Highlights

Hydrogen can regard a kind of 0 carbon as the sources of energy, have source rich, clean environmental protection, combustion is worth tall, free from contamination, but store a series of advantages such as carry, be known as 21 centuries to provide 2 the sources of energy that expand latent capacity most. Hydrogen can use a form extensive, lash-up of station of power station of cell of forklift of cell of car of hydrogenous fuel cell, fuel, fuel, communication radical reserves the hydrogen such as power source can use typical product progressively already promotion, the sources of energy that this is faced with to solving the world and environmental problem have important sense.

Hydrogen can use complete chain to include production, store, carry, a few respects such as application, and the Chu Qing technology that decides the key that hydrogen can use whether extensively is on the safe side. The car carries Chu Qing technology to basically include high-pressured gaseous state Chu Qing of Chu Qing, microtherm liquid state, solid Chu Qing and organic liquid Chu Qing. Among them, because high-pressured Chu Qing has equipment structure simple, reduce hydric preparation specific power consumption low, fill install and discharge speed to wait for an advantage quickly and suffer fully take seriously, it is the hydrogen that takes absolutely dominant place at present can store lose way.

Integrated consideration compresses specific power consumption, add to sail the element such as construction of course of development, infrastructure, safety, high-pressured Chu Qing enrages the nominal actuating pressure of bottle to be 35-70MPa commonly. High-pressured Chu Qing enrages bottle of main component to be 4 types: Complete metal gas cylinder (Ⅰ ) , gas cylinder of hoop winding of fiber of the bravery inside the metal (Ⅱ ) , fiber of the bravery inside the metal twines gas cylinder completely (Ⅲ ) , metalloid inside bravery fiber twines gas cylinder completely (Ⅳ ) . Among them, Ⅰ , Ⅱ heavy look is compared big, satisfy the Chu Qing density of car of hydrogenous fuel cell to ask hard. Ⅲ , because Ⅳ bottle used fiber to twine a structure completely, have heavy look more advanced than density of Chu Qing of quality of small, unit advantage, apply extensively already at car of hydrogenous fuel cell at present.

One, of bottle of each type Chu Qing quite

Accompany the rapid development of hydrogenous fuel cell and electric car and industrialization, hydrogen store the research heat that the difficult problem of carry is making a whole world. Chu Qing bottle is among them very important a kind store carry medium, next watches listed each function of bottle of different Chu Qing to contrast.

Express bottle of 1 Ι~ Ⅳ Chu Qing

Accompany the rapid development of hydrogenous fuel cell and electric car and industrialization, gas cylinder of Ⅳ Chu Qing because its quality is light, be able to bear or endure the research heat that the characteristic such as exhaustion is making a whole world, gas cylinder of the Ⅳ of the country such as Japan, Korea, United States and Norway Chu Qing already all was measured produce, the others country also has relevant plan to increase the research strength of Ⅳ gas cylinder.

The production cost of bottle of IV Chu Qing is in 3000~3500 dollar, basically include: Composite material, valve, adjuster, assemble examination, hydric etc, among them the 75% above that the cost of composite material holds totle drilling cost, and the cost of hydric itself is occupied only about 0.5% . The development trend of technology of Chu Qing bottle is light quantify, density of high-pressured force, tall Chu Qing, macrobian life, compare conventional metallic data, high polymer composite material can be in hold identical compression order and degree while, reduce storage tank wall thick, improve capacity and hydrogenous memory efficiency, reduce the cost of specific power consumption in line-haul process. Accordingly, the function of composite material and cost are the key of preparation of gas cylinder of IV Chu Qing.

2, structure of bottle of IV Chu Qing and material

Gas cylinder of composite material Chu Qing by inside liner material includes outside coming, transfer layer, fiber twines a layer, outside covering layer, resilient coating. The periodic possibility that Chu Qing gas cylinder has aerating is longer, and hydric have again below high pressure very strong osmotic, so liner material should have hydric storage tank to cut off goodly function, store in order to make sure major morale physical ability is enough in container.

The structure of bottle of IV Chu Qing basically includes the following share:

(The bravery inside 1)

Bottle wall total ply is 20~30mm about, most of lining and hydric and direct contact is block gas layer, ply is 2~3mm about, material is PA6, PA612, PA11, HDPE, cut off since hydric action.

(Among 2) layer

Compare thick compression layer, material is CFRP carbon fiber enhances composite material, form by carbon fiber and epoxy resin, below the premise that assures compression grade, reduce this thickness as far as possible in order to improve Chu Qing efficiency.

(3) surface layer

The outerest it is exterior covering layer, ply is 2~3mm about, material is GFRP Bo fine enhances composite material, form by fibre glass and epoxy resin.

The structure of bottle of graph 1 IV Chu Qing

2.1 inside the raw material of bravery and shape craft

Plastic inside the gas cylinder of complete composite material of bravery (Ⅳ bottle) , use high polymer material to do inside bravery, carbon fiber composite material is twined as bear force layer, quality comparing can amount to Chu Qing 6% above, the most high-energy achieve 7% , then cost can be reduced further.

Graph the 2 bravery inside Chu Qing bottle

(1) is able to bear or endure hydric osmotic with hear resistance

Hydric element is passed through extremely easily plastic inside the housing data of bravery, the hydrogenous vapour lock that raw material must consider when select material separates function. In addition, hydric after the reduce expenditure action in course valve, aeriform temperature will be elevatory, subsequently gas is compressed gas cylinder actuating pressure, temperature is likewise elevatory, bravery raw material needs to have inside appropriate hydric osmotic with heat-resisting function.

PA6 colophony is in prevent hydric permeate a respect to have outstanding property, have excellent mechanical performance, include to be able to bear or endure to fill up and be discharged hydric when the impact resistance below the wear that storage tank temperature changes suddenly and microtherm environment. Can pass osmotic to PA6 material the modified processing that had raw material level, the bate temperature that raises material is controlled to 180 ℃ , can satisfy use requirement.

(The low temperature with good 2) is mechanical function

Note temperature to avoid to add exorbitant internally bravery raw material causes loss, have gas cause cooling normally, general refrigeration comes - 40 ℃ , when microtherm hydric fill gas cylinder interior, bravery will harden below microtherm inside and fragile, easy burst, inside the low temperature of bravery raw material is mechanical function appears particularly important.

(The craft sex with good 3)

Plastic inside bravery shapes the technology includes to note model to shape, rotational moulding shapes, blow model to shape etc. At present Feng Tian, contemporary the bravery inside gas cylinder of the Ⅳ that waits for place of fuel cell car to use Chu Qing shapes craft all is the craft that note model. The craft that note model is cost inferior, apply relatively extensive also inside bravery shapes means, need the welder order that cooperates sequel at the same time, ability shapes inside bravery.

The bravery inside bottle of 2.2IV Chu Qing shapes craft

Inside traditional aluminium bravery twines gas cylinder intensity completely in the design, take no account of commonly inside bravery bears the weight of, the internal pressure of theoretic gas cylinder is complete by enhance fiber to assume. But in fact, the bravery inside gas cylinder is in from beginning to end below actuating pressure draw stress position, this is the key that restricts life of gas cylinder exhaustion. To satisfy weight of Chu Qing gas cylinder at the same time light, fatigue resistance asks well, the choice is right inside bravery appearance and dimension sense are great.

The bravery inside IV bottle uses polyethylene of PA6, high density more (HDPE) and PET polyester are plastic etc, shape correspondingly craft basically is note model, blow model and rotational moulding to shape. Feng Tian, contemporary already measured the IV that produce bottle to all be note model + welder art, this kinds shape means cost is low, apply more extensive, but fine is tasted rate is inferior also, and the welder foreword that must cooperate sequel.

Express the 2 bravery inside Chu Qing bottle to shape craft

3, matrix of colophony of bottle of IV Chu Qing

Matrix of colophony of gas cylinder of carbon fiber Chu Qing needs to satisfy gas cylinder to be opposite not only the requirement of mechanical intensity and tenacity, because be in,aerate for a long time at the same time in the use environment of deflate, incidental exhaustion injures matrix, because this needs excel in pliable but strong, be able to bear or endure fatigue resinite is the service life with ensuring gas cylinder. Wet twine shape uses colophony matrix, besides wanting to satisfy corresponding function, beg its to be had below working temperature even inferior initiative viscosity and longer working life is had below this temperature. Epoxy resin has cohere strength shrinkage of tall, solidify is small, shape without young member volatile, craft the gender is good, hear resistance, chemical stability good, cost is low advantage, and have very large modified space, and its origin extensive, price is reasonable, apply to wet twine craft system.

Chu Qing of IV high pressure enrages the colophony of bottle of composite material layer to basically use epoxy resin. Epoxy resin is the resin of hot solid sex that at present composite material middling uses colophony radical one of matrix, have cohere strength shrinkage of tall, solidify is small, shape without young member volatile, craft the gender is good, hear resistance, chemical stability good, cost is low advantage and use extensively at fiber to twine craft.

(The mechanical performance with good 1)

Colophony is in the action in composite material is fixed fiber, deliver load through the interface between colophony and fiber, make fiber intensity play comes the biggest change. Need colophony has taller tenacity and strength, but both be contradiction, mutual the balance between is difficulty of technology of colophony modified key.

(The thermal stability with good 2)

To gas cylinder of Ⅳ Chu Qing, need makes solidify temperature under plastic inside bravery bate temperature, and structure of the bravery inside protection. Be in safe condition completely in using a process actually to assure gas cylinder, with respect to need temperature of colophony vitrification transition is more than 105 ℃ , generally speaking, solidify temperature is lower, the vitrification temperature after solidify is lower also, this and protection are plastic inside bravery structure stability formed contradictory body, need undertakes corresponding modified to colophony.

(The technical properties with good 3)

Colophony working life is appropriate, viscosity moderate, it is the main show of colophony craft sex. The car carries Chu Qing to enrage the ply of composite material layer of bottle to be commonly between 20 ～ 30mm, twine time longer, colophony working life is briefer, can make colophony wellability becomes poor, affect composite material performance. Of solidify furnace heat means is to pass air convection, heat radiation undertakes heating to gas cylinder, make its solidify shapes, viscosity is improper, make colophony more difficult eduction bleb, and quantity of heat is delivered to interior by the surface, inside and outside is put in temperature gradient, the meeting after solidify forms bleb in the surface, interior forms the blemish such as hole, affect product performance badly even.

Feng Tian Motor Corporation invented a kind of method that can reduce bleb of gas cylinder surface, the resorcinol that is used at gas cylinder is two kinds, one kind is mold the first resin that twines a layer with carbon fiber, another kind is the 2nd resin that molds covering layer with fibre glass. Temperature of gel of the 2nd resinous is higher than temperature of gel of the first colophony, below temperature of gel of the first colophony, viscosity of the 2nd resinous is lower than viscosity of the first colophony, accordingly, the gas that interior of Yu Shu fat remains in layer solidify process is twined in carbon fiber from covering layer outward eduction, the colophony of low viscosity makes before solidify can the gas with more eduction, restrain the remain of bleb of gas cylinder surface thereby, raise exterior character.

Graph bottle of the Ⅳ that 3 abundant cropland develops Chu Qing

4, bottle fiber twines IV Chu Qing shape craft

Carbon fiber is twined shape craft can be divided for wet twine and do a law to twine, among them wet because its cost is inferior,twine, craft sex is good, application is relatively accordingly wide, wet twine equipment to basically include fiber wearing, tension to control chamfer of equipment, impregnation, spin the mouth and rotate core model structure. The more advanced 6 dimension on international twine a technology to be able to control fiber trend well, implementation hoop winding, come back to twine and plane twines photograph union. Use more in actual production come back to wind the way that ties with hoop winding photograph, the annulus that hoop winding can eliminate gas cylinder to get internal pressure and arises to stress, come back to twine can offer fore-and-aft stress, promote gas cylinder whole property.

Fiber twines the design of the layer to need to consider fibrous anisotropy, according to its the structure asks, use layer board theory and reseau theory to calculate normally the stress that container seals head, liner, fiber to twine a layer distributings circumstance, choice of the tension in twining craft certainly then and line distributing. Through hoop winding and come back to twine undertake coming true alternately mutiple level structure, the choice is proper fiber pile area and fore-and-aft twine angle and come back to winding pattern, satisfy intensity requirement not only, make seal a point at the same time can reasonable shop Fu.

4.1 dry methods twine craft

Dry method twines craft in order to pass beforehand impregnation handles beforehand dip belt is raw material, via heating on twister bate comes stick core model is twined to go up after sorting voice. Its advantage basically has:

(1) major produces beforehand dip yarn / belt, can assure to control fiber and colophony strictly (come accurately 2% less than) content scale, product quality is good and stable;

(2) production efficiency is tall, winding rate can amount to 100~200m/min;

(3) twines equipment and manufacturing environment sanitation neat, facilitate clear, the service life of twister is longer also.

Graph 4 dry methods twine technological process graph

Graph 5 dry methods are twined

4.2 wet twine craft

Wet twining craft is carbon fiber silk bundle after the macerate in specific impregnation device is handled, twine core model to go up directly below tensional control again, pass solidify finally shape method. Its advantage basically is as follows:

(1) production cost is inferior, twine than working a way about low 40% . Involved technological equipment is simpler, installation cost is small, and relatively inferior to raw material requirement.

(2) product air-tightness is good, in twining a process, through tension control can make redundant colophony glue fluid squeezes bleb piece, and cram is interstitial.

(The colophony glue fluid of macerate of surface of 3) carbon fiber can reduce fiber effectively to wear away.

(It is good that 4) fiber arranges parallelism.

Graph 6 wet twine technological process graph

Graph 7 wet twine

4.3 basically wind way

(1) hoop winding

Hoop winding is twine along what circumferential direction has container. Twine Shi Xinmo to circle him axes to make uniform motion, the motion of canister body interval in direction of axes of parallel Yu Xinmo. Core model every turn a week, distance of shift of seal wire head is a gauze piece wide. Such loop goes down, till gauze piece bestrew core model cylinder equably paragraph till the surface.

The characteristic of hoop winding is to twine can undertake in canister figure only, cannot tangle to seal a head to go up. Adjacent gauze piece connect and do not overlap, fibrous twines horn to be normally between 85°~90° .

Graph sketch map of 8 hoop winding

(2) helix is twined

Helix is twined also say geodesic twine. Model of the core when twining circles him axes divide evenly fast roll, seal wire head presses reciprocate of direction of axes of model of core of specific rate edge, mix with respect to the canister body in core model so helix came true to twine on the head, its twine horn to be 12°~70° about. Twine in helix in, fiber is twined undertake in canister figure not only, and sealing a head to go up to also undertake. Its twine a process to be: Fiber from container one aspect of the matter extremely dot of the some on Kong Yuan week sets out, go up along the curved surface that seal a head with extremely Kong Yuan's tangent curve bypasses a head, bypass by corkscrewed yarn contrail cylinder paragraph, enter another end to seal a head, return cylinder again next paragraph, final retrace seals a head to what begin to twine, such loop goes down, till core model surface is even,bestrew fiber till. Such, when fiber pesters surface of full core model equably, formed layer of double deck fiber. Satisfy use pressure requirement to assure to twine the gas cylinder after, its twine means to choose hoop winding and helix to wind the way that ties commonly.

Graph 9 helix twine sketch map

Graph 10 Chu Qing bottle twines craft

The place on put together is narrated, the production of bottle of IV Chu Qing makes circuit following plan institute are shown. Can see the manufacturing process of high-pressured hydrogen bottle basically includes:

(1) liner is machined (will thermoplastic alkene polymer is made inside bravery)

(2) fiber is twined shape

(3) examination examines

Bottle of Ⅳ of graph 11 Chu Qing produces flow

Product line of bottle of Ⅳ of graph 12 Chu Qing

5, the new challenge of bottle of V Chu Qing

With the level that at storing below high pressure the development of aeriform pressure vessel and storage tank experienced 4 to differ, of the complete composite material of — of the 5th phase of pressure vessel without inside bravery storage tank (V) , it is to point to do not contain any inside the pressure vessel that use composite material bravery, completely to machine and becomes, long-term since the commanding elevation that V pressure vessel is considered as product of pressure vessel industry and technology all the time.

The structure of surface layer three-layer of the intermediate layer that compares layer of colophony of aggrandizement of the bravery inside the colophony liner at IV bottle, carbon fiber and layer of colophony of fibre glass aggrandizement, v bottle is to not have inside two structures of bravery, namely housing of carbon fiber composite material and dome defend layer. Comparative IV bottle, actuating pressure can amount to V bottle 70~100MPa, without hydrogen fragile, the advantage is waited a moment in can amounting to 30 years of above, cost without caustic, service life, yi Ke is used at spaceflight and car to carry a territory. The technology of V bottle still is in on the market at present start level, each industry is paying close attention to the development of the technology of V bottle and opportunity closely.

Core model is cast partly by cent of water-solubility core material, agglutinate is made, the wall is large 30 millimeter. Interior has annular reinforcement, conduce to the pressure of the generation in bearing to reverse load and fiber solidify course in what fiber arises in process of automatic lay up.

Beforehand dip expects accurate cut becomes the tape with wide 6.35mm, twine gross length 22000 meters. Twine a process to use helix of special software control and annular twine. Twine 24 layer, ply to amount to 5.5mm.

Dissolubility of graph 13 V bottle core model

Graph 14 V bottle twines equipment

Epilogue

Ⅳ Chu Qing enrages the research and development of bottle to be contacted together besides need and composite material, need to be contacted cheek by jowl together with plastic treatment workmanship and plastic and sealed structure more. To our country character, the technology still lies related Ⅳ gas cylinder the phase of a ceaseless development, ceaseless enterprising, need to try hard to perfect corresponding technology theory ceaselessly, for henceforth model the research and development of gas cylinder lays next solid foundations.

Bibliographical reference

1.Chu Qing bottle uses carbon fiber circuit: Hydrogenous wind already came, be well worth doing - the country contains negotiable securities

2.Fang Kun, liu Kang, v complete composite material is able to bear or endure canister of tall calm sb's anger (bottle) newest development, 2022

3.Suo cropland , element of tall water uses of Zuo of CFRP container の , ENEOS Technical Review

Article origin: Shanghai hydrogen seminar of science and technology