is 17 °, the thickness of each winding layer is 0.6mm, and the winding thickness of pbo fiber composite material external structure layer 4 is 3.6mm; Screw twines two layers and hoop winding triplex glass fibrous composite in the step 4, and the screw winding angle is 35 °, and each winding layer thickness is 0.5mm, and the winding thickness of glass fiber compound material external protection coating 5 is 2.5mm; Solidifying temperature is 65 ℃ in the step 5, and insulation 2.5h is warming up to 115 ℃ then, and insulation 3h is warming up to 150 ℃ at last again, insulation 4h.Other step is identical with embodiment two.
Embodiment five: the difference of present embodiment and embodiment two is that the brushing thickness of the elastic adhesive layer 2 of step 1 is 0.7mm; Carrying out two helical layers in the step 2 successively twines and the winding of one deck hoops to winding, two layers of hoop winding, the winding of two helical layers, two layers of hoop winding, three helical layer, the winding angle that screw twines is 19.5 °, the thickness of each winding layer is 0.7mm, and the winding thickness of carbon fiber composite inner structure layer 3 is 8.4mm; Adopt three helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of three helical layers and one deck hoop, the winding angle that screw twines is 19.5 °, the thickness of each winding layer is 0.5mm, and the winding thickness of pbo fiber composite material external structure layer 4 is 4mm; Screw twines three layers and hoop winding triplex glass fibrous composite in the step 4, and the screw winding angle is 45 °, and each winding layer thickness is 0.5mm, and the winding thickness of glass fiber compound material external protection coating 5 is 3mm; Solidifying temperature is 60 ℃ in the step 5, and insulation 2h is warming up to 120 ℃ then, and insulation 3h is warming up to 155 ℃ at last again, insulation 3h.Other step is identical with embodiment two.
According to the stress of column high-pressure hydrogen storage cylinder and the mechanics feature of pbo fiber and carbon fiber, to have outstanding compression performance, the carbon fiber design of low strain and good and interface performance resin matrix at the internal layer of container with the compressive load of carrying container with carry out effective Stress Transfer, to have the impulsive load that the design of excellent tensile property and impact toughness pbo fiber presses in main carrying container the tension load that causes and external environment condition to cause at the skin of container, so both can remedy the failure damage that the pressurized container made by single carbon fiber composite causes because of its low shock resistance and low strain level, can remedy the failure damage that the pressurized container made by the composite material of single pbo fiber causes because of compression performance a little less than it and low interface shearing stress again, two kinds of lamination coatings are learnt from other's strong points to offset one's weaknesses, reach the purpose of fiber hybrid composite structure optimization, realized the combination property optimization of hydrogen storage vessel structure.Improve composite material high-pressure bottle working life and safety reliability.

Claims (2)

1, the preparation method of pbo fiber and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder is characterized in that this preparation method's step is as follows:
Step 1, even brushing one deck elastic interface adhesives layer (2) on the outer surface of aluminium alloy lining layer (1) at first;
Step 2, adopt fiber wet method winding process to carry out the making of carbon fiber composite inner structure layer (3) at the outer surface of elastic interface adhesives layer (2), twine according to hocket carbon fiber composite screw and hoop of screw and hoop successively, the winding angle that screw twines is 15.5 °～19.5 °, each winding layer thickness is 0.6mm～0.7mm, and the winding thickness of carbon fiber composite inner structure layer (3) is 4.8mm～8.4mm;
Step 3, on the outer surface of the carbon fiber composite inner structure layer (3) of step 2, adopting the hocket winding of pbo fiber composite material external structure layer (4) of screw and hoop, the winding angle that screw twines is 16.0 °～19.5 °, each winding layer thickness is 0.4mm～0.5mm, and the winding thickness of pbo fiber composite material external structure layer (4) is 2.0mm～4.0mm;
Step 4, twine two～three layers and hoop at the outer surface screw of the pbo fiber composite material external structure layer (4) of step 3 and twine two～triplex glass fibrous composite external protection coating (5), the screw winding angle is 25 °～45 °, each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating (5) is 2mm～3mm;
Step 5, the bottle behind the above-mentioned stack winding shaping is put into curing oven be cured, the initial solidification temperature is 60 ℃～70 ℃, insulation 2h～3h, be warming up to 110 ℃～120 ℃, insulation 2h～4h, be warming up to 145 ℃～155 ℃, insulation 3h～5h at last, bottle naturally cools to room temperature with stove and comes out of the stove, and promptly makes pbo fiber and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder.
2, the preparation method of pbo fiber according to claim 1 and carbon fiber hybrid composite material high-pressure hydrogen storage cylinder is characterized in that the brushing thickness of the elastic interface adhesives layer (2) of step 1 is 0.7mm; Carrying out two helical layers in the step 2 successively twines and the winding of one deck hoops to winding, two layers of hoop winding, the winding of two helical layers, two layers of hoop winding, three helical layer, the winding angle that screw twines is 19.5 °, the thickness of each winding layer is 0.7mm, and the winding thickness of carbon fiber composite inner structure layer (3) is 8.4mm; Adopt three helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of three helical layers and one deck hoop, the winding angle that screw twines is 19.5 °, the thickness of each winding layer is 0.5mm, and the winding thickness of pbo fiber composite material external structure layer (4) is 4mm; Screw twines three layers and hoop winding triplex glass fibrous composite external protection coating (5) in the step 4, and the screw winding angle is 45 °, and each winding layer thickness is 0.5mm, and the winding thickness of glass fiber compound material external protection coating (5) is 3mm; Solidifying temperature is 70 ℃ in the step 5, and insulation 2h is warming up to 120 ℃ then, and insulation 3h is warming up to 155 ℃ at last again, insulation 3h.
CNB2006101509885A 2006-11-06 2006-11-06 High pressure hydrogen storage bottle made of PBO fiber and carbon fiber mixed composite material and preparation method Expired - Fee Related CN100430641C (en)

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CN102085724A (en) * 2009-12-02 2011-06-08 上海康巴赛特科技发展有限公司 Wet fully-winding and curing process for preparing hydrogen cylinder with carbon fiber lining
CN102135178B (en) * 2010-12-30 2013-01-23 西安航天复合材料研究所 Dry yarn winding forming method for pressure container
CN105333302B (en) * 2015-09-25 2018-01-02 石家庄安瑞科气体机械有限公司 A kind of preparation method of Large Copacity high-pressure hydrogen storage winding composite shell
CN105640780A (en) * 2016-03-23 2016-06-08 潍坊孕宝网络科技有限公司 Anti-falling glass milk bottle and production method therefor
CN111765366B (en) * 2020-06-24 2021-11-16 武汉理工大学 Novel vehicle-mounted high-density hydrogen storage bottle with multilayer inner container
CN114105660B (en) * 2020-08-28 2023-11-24 上海市洁能科技有限公司 Material composition for hydrogen storage structure, material for hydrogen storage structure, and hydrogen storage single tube
CN112097094A (en) * 2020-09-09 2020-12-18 沈阳中钛装备制造有限公司 Titanium alloy seamless gas cylinder and manufacturing method thereof
CN114110413B (en) * 2021-11-10 2023-07-28 航天材料及工艺研究所 Carbon fiber composite material thick-wall gas cylinder and preparation method thereof

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