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储氢方法。

Hydrogen storage methods.

作者信息

Züttel Andreas

机构信息

Physics Department, University of Fribourg, Pérolles, 1700 Fribourg, Switzerland.

出版信息

Naturwissenschaften. 2004 Apr;91(4):157-72. doi: 10.1007/s00114-004-0516-x. Epub 2004 Mar 17.

Abstract

Hydrogen exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly. There are two reasons why hydrogen is not the major fuel of today's energy consumption. First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water and hydrocarbons. This implies that we have to pay for the energy, which results in a difficult economic dilemma because ever since the industrial revolution we have become used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K (i.e. hydrogen is a gas at ambient temperature). For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is crucial. Hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with a large specific surface area (at T<100 K), (4) absorbed on interstitial sites in a host metal (at ambient pressure and temperature), (5) chemically bonded in covalent and ionic compounds (at ambient pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water. The most common storage systems are high-pressure gas cylinders with a maximum pressure of 20 MPa (200 bar). New lightweight composite cylinders have been developed which are able to withstand pressures up to 80 MPa (800 bar) and therefore the hydrogen gas can reach a volumetric density of 36 kg.m(-3), approximately half as much as in its liquid state. Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems. The volumetric density of liquid hydrogen is 70.8 kg.m(-3), and large volumes, where the thermal losses are small, can cause hydrogen to reach a system mass ratio close to one. The highest volumetric densities of hydrogen are found in metal hydrides. Many metals and alloys are capable of reversibly absorbing large amounts of hydrogen. Charging can be done using molecular hydrogen gas or hydrogen atoms from an electrolyte. The group one, two and three light metals (e.g. Li, Mg, B, Al) can combine with hydrogen to form a large variety of metal-hydrogen complexes. These are especially interesting because of their light weight and because of the number of hydrogen atoms per metal atom, which is two in many cases. Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal. Finally, the metal hydroxides can be thermally reduced to metals in a solar furnace. This paper reviews the various storage methods for hydrogen and highlights their potential for improvement and their physical limitations.

摘要

氢在所有化学燃料中具有最高的单位质量发热量。此外,氢是可再生且环境友好的。氢并非当今能源消耗的主要燃料,原因有两点。首先,氢只是一种能量载体。而且,尽管它是宇宙中最丰富的元素,但在地球上它仅以水和碳氢化合物的形式存在,因此必须进行生产。这意味着我们必须为能源付费,这就导致了一个艰难的经济困境,因为自工业革命以来,我们已习惯于免费消耗能源。氢作为能量载体的第二个难题是其33K的低临界温度(即氢在环境温度下是气体)。对于移动应用以及在许多情况下的固定应用而言,存储材料中氢的体积密度和重量密度至关重要。氢可以通过六种不同的方法和现象进行存储:(1)高压气瓶(高达800巴);(2)低温罐中的液态氢(在21K);(3)吸附在具有大比表面积的材料上的氢(在T<100K);(4)吸收在主体金属的间隙位置上(在环境压力和温度下);(5)共价和离子化合物中的化学键合(在环境压力下);或(6)通过活性金属(例如锂、钠、镁、铝、锌)与水的氧化反应。最常见的存储系统是最大压力为20MPa(200巴)的高压气瓶。已经开发出新型轻质复合气瓶,其能够承受高达80MPa(800巴)的压力,因此氢气的体积密度可以达到36kg·m⁻³,大约是液态氢密度的一半。液态氢存储在21.2K和环境压力下的低温罐中。由于氢的临界温度较低(33K),液态氢只能存储在开放系统中。液态氢的体积密度为70.8kg·m⁻³,在热损失较小的大体积存储中,氢气可以达到接近1的系统质量比。金属氢化物中氢的体积密度最高。许多金属和合金能够可逆地吸收大量氢。充电可以使用分子氢气或来自电解质的氢原子来完成。第一族、第二族和第三族轻金属(例如锂、镁、硼、铝)可以与氢结合形成多种金属 - 氢配合物。这些特别有趣,因为它们重量轻,并且在许多情况下每个金属原子的氢原子数为两个。氢也可以间接存储在活性金属如锂、钠、铝或锌中。这些金属很容易与水反应生成相应的氢氧化物,并从水中释放出氢。由于水是氢与氧气或空气燃烧的产物,它可以在闭环中循环并与金属反应。最后,金属氢氧化物可以在太阳能炉中热还原为金属。本文综述了氢的各种存储方法,并强调了它们改进的潜力及其物理局限性。

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