Journal of Pressurized Equipment and Systems 2 (2004) 59-63

State-of-the-art of fiber-reinforced high-pressure hydrogen storage tanks

Fangming Kai a,*, Zhongqiang Liu a, Qiang Fu a, Jinyang Zheng a, Changpin Chen b
a

Institute of Chemical Process Equipment, Zhejiang University, Hangzhou 310027,China, b Institute of Metal Materials, Zhejiang University, Hangzhou 310027,China

Abstract The state-of-the-art of gaseous hydrogen storage tanks is reviewed in this paper. The structure, design and testing methods of fiber-reinforced composite tanks are introduced. The tank mainly consists of a permeation resistant polymer or metal liner, carbon-fiber-reinforced layer which takes almost all the loads due to inner pressure, impact-resistant layer and external protective layer. Keywords: Hydrogen storage tanks; Composite materials; High-pressure tanks.

1. Introduction Mass consumption of fossil fuel has caused environment problems in many countries. Increase in the CO2, NO2 and SOx emissions due to this huge consumption of fossil fuel has led to the greenhouse effect and air pollution. Hydrogen energy is one of the most important energy sources, which is clean and efficient. Many countries are engaged in the development of the hydrogen related energy technology. Hydrogen storage is one of the key issues in the hydrogen energy technology. At present, there have been four different hydrogen storage methods: liquified hydrogen, compressed hydrogen gas, metal hydride and nanostructure carbon hydrogen storage [1]. The technique using compressed hydrogen gas is widely used due to its simplicity of the storage system and low cost for storage and transport compared with the other techniques. This paper summarizes the recent progresses in lightweight high-pressure hydrogen storage tanks. 2. Recent progresses in high-pressure hydrogen storage technology 2.1. Development of high-pressure hydrogen storage tanks The energy volumetric density of hydrogen is less than traditional fuel. To improve hydrogen storage mass efficiency and reduce transportation cost, the tanks should stand a higher storage pressure with less weight. In 2000, the Quantum Technologies, Lawrence Liv*

ermore National Laboratory and Thiokol achieved the hydrogen storage mass efficiency of 11.3 weight percentage on a prototype 35 MPa tank and demonstrated proof-of-concept 70 MPa tank [2]. In 2002, the storage mass efficiency got 13.36% on a 35 MPa Aerospace demonstration. In July 2002, the Lincoln Composites has successfully tested a Tuffshell hydrogen storage tank with an operating pressure of 70 MPa and a burst pressure of 175 MPa [3]. In Mar 1, 2002, Honda announced that it had received Japanese Ministry of Land, Infrastructure and Transport approval for the FCX V4 fuel cell vehicle equipped with a 35 MPa high-pressure hydrogen tank. Honda has applied the high-pressure tank technology accumulated through natural vehicle development to fit the FCX-V4 with a 35 MPa high-pressure hydrogen tank. In the high-pressure hydrogen storage technology, China is at the beginning stage in general. But there are mature storage techniques of CNG (Compressed Natural Gas). In many cities, CNG fuel vehicles are used. For example, in Chengdu city in southwest of China, all the taxis use CNG as the fuel. Normally, the operating pressure of the composite CNG tank is 20 MPa [4]. Some companies are devoting to research and produce CNG tanks. Because the working condition of the high-pressure hydrogen tanks is similar to CNG tanks, the technology of CNG tanks are useful to the hydrogen storage tanks [5]. Chinese government is keen to develop the technology and includes it in the 863 high tech programs. Zhejiang University and other research institutes have devoted to the research of CH4 tank and began to test a hydrogen storage tank with an operating pressure of 40 MPa. 2.2. Codes and standards for the high-pressure hydrogen storage tanks

Corresponding author. E-mail address: seeyouseeme@zju.edu.cn (FangMing Kai).

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So far, there is no international standard approved for the hydrogen storage tanks. International Standard Organization has established the draft of ISO 15869, Gaseous hydrogen and hydrogen blends-Land vehicle fuel tanks. In March 2003, ASME was given the lead in developing standards for composite containers, pipelines, and equipment relating to the category of hydrogen delivery and storage in USA. Because of the similarity between CNG tanks and hydrogen storage tanks, hydrogen storage tanks can be designed and manufactured by referring to the CNG tank codes and standards, such as ISO 11439-2000, High-pressure Cylinders for the On-board Storage of Natural Gas as a Fuel for Automotive Vehicles and ANSI (the American National Standards Institute) code, NGV2-2000, Basic Requirements for Compressed Natural Gas Vehicle (NGV) Fuel Containers. For some composite hydrogen storage tanks, the ASME Code, Section X, Fiber-reinforced Plastic Pressure Vessels, EN 12245, Transportable gas cylinders. Fully wrapped composite cylinders and EN 13923, Filament wound FRP pressure tanks can also be used. Now, there are still no national standards available for the hydrogen storage tanks in China. For designing of steel tanks of the maximum design pressure of 35 MPa, GB150-1998, Steel Pressure Vessels can be used. Standards of CNG tanks, such as GB 17258-1998, High-pressure tanks for the On-board Storage of Natural Gas can also be referred to. For the fiber-reinforced tanks, the standards such as, GB6058-1985, Fabrication and pressure testing of the fiber-wrapped pressure tanks are available. 3. Fiber-reinforced high-pressure hydrogen storage tanks 3.1. Structure Because composite material is low in density, high in strength and modulus, the advanced hydrogen storage tanks adopt multi-layers composite structure. Such composite tank shown in Fig. 1 mainly consists of internal liner, transition layer that is overwrapped with carbon fiber-reinforced layer, impact-resistant layer, and fiberglass-reinforced external protective layer. Internal liner. The main function of internal liner is to provide hydrogen permeation barrier, preventing compressed hydrogen gas form leaking. It also serves as the mandrel during winding process. The liner doesnt share any of the shell membrane loads. But the liners low modulus makes it easier in deformation during pressurization. So the liner can transfer the loads to the carbon fiber-reinforced layer. The permeability of high-pressure hydrogen is very important. The American Gas Association (AGA) prescripts that the liner must be of sufficient thickness such that the tank will meet the permeability limit of

0.25 cc/hr/liter [6]. Though relatively light and inexpensive, the engineering plastic has a low permeation rate, good corrosion resistance and mechanical properties. Its easily formed. Overlayed the metal on the surface of the polymer, it has better performance as permeation barriers. Though the polymer liner couldnt resist the loads, it reduces the weight of the tank. The polymer liner is 30% lighter than the metal and the cost is reduced by 50% [7]. The liner consists of one cylinder and two domed ends made by blow molding. A metal boss is disposed in a polar opening in the domed ends of the liner. The domed ends are injection molded around the tank boss. The structure is shown in Fig. 2. The modulus of the polymer and the metal are different, so the stiffness isnt continuous at the interface of two materials. Therefore the transition must be smooth so that the boss will not be off when subjected to the loads. The polymer material is sensitive to the temperature and its much easier to aging with change in temperature during the charging operation. The difference in the coefficient of thermal expansion between liner and boss may cause the joint leak with increase of temperature cycle number. And the impact-resistant character of the polymer liner tanks is not as good as the metal liner tanks. Some metal liners have better performance for preventing permeation of hydrogen. Besides this, they can resist a part of the loads. At the same time, the other loads are transferred to the fiber-reinforced layer. The material could be alloy of aluminum, steel and others. The structure of the metal liner is similar to the polymer one. The metal boss is threaded connected with the nozzle embedded in the polar opening of the domed ends. The metal liner enhances the reliability and impact-resistant performance. But the design ability of the metal need improve. Carbon fiber-reinforced layer. The fiber-reinforced layer takes all or large part of the loads. The layer is wound by the carbon fiber/epoxy on a professional numerical control winding machine. Carbon fiber is selected because of its high strength-to-weight ratio, high modulus-to-weight ratio, excellent fatigue resistant characteristics, insensitivity to environmental degradation, and perfect reliability. It is a good material for making lightweight high-pressure tanks. The carbon fiber, T1000G, produced by Toray has excellent performances, its tensile strength is 6370 MPa, tensile modulus 294 GPa, elongation percentage 2.2%, and density 1.8 g/cm3 [8]. The fiber-reinforced structure can greatly reduce the weight and the cost of tank. For the fiber-reinforced CNG tank, the weight is only 1/4 of that of the metal tank. Zoltek plans to at least reduce the price to 11 dollars/kg before 2003~2004 [9]. When the price of the carbon fiber is 17.6 dollars/kg, the cost of the tank is 22.3% of the metal tank. Even the price is 28.6 dollars/kg, the cost is only 27.3% of the metal ones [10].

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1. Boss

2. Nozzle 3. Impact-resistant layer 4. Fiberglass-reinforced external protective layer 5.Carbon-fiber-reinforced layer 6. Transition layer 7.Iinternal liner Fig. 1. Construction of fiber-reinforced composite tanks.
1 2 3 4 5 6

1. Impact-resistant layer 4. Transition layer

2. Fiberglass-reinforced external protective layer 3. Boss 5. Carbon-fiber-reinforced layer 6. Internal liner

Fig. 2. Traditional dome construction of the fiber-reinforced composite tanks.

The liner is overwrapped with both low-angle and high-angle helical filament. The continuous carbon fiber dipped in the resin applicator, were wrapped on the surface of the liner under the initial force. And then, the fiber-reinforced layer is solidified and shaped at the moderate temperature. The prior art designs are disadvantageous in failing to adequately strengthen at the cylinder-to-dome transition area. Now, high angle helical windings at angles from 60o to 88o to the longitudinal axis of the tank cross the transition points. It eliminates the slippage and void occurrence and reduced strength properties in this area [6]. To prevent the tank from buckling, it could be subjected to some internal pressure during winding. Furthermore, this layer could be made of multi-fibers, such as carbon fiber and fiberglass. This structure can reduced the cost and adjust the performance of the layer. Gunfire test shows that a 50/50 carbon/fiberglass hybrid is an optimum, low-cost overwrap design and the fiberglass makes a significant contribution to gunfire toughness [11]. Transition layer. The difference in properties be-

tween the internal liner and the fiber-reinforced layer makes the tendency of relative displacement under internal pressure. It creates shear stresses between the two layers. The buffer material with high shear modulus is intercalated between these two layers. The shear strain of the buffer material is lower. So the fatigue life of the tank is improved. Rubber as the traditional buffer material is stick on the surface of the liner by adhesive. It is not easy to manufacture. In this tank, the adhesive with high shear modulus is used as the buffer material. It replaces the rubber and the adhesive in the prior structure. The winding process on the buffer layer is easier than on the metal liner. In particular, the fiber slippage could be avoided. The entirety of the tank is improved. Sometimes, its lighter than the rubber layer. Impact-resistant layer. When a tank drops, the impact could damage the tank and make fiber fracture. The impact-resistant layer will deform to absorb the energy of the impact, mitigate the peak load and distribute the induced load over an enlarged area. Normally the damage mitigating material is light and

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could be polystyrene, polyurethane, polyethylene or polypropylene foam and other polymers. They have good thermal insulation, heat endurance and compressibility. Traditionally, this layer is embedded between the fiberglass-reinforced external protective layer and the carbon fiber-reinforced layer. It is integrated in the area of the dome-shaped end as shown in Fig. 2. This area is quite effective because such an elongated tank, when dropped, normally will land on one of its ends and/or bounce back and forth between its ends [12]. Traditional structure could release the impact energy and protect the tank when the impact angle to the o axial of the tank is 45 . With the increase or decrease of the impact angle, the damage mitigating system could not work very well. The boss, the dome and the side of the tank could be damaged. Because of the existence of the damage mitigating material, the winding process of the layer becomes more difficult. The structure of this tank can resist the small or large angle impact and protect the boss, the dome and the side of the tank. Moreover, the impact-resistant layer is easier to be fixed on the dome of the carbon-fiber shell and wound with the glass-fiber. Though this system increases the dimension of the tank, its more effective. Fiberglass-reinforced external protective layer. Carbon fiber is a kind of material perfect for the fiber-reinforced layer. Normally, the wall of the fiber-reinforced layer is too thin to have enough stiffness. Fiberglass-reinforced external protective layer is introduced to supply extensive protection and add the stiffness of the tank. With the increase of wall thickness, the stability of the tanks cross section is improved. Furthermore, by increasing the thickness, the effect of damage to a tanks outer layer is lesser because the ratio of damage layers to undamaged layers is decreased under the same shock [13]. The damage tolerance is enhanced. It needs the fiberglass layer to provide more strength, improve damage tolerance of the tank and protect the internal layers as the sacrificial layer. The use of fiberglass is high cost effective compared with simply adding more carbon fiber to the wall. The winding process of the fiberglass layer is the same as the carbon fiber layer. But it shall not be included in the determination of the required wall thickness. 3.2. Design The theories of mechanics of composite materials such as the netting theory, the laminated plate theory can be used. Finite element analysis and other numerical methods are used to evaluate tank design. The netting theory assumes that resin carries no load. This could be a reasonable assumption of the actual condition in filament-wound composites. Other element will not work on it. According to this theory,

the hoop strength and the longitudinal strength of the fiber and the thickness of the laminate could be calculated. This design method is based on prototype testing. A prototype is designed and manufactured identically to a purchased tank but only can be used for testing purpose. The parameter of the laminate should be amended according to the experimental findings. The experimental result could be effected by the dimension of the prototype and fabrication processing [14]. In the application of the laminate theory, certain assumptions are made. Interlaminar or transverse shear is not addressed. Laminate stress resultants and moment resultants are taken as an average of ply stresses across the thickness of the laminate. The laminate is assumed to consist of perfectly bonded lamina, i.e. displacements are continuous and no lamina slips relative to another. This theory requires that four elastic constants (longitudinal and transverse tensile modulus, in-plane shear modulus, and Poissons ratio) and five strength constants (longitudinal and transverse tensile strength, longitudinal and transverse compressive strength, and in-plane shear strength) for the lamina be determined through the test. The test coupon should represent the orthotropic lamina under consideration. The laminate theory is a mathematical treatment of the mechanics governing the behavior of unidirectional orthotropic lamina and the interrelation between multiple laminas. The winding pattern shall be considered as a laminate. Laminate theory shall be used to determine the in-plane and flexural modulus components that define the stress-strain and moment-curvature relationships and the effective engineering constants of the laminate. At the same time, it can examine the strength of a laminate based on the strain state of individual lamina reacting to impose moment and stress resultants. Finite element method could be an effective tool for stress analysis. Applying commercial finite element analysis software such as NASTRAN, the two-dimension axisymmetrical model of the tank is constructed with considerable effort towards the accurate representation of the geometries and material properties. The stress, especially in the transition of the cylinder and the head could be calculated [15]. Moreover, the fatigue life of the tank can be evaluated. After the initial design, the method of parametric unitary optimization of the tank is proposed. An optimization strategy for such the weight as the tank is also proposed. 3.3. Testing Hydrogen is a kind of inflammable gas. It is very important to ensure the safety and the reliability of the high-pressure hydrogen storage tanks. The tank must be tested through multiple independence methods. The programs generally follow the tests developed for

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CNG tanks. They include burst tests, fatigue, extreme temperature, hydrogen cycling, bonfire, severe drop impact test, flaw tolerance and gunfire penetration, accelerated stress, permeation, material tests, etc.

lems. So the use of the hydrogen energy should be a desirable way to solve the problems. As an important element of the hydrogen energy technology, the lightweight high-pressure storage tanks should be developed through absorbing the existing experiences and theories. New materials and structures are the key to improve the performance of hydrogen storage tanks which deserve further research efforts. Acknowledgement

(a)

This study is sponsored by 863 Hi-Tech Research and Development Program of China, Project No.2002AA515020.

(b) Fig. 3. Cylinders vs. a conformable tank in a rectangular envelope.

References
[1] Chang QY, Chen QS. Hydrogen Storage in Carbon-based Nanomaterials. In: Proceedings of The International Hydrogen Energy Forum, Beijing, 2004, p.186-191. [2] Neel Sirosh. Hydrogen Composite Tank Program. The 2002 U.S.DOE Hydrogen Progm Review Meeting. Colorado:2002. [3] Lincoln Composites demos 10000 psi. hydrogen tank. Fuel Cells Bulletin 2002,(7): 6. [4] Cheng RX. The design of the composite natural gas storage tanks. Material of Spatial Technology 2001; (6): 5-57. [5] Varga L, Nagy A, Kovcs A. Design of CNG tank made of Aluminum and reinforced plastic. Composites 1995; 26(6): 457-463. [6] Darton Greist, Irving EF. Thermoplastic liner for and method of overwrapping high-pressure tanks, U.S. : 5499739, 3. 19, 1996.. [7] Liu YC, Dong YD, Wang BQ. The study of the composite CNG tanks (II). Fiber Composite Materials 2000; 49(4): 49-50. [8] Zhao JX. The development of carbon fiber and the composite material of the Toray. Material of Spatial Technology 2000; (6): 53-56. [9] Zhao JX. Exploiture of the carbon fiber and the composite material at home and abroad. Utility of Engineering Plastic 2001; 29(1): 46-48. [10] Luo YF. Five markets of the composite material in future. Contemporary Chemical Engineer 1996; (12): 40-42. [11] Dale BT, John JW. Development of Integrated Storage System for A Mid-size Automobile. International Gas Conference and Exhibition. Cologne, 1998. [12] Paul FD, Ayodeji JA, Alvin C. Pressure tank with damage mitigating system, U.S. : 5476189, 12. 19, 1995. [13] Donald B, Norman N, Him KL. High-pressure Composite Accumulator Bottles. Second International Conference on Composite Materials of Offshore Operations (CMOO-2), Houston: 1997. [14] Liu XL, Wang BQ. The introduce of the composite material. Beijing: China Construction Publication, 1984. [15] Frank CS. A filament-wound structure technology overview. Materials Chemistry and Physics 2001; 51(3): 273-283. [16] Michael DB, Richard K, Mark JW. Composite conformable pressure tank, U.S. : 6095367, 8. 1, 2000.

4. Trend of development Now, the high-pressure hydrogen storage tanks are developing toward lightweight and high-pressure. Light, efficient, cost-effective and reliable hydrogen storage systems and the relative standards are the goals. The increase of the operating pressure is not the final aim. The storage mass efficiency of the Quantums 35 MPa tank increased from 11.3% (wt) to 13.36% (wt). It illuminates that the storage mass efficiency could be improved even if the operating pressure is not very high. With the increase of pressure, the requirement of the material and the structure, the cost and the damage of the accident will be improved. Because the energy density of the hydrogen is significantly less, the large volume of hydrogen gas is required. So the multi-tank structure is required. The cylinder tank is near-optimum pressure tank structure, but the cylinder geometry of these tanks does not lend the efficient usage of the normal rectangular envelope as shown in Fig. 3(a). The transportation cost is increased. The problem is addressed through the development of the conformable pressure tank abroad as shown in Fig. 3(b) [16]. This structure consists of two end tanks and multiple interior tanks. The internal volume of the conformable tank at least gets 70% of a rectangular envelop volume. Its larger than the internal volume of the multiple cylinders in the same envelope. Currently, an international standard is needed to clear the technical barrier between the countries. The intercommunication should be enhanced to accelerate the development of this technology. In China, the per capita energy resource is very limited. There are serious environment and energy prob-