Hydrogen storage describes the methods for storing H2 for subsequent use. The methods span many approaches, including high pressures, cryogenics, and chemical compounds that reversibly release H2 upon heating. Hydrogen storage is a topical goal in the development of a hydrogen economy.
Most research into hydrogen storage is focused on storing hydrogen as a lightweight, compact energy carrier for mobile applications.
Liquid hydrogen or slush hydrogen may be used, as in the Space Shuttle. However liquid hydrogen requires cryogenic storage and boils around 20.268 K (–252.882 °C or -423.188 °F). Hence, its liquefaction imposes a large energy loss (as energy is needed to cool it down to that temperature). The tanks must also be well insulated to prevent boil off. Insulation by design for liquid hydrogen tanks is adding costs for this method. Liquid hydrogen has less energy density by volume than hydrocarbon fuels such as gasoline by approximately a factor of four. This highlights the density problem for pure hydrogen: there is actually about 64% more hydrogen in a liter of gasoline (116 grams hydrogen) than there is in a liter of pure liquid hydrogen (71 grams hydrogen). The carbon in the gasoline also contributes to the energy of combustion.
Compressed hydrogen, in comparison, is quite different to store. Hydrogen gas has good energy density by weight, but poor energy density by volume versus hydrocarbons, hence it requires a larger tank to store. A large hydrogen tank will be heavier than the small hydrocarbon tank used to store the same amount of energy, all other factors remaining equal. Increasing gas pressure would improve the energy density by volume, making for smaller, but not lighter container tanks (see hydrogen tank). Compressed hydrogen will require 2.1% of the energy content[1] to power the compressor. Higher compression without energy recovery will mean more energy lost to the compression step. Compressed hydrogen storage can exhibit very low permeation.[2]
Some researchers have investigated underground hydrogen storage to provide grid energy storage for intermittent energy sources, like wind power.
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Targets were set by the FreedomCAR Partnership in January 2002 between the United States Council for Automotive Research (USCAR) and U.S. DOE (Targets assume a 5-kg H2 storage system). The 2005 targets were not reached in 2005.[3] The targets were revised in 2009 to reflect new data on system efficiencies obtained from fleets of test cars.[4] The ultimate goal for volumetric storage is still above the theoretical density of liquid hydrogen.[5]
It is important to note that these targets are for the hydrogen storage system, not the hydrogen storage material. System densities are often around half those of the working material, thus while a material may store 6 wt% H2, a working system using that material may only achieve 3 wt% when the weight of tanks, temperature and pressure control equipment, etc., is considered.
In 2010, only two storage technologies were identified as being susceptible to meet DOE targets: MOF-177 exceeds 2010 target for volumetric capacity, while cryo-compressed H2 exceeds more restrictive 2015 targets for both gravimetric and volumetric capacity (see slide 6 in [6]).
Compressed hydrogen is the gaseous state of the element hydrogen which is kept under pressure. Compressed hydrogen in hydrogen tanks at 350 bar (5,000 psi) and 700 bar (10,000 psi) is used for in hydrogen vehicles. Car manufacturers have been developing this solution, such as Honda[7] or Nissan.[8]
BMW has been working on liquid tank for cars, producing for example the BMW Hydrogen 7.
Hydrogen storage technologies can be divided into physical storage, where hydrogen molecules are stored (including pure hydrogen storage via compression and liquefication), and chemical storage, where hydrides are stored.
Metal hydrides, such as MgH2, NaAlH4, LiAlH4, LiH, LaNi5H6, and TiFeH2, with varying degrees of efficiency, can be used as a storage medium for hydrogen, often reversibly.[9] Some are easy-to-fuel liquids at ambient temperature and pressure, others are solids which could be turned into pellets. These materials have good energy density by volume, although their energy density by weight is often worse than the leading hydrocarbon fuels.
Most metal hydrides bind with hydrogen very strongly. As a result high temperatures around 120 °C (248 °F) - 200 °C (392 °F) are required to release their hydrogen content. This energy cost can be reduced by using alloys which consists of a strong hydride former and a weak one such as in LiNH2, NaBH4 and LiBH4. These are able to form weaker bonds, thereby requiring less input to release stored hydrogen. However if the interaction is too weak, the pressure needed for rehydriding is high, thereby eliminating any energy savings. The target for onboard hydrogen fuel systems is roughly <100 °C for release and <700 bar for recharge (20-60 kJ/mol H2 ).[10][11]
Currently the only hydrides which are capable of achieving the 9 wt. % gravimetric goal for 2015 (see chart above) are limited to lithium, boron and aluminum based compounds; at least one of the first-row elements or Al must be added. Research is being done to determine new compounds which can be used to meet these requirements.
Proposed hydrides for use in a hydrogen economy include simple hydrides of magnesium[12] or transition metals and complex metal hydrides, typically containing sodium, lithium, or calcium and aluminium or boron. Hydrides chosen for storage applications provide low reactivity (high safety) and high hydrogen storage densities. Leading candidates are Lithium hydride, sodium borohydride, lithium aluminium hydride and ammonia borane. A French company McPhy Energy [5] is developing the first industrial product, based on Magnesium Hydrate, already sold to some major clients such as Iwatani and ENEL.
New Scientist [13] stated that Arizona State University is investigating using a borohydride solution to store hydrogen, which is released when the solution flows over a catalyst made of ruthenium.
Carbohydrates (Polymeric C6H10O5) releases H2 in an bioreformer mediated by the enzyme cocktail—cell-free synthetic pathway biotransformation. Carbohydrate provides high hydrogen storage densities as a liquid with mild pressurization and cryogenic constraints: It can also be stored as a solid power. Carbohydrate is the most abundant renewable bioresource in the world.
In May 2007 biochemical engineers from the Virginia Polytechnic Institute and State University and biologists and chemists from the Oak Ridge National Laboratory announced a method of producing high-yield pure hydrogen from starch and water.[14] In 2009, they demonstrated to produce nearly 12 moles of hydrogen per glucose unit from cellulosic materials and water.[15] Thanks to complete conversion and modest reaction conditions, they propose to use carbohydrate as a high energy density hydrogen carrier with a density of 14.8 wt %.[16]
An alternative to hydrides is to use regular hydrocarbon fuels as the hydrogen carrier. Then a small hydrogen reformer would extract the hydrogen as needed by the fuel cell. However, these reformers are slow to react to changes in demand and add a large incremental cost to the vehicle powertrain.
Direct methanol fuel cells do not require a reformer, but provide a lower energy density compared to conventional fuel cells, although this could be counter balanced with the much better energy densities of ethanol and methanol over hydrogen. Alcohol fuel is a renewable resource.
Solid-oxide fuel cells can operate on light hydrocarbons such as propane and methane without a reformer, or can run on higher hydrocarbons with only partial reforming, but the high temperature and slow startup time of these fuel cells are problematic for automotive applications.
Ammonia (NH3) releases H2 in an appropriate catalytic reformer. Ammonia provides high hydrogen storage densities as a liquid with mild pressurization and cryogenic constraints: It can also be stored as a liquid at room temperature and pressure when mixed with water. Ammonia is the second most commonly produced chemical in the world and a large infrastructure for making, transporting, and distributing ammonia exists. Ammonia can be reformed to produce hydrogen with no harmful waste, or can mix with existing fuels and under the right conditions burn efficiently. Pure ammonia burns poorly at the atmospheric pressures found in natural gas fired water heaters and stoves. Under compression in an automobile engine it is a suitable fuel for slightly modified gasoline engines. Ammonia is a toxic gas at normal temperature and pressure and has a potent odor.[17]
In September 2005 chemists from the Technical University of Denmark announced a method of storing hydrogen in the form of ammonia saturated into a salt tablet. They claim it will be an inexpensive and safe storage method.[18]
Prior to 1980, several compounds were investigated for hydrogen storage including complex borohydrides, or aluminohydrides, and ammonium salts. These hydrides have an upper theoretical hydrogen yield limited to about 8.5% by weight. Amongst the compounds that contain only B, N, and H (both positive and negative ions), representative examples include: amine boranes, boron hydride ammoniates, hydrazine-borane complexes, and ammonium octahydrotriborates or tetrahydroborates. Of these, amine boranes (and especially ammonia borane) have been extensively investigated as hydrogen carriers. During the 1970s and 1980s, the U.S. Army and Navy funded efforts aimed at developing hydrogen/deuterium gas-generating compounds for use in the HF/DF and HCl chemical lasers, and gas dynamic lasers. Earlier hydrogen gas-generating formulations used amine boranes and their derivatives. Ignition of the amine borane(s) forms boron nitride (BN) and hydrogen gas. In addition to ammonia borane (H3BNH3), other gas-generators include diborane diammoniate, H2B(NH3)2BH4.
In 2006 researchers of EPFL, Switzerland, reported the use of formic acid as a hydrogen storage material.[19] Carbon monoxide free hydrogen has been generated in a very wide pressure range (1-600 bar). A homogeneous catalytic system based on water soluble ruthenium catalysts selectively decompose HCOOH into H2 and CO2 in aqueous solution.[20] This catalytic system overcomes the limitations of other catalysts (e.g. poor stability, limited catalytic lifetimes, formation of CO) for the decomposition of formic acid making it a viable hydrogen storage material.[21] And the co-product of this decomposition, carbon dioxide, can be used as hydrogen vector by hydrogenating it back to formic acid in a second step. The catalytic hydrogenation of CO2 has long been studied and efficient procedures have been developed.[22][23] Formic acid contains 53 g L−1 hydrogen at room temperature and atmospheric pressure. By weight, pure formic acid stores 4.3 wt% hydrogen. Pure formic acid is a liquid with a flash point 69 °C (cf. gasoline -40 °C, ethanol 13 °C). 85% formic acid is not inflammable.
In 2007 Dupont J. and others reported hydrogen-storage materials based on imidazolium ionic liquids. Simple alkyl(aryl)-3-methylimidazolium N-bis(trifluoromethanesulfonyl)imidate salts that possess very low vapour pressure, high density, and thermal stability and are not inflammable can add reversibly 6-12 hydrogen atoms in the presence of classical Pd/C or Ir0 nanoparticle catalysts and can be used as alternative materials for on-board hydrogen-storage devices. These salts can hold up to 30 g L−1 of hydrogen at atmospheric pressure.[24]
In 2006 researchers of University of Windsor reported on reversible hydrogen storage in a non-metal phosphonium borate frustrated Lewis pair[25][26][27]:
The phosphino-borane on the left accepts one equivalent of hydrogen at one atmosphere and 25 °C and expels it again by heating to 100 °C. The storage capacity is 0.25 wt% still rather below the 6 to 9 wt% required for practical use.
Research has proven that graphene can store hydrogen efficiently. After taking up hydrogen, the substance becomes graphane. After tests, conducted by dr André Geim at the University of Manchester, it was shown that not only can graphene store hydrogen easily, it can also release the hydrogen again, after heating to 450 °C.[28][29]
Cryo-compressed storage of hydrogen is the only technology that meets 2015 DOE targets for volumetric and gravimetric efficiency (see "CcH2" on slide 6 in [6]).
Furthermore, another study has shown that cryo-compressed exhibits interesting cost advantages : ownership cost ($ per mile) and storage system cost ($ per vehicle) are actually the lowest when compared to any other technology (see third row in slide 13 of [30]). For example, a cryo-compressed H2 system would cost $0.12 per mile (including cost of fuel and every associated other cost), while conventional gasoline vehicles cost between $0.05 and $0.07 per mile.
Alike liquid storage, cryo-compressed uses very cold H2 (20.3 K and slightly above) in order to reach a high energy density. However, the main difference is that, when the hydrogen would warm-up due to heat transfer with the environment ("boil off"), the tank is allowed to go to pressures much higher (up to 350 bars versus a couple of bars for liquid storage). As a consequence, it takes more time before the hydrogen has to vent, and in most driving situations, enough hydrogen is used by the car to keep the pressure well below the venting limit.
Consequently, it has been demonstrated that a high driving range could be achieved with a cryo-compressed tank : more than 650 miles (1,050 km) were driven with a full tank mounted on a H2 engine Prius.[31] Research is still on its way in order to study and demonstrate the full potential of the technology.[32]
As of 2010, the BMW Group has started a thorough component and system level validation of cryo-compressed vehicle storage on its way to a commercial product.[33]
Hydrogen carriers based on nanostructured carbon (such as carbon buckyballs and nanotubes) have been proposed. Despite initial claims of greater than 50 wt% hydrogen storage, it has generally come to be accepted that less than 1 wt% is practical.[34]
Metal-organic frameworks represent another class of synthetic porous materials that store hydrogen and energy at the molecular level. MOFs are highly crystalline inorganic-organic hybrid structures that contain metal clusters or ions (secondary building units) as nodes and organic ligands as linkers. When guest molecules (solvent) occupying the pores are removed during solvent exchange and heating under vacuum, porous structure of MOFs can be achieved without destabilizing the frame and hydrogen molecules will be adsorbed onto the surface of the pores by physisorption. Compared to traditional zeolites and porous carbon materials, MOFs have very high number of pores and surface area which allow higher hydrogen uptake in a given volume. Thus, research interests on hydrogen storage in MOFs have been growing since 2003 when the first MOF-based hydrogen storage was introduced. Since there are infinite geometric and chemical variations of MOFs based on different combinations of SBUs and linkers, many researches explore what combination will provide the maximum hydrogen uptake by varying materials of metal ions and linkers.
In 2006, chemists at UCLA and the University of Michigan have achieved hydrogen storage concentrations of up to 7.5 wt% in MOF-74 at a low temperature of 77K.[35][36] In 2009, researchers at University of Nottingham reached 10 wt% at 77 bar (1,117 psi) and 77 K with MOF NOTT-112.[37] Most articles about hydrogen storage in MOFs report hydrogen uptake capacity at a temperature of 77K and a pressure of 1 bar because such condition is commonly available and the binding energy between hydrogen and MOF is large compare to the thermal vibration energy which will allow high hydrogen uptake capacity. Varying several factors such as surface area, pore size, catenation, ligand structure, spillover, and sample purity can result different amount of hydrogen uptake in MOFs.
H2 caged in a clathrate hydrate was first reported in 2002, but requires very high pressures to be stable. In 2004, researchers from Delft University of Technology and Colorado School of Mines showed solid H2-containing hydrates could be formed at ambient temperature and 10s of bar by adding small amounts of promoting substances such as THF.[38] These clathrates have a theoretical maximum hydrogen densities of around 5 wt% and 40 kg/m3.
In 2006, a team of Korean researchers led by Professor Jisoon Ihm at Department of Physics and Astronomy of Seoul National University proposed a new material with the hydrogen storage efficiency of 7.6 percent based on first-principles electronic structure calculations for hydrogen binding to metal-decorated polymers of many different kinds. According to these researchers, hydrogen can be stored in a solid material at ambient temperatures and pressures by attaching a titanium atom to a polyacetylene. [6][7]
A team of Russian, Israeli and German scientists have collaboratively developed an innovative technology based on glass capillary arrays for the safe infusion, storage and controlled release of hydrogen in mobile applications [8][9]. The C.En [10] technology has achieved the US Department of Energy (DOE) 2010 targets for on-board hydrogen storage systems.[39]
Hollow glass microspheres (HGM) can be utilized for controlled storage and release of hydrogen.[40][41]
Keratine, a compound found in bird feathers, has been found to be useful to increase the interior surface (and thus the hydrogen storage capacity) of tanks. The research stated that the use of carbonized chicken feather fibres would result in far lower manufacturing costs than other common hydrogen tanks on the market. The research was conducted by Richard Wool and Erman Senoz.[42]
Unlike mobile applications, hydrogen density is not a huge problem for stationary applications. As for mobile applications, stationary applications can use established technology:
Underground hydrogen storage is the practice of hydrogen storage in underground caverns, salt domes and depleted oil and gas fields. Large quantities of gaseous hydrogen have been stored in underground caverns by ICI for many years without any difficulties.[43] The storage of large quantities of hydrogen underground can function as grid energy storage which is essential for the hydrogen economy.
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