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Wednesday, December 1, 2021

Hydrogen storage

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Hydrogen_storage

Hydrogen storage is a term used for any of several methods for storing hydrogen for later use. These methods encompass mechanical approaches such as high pressures and low temperatures, or chemical compounds that release H₂ upon demand. While large amounts of hydrogen are produced, it is mostly consumed at the site of production, notably for the synthesis of ammonia. For many years hydrogen has been stored as compressed gas or cryogenic liquid, and transported as such in cylinders, tubes, and cryogenic tanks for use in industry or as propellant in space programs. Interest in using hydrogen for on-board storage of energy in zero-emissions vehicles is motivating the development of new methods of storage, more adapted to this new application. The overarching challenge is the very low boiling point of H₂: it boils around 20.268 K (−252.882 °C or −423.188 °F). Achieving such low temperatures requires significant energy.

Established technologies

Net storage density of hydrogen

Compressed hydrogen

Compressed hydrogen is a storage form whereby hydrogen gas is kept under pressures to increase the storage density. Compressed hydrogen in hydrogen tanks at 350 bar (5,000 psi) and 700 bar (10,000 psi) is used for hydrogen tank systems in vehicles, based on type IV carbon-composite technology. Car manufacturers have been developing this solution, such as Honda or Nissan.

Liquefied hydrogen

Liquid hydrogen tanks for cars, producing for example the BMW Hydrogen 7. Japan has a liquid hydrogen (LH2) storage site in Kobe port. Hydrogen is liquefied by reducing its temperature to −253 °C, similar to liquefied natural gas (LNG) which is stored at −162 °C. A potential efficiency loss of only 12.79% can be achieved, or 4.26 kW⋅h/kg out of 33.3 kW⋅h/kg.

Chemical storage

Hydrogen gravimetric capacity of proposed storage materials for hydrogen fuel as a function of hydrogen release temperature. The targets have since been lowered.

Chemical storage could offer high storage performance due to the high storage densities. For example, supercritical hydrogen at 30 °C and 500 bar only has a density of 15.0 mol/L while methanol has a density of 49.5 mol H₂/L methanol and saturated dimethyl ether at 30 °C and 7 bar has a density of 42.1 mol H₂/L dimethyl ether.

Regeneration of storage material is problematic. A large number of chemical storage systems have been investigated. H2 release can be induced by hydrolysis reactions or catalyzed dehydrogenation reactions. Illustrative storage compounds are hydrocarbons, boron hydrides, ammonia, and alane etc. A most promising chemical approach is electrochemical hydrogen storage, as the release of hydrogen can be controlled by the applied electricity. Most of the materials listed below can be directly used for electrochemical hydrogen storage.

As shown before, nanomaterials offer advantage for hydrogen storage systems. Nanomaterials offer an alternative that overcomes the two major barriers of bulk materials, rate of sorption and release temperature.

Enhancement of sorption kinetics and storage capacity can be improved through nanomaterial-based catalyst doping, as shown in the work of the Clean Energy Research Center in the University of South Florida. This research group studied LiBH₄ doped with nickel nanoparticles and analyzed the weight loss and release temperature of the different species. They observed that an increasing amount of nanocatalyst lowers the release temperature by approximately 20 °C and increases the weight loss of the material by 2-3%. The optimum amount of Ni particles was found to be 3 mol%, for which the temperature was within the limits established (around 100 °C) and the weight loss was notably greater than the undoped species.

The rate of hydrogen sorption improves at the nanoscale due to the short diffusion distance in comparison to bulk materials. They also have favorable surface-area-to-volume ratio.

The release temperature of a material is defined as the temperature at which the desorption process begins. The energy or temperature to induce release affects the cost of any chemical storage strategy. If the hydrogen is bound too weakly, the pressure needed for regeneration is high, thereby cancelling 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). A modified van ’t Hoff equation, relates temperature and partial pressure of hydrogen during the desorption process. The modifications to the standard equation are related to size effects at the nanoscale.

${\displaystyle ln(p_{\mathrm {H_{\mathrm {2} }} })={\frac {\Delta H(r)}{RT}}+{\frac {3V_{\mathrm {m} }\gamma }{rRT}}+{\frac {\Delta S(r)}{R}}}$

Where $p H 2$ is the partial pressure of hydrogen, $Δ H$ is the enthalpy of the sorption process (exothermic), $Δ S$ is the change in entropy, $R$ is the ideal gas constant, T is the temperature in Kelvin, $V m$ is the molar volume of the metal, $r$ is the radius of the nanoparticle and $γ$ is the surface free energy of the particle.

From the above relation we see that the enthalpy and entropy change of desorption processes depend on the radius of the nanoparticle. Moreover, a new term is included that takes into account the specific surface area of the particle and it can be mathematically proven that a decrease in particle radius leads to a decrease in the release temperature for a given partial pressure.

Hydrogenation of CO₂

The CO₂ emission is causing an unclouded carbon cycle. The climate change and related issue requires immediate attention. Current approach to reduce CO₂ includes capturing and storing from facilities across the world. However, storage posts technical and economic barriers preventing global scale application.To utilize CO₂ at the point source, CO₂ hydrogenation is a realistic and practical approach. Conventional hydrogenation reduces saturated organic compounds by addition of H₂. One pathway of CO₂ hydrogenation is CO₂ to methanol pathway. Methanol can be used to produce long chain hydrocarbons. Some barriers of CO₂ hydrogenation includes purification of captured CO₂, H₂ source from splitting water and energy inputs for hydrogenation. To overcome these barriers, we can further develop green H2 technology and encourage catalyst research at industrial and academic level. For industrial applications, CO₂ is often converted to methanol. Till now, much progress has been made for CO₂ to C1 molecules. However, CO₂ to high value molecules still face many roadblocks and the future of CO₂ hydrogenation depends on the advancement of catalytic technologies.

Metal hydrides

Metal hydride hydrogen storage

Metal hydrides, such as MgH₂, NaAlH₄, LiAlH₄, LiH, LaNi₅H₆, TiFeH₂, ammonia borane, and palladium hydride represent sources of stored hydrogen. Again the persistent problems are the % weight of H2 that they carry and the reversibility of the storage process. Some are easy-to-fuel liquids at ambient temperature and pressure, whereas others are solids which could be turned into pellets. These materials have good energy density, although their specific energy is often worse than the leading hydrocarbon fuels.

LiNH₂, LiBH₄, and NaBH₄.

An alternative method for lowering dissociation temperatures is doping with activators. This strategy has been used for aluminium hydride, but the complex synthesis makes the approach unattractive.

Proposed hydrides for use in a hydrogen economy include simple hydrides of magnesium 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 is developing the first industrial product, based on magnesium hydride, already sold to some major clients such as Iwatani and ENEL.

Reversible hydrogen storage is exhibited by frustrated Lewis pair, which produces a borohydride.

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%.

Aluminium

Hydrogen can be produced using aluminium by reacting it with water. To react with water, however, aluminium must be stripped of its natural oxide layer, a process which requires pulverization, chemical reactions with caustic substances, or alloys. The byproduct of the reaction to create hydrogen is aluminum oxide, which can be recycled back into aluminium with the Hall–Héroult process, making the reaction theoretically renewable. However, this requires electrolysis, which consumes a large amount of energy

Magnesium

Mg-based hydrogen storage materials can be generally fell into three categories, i.e., pure Mg, Mg-based alloys, and Mg-based composites. Particularly, more than 300 sorts of Mg-based hydrogen storage alloys have been receiving extensive attention because of the relatively better overall performance. Nonetheless, the inferior hydrogen absorption/desorption kinetics rooting in the overly undue thermodynamic stability of metal hydride make the Mg-based hydrogen storage alloys currently not appropriate for the real applications, and therefore, massive attempts have been dedicated to overcoming these shortages. Some sample preparation methods, such as smelting, powder sintering, diffusion, mechanical alloying, hydriding combustion synthesis method, surface treatment, and heat treatment, etc., have been broadly employed for altering the dynamic performance and cycle life of Mg-based hydrogen storage alloys. Besides, some intrinsic modification strategies, including alloying, nanostructuring, doping by catalytic additives, and acquiring nanocomposites with other hydrides, etc., have been mainly explored for intrinsically boosting the performance of Mg-based hydrogen storage alloys.

Of the primary hydrogen storage alloys progressed formerly, Mg and Mg-based hydrogen storage materials are believed to provide the remarkable possibility of the practical application, on account of the advantages as following: 1) the resource of Mg is plentiful and economical. Mg element exists abundantly and accounts for ~2.35% of the earth’s crust with the rank ofthe eighth; 2) low density ofmerely 1.74 g cm-3; 3) superior hydrogen storage capacity. The theoretical hydrogen storage amounts of the pure Mg is 7.6 wt % (weight percent), and the Mg2Ni is 3.6 wt%, respectively.

Alanates Based-Systems

Sodium Alanate(NaAlH4) is a complex hydride for H2 storage.The crystal structure was first determined through a single crystal X-ray diffracrion study in 1979. The atomic structure consisted of isolated [AlH4]⁻ tetrahedra in which the Na atoms are surrounded by eight [AlH4]⁻ tetrahedra in a distorted square. Hydrogen release from NaAlH4 is known since the 1950's. In 1997, Bogdanovic discovered that Tio2 doping of materials makes the process reversible at modest temperature and pressure. TiO2-doped materials are reversible in hydrogen storage, NaAlH4 is currently the state of the art reversible solid state hydrogen storage material which can be used in low temperature and has 5.6 wt.% hydrogen contained. The chemical reaction is, 3NaAlH4 ← catalyst → Na3AlH6 + 2Al + 3H2 ← catalyst → 3NaH + Al + 3/2H2. The heat required to change from NaAlH4 to Na3AlH6 is 37 kJ/mol. The heat required to change from Na3AlH6 to NaH is 47 kJ/mol. In principle, the first step of NaAlH4 releases 3.7 wt.% hydrogen at about 190 °C and the second step releases 1.8 wt.% hydrogen at about 225 °C upon heating. Further dehydrogenation of NaH occurs only at temperature higher than 400 °C. This temperature is too high for technical applications, therefore, can not be used in a fuel cell vehicle.

Lithium alanate (LiAlH4) was synthesized for the first time in 1947 by dissolution of lithium hydride in an ether solution of aluminium chloride. LiAlH4 has a theoretical gravimetric capacity of 10.5 wt %H2 and dehydrogenates in the following three steps: 3LiAlH4 ↔ Li3AlH6 + 3H2 + 2Al (423–448 K; 5.3 wt %H2; ∆H = −10 kJ·mol−1 H2); Li3AlH6 ↔ 3LiH + Al + 3/2H2 (453–493 K; 2.6 wt %H2; ∆H = 25 kJ·mol−1 H2); 3LiH + 3Al ↔ 3LiAl + 3/2H2 (>673 K; 2.6 wt %H2; ∆H = 140 kJ·mol−1 H2). The first two steps lead to a total amount of hydrogen released equal to 7.9 wt %, which could be attractive for practical applications, but the working temperatures and the desorption kinetics are still far from the practical targets. Several strategies have been applied in the last few years to overcome these limits, such as ball-milling and catalysts additions.

Potassium Alanate (KAlH4) was first prepared by Ashby et al. by one-step synthesis in toluene, tetrahydrofuran, and diglyme. Concerning the hydrogen absorption and desorption properties, this alanate was only scarcely studied. Morioka et al., by temperature programmed desorption (TPD) analyses, proposed the following dehydrogenation mechanism: 3KAlH4 →K3AlH6 + 2Al + 3H2 (573 K, ∆H = 55 kJ·mol−1 H2; 2.9 wt %H2), K3AlH6 → 3KH + Al + 3/2H2 (613 K, ∆H = 70 kJ·mol−1 H2; 1.4 wt %H2), 3KH → 3K + 3/2H2 (703 K, 1.4 wt %H2). These reactions were demonstrated reversible without catalysts addition at relatively low hydrogen pressure and temperatures. The addition of TiCl3 was found to decrease the working temperature of the first dehydrogenation step of 50 K, but no variations were recorded for the last two reaction steps.

Organic hydrogen carriers

Reversible hydrogenation of N-ethylcarbazole.

Unsaturated organic compounds can store huge amounts of hydrogen. These Liquid Organic Hydrogen Carriers (LOHC) are hydrogenated for storage and dehydrogenated again when the energy/hydrogen is needed. Using LOHCs relatively high gravimetric storage densities can be reached (about 6 wt-%) and the overall energy efficiency is higher than for other chemical storage options such as producing methane from the hydrogen. Both hydrogenation and dehydrogenation of LOHCs requires catalysts. It was demonstrated that replacing hydrocarbons by hetero-atoms, like N, O etc. improves reversible de/hydrogenation properties.

Cycloalkanes

Research on LOHC was concentrated on cycloalkanes at an early stage, with its relatively high hydrogen capacity (6-8 wt %) and production of CO_x-free hydrogen. Heterocyclic aromatic compounds (or N-Heterocycles) are also appropriate for this task. A compound featuring in LOHC research is N-Ethylcarbazole^[de] (NEC) but many others do exist. Dibenzyltoluene, which is already used as a heat transfer fluid in industry, was identified as potential LOHC. With a wide liquid range between -39 °C (melting point) and 390 °C (boiling point) and a hydrogen storage density of 6.2 wt% dibenzyltoluene is ideally suited as LOHC material. Formic acid has been suggested as a promising hydrogen storage material with a 4.4wt% hydrogen capacity.

Cycloalkanes reported as LOHC include cyclohexane, methyl-cyclohexane and decalin. The dehydrogenation of cycloalkanes is highly endothermic (63-69 kJ/mol H₂), which means this process requires high temperature. Dehydrogenation of decalin is the most thermodynamically favored among the three cycloalkanes, and methyl-cyclohexane is second because of the presence of the methyl group. Research on catalyst development for dehydrogenation of cycloalkanes has been carried out for decades. Nickel (Ni), Molybdenum (Mo) and Platinum (Pt) based catalysts are highly investigated for dehydrogenation. However, coking is still a big challenge for catalyst's long-term stability.

The addition of second metal such as W,Ir, Re, Rh and Pd etc. and/or promoter (such as Ca) and selection of suitable support (such as CNF and Al2O3) are effective against coking. For cyclohexane, there are two dehydrogenation mechanisms, the sextet mechanism and the doublet mechanism. The difference between the two mechanisms lies in whether they are intermediate products during dehydrogenation. In the sextet mechanism, cyclohexane overlies on the catalyst surface and undergoes dehydrogenation directly to benxzene. In contrast, in the double mechanism, hydrogen will be released step by step because of the C=C double bound.

N-Heterocycles

The temperature required for hydrogenation and dehydrogenation drops significantly for heterocycles vs simple carbocycles. Among all the N-heterocycles, the saturated-unsaturated pair of dodecahydro-N-ethylcarbazole (12H-NEC) and NEC has been considered as a promising candidate for hydrogen storage with a fairly large hydrogen content (5.8wt%). The figure on the top right shows dehydrogenation and hydrogenation of the 12H-NEC and NEC pair. The standard catalyst for NEC to 12H-NEC is Ru and Rh based. The selectivity of hydrogenation can reach 97% at 7 MPa and 130 °C-150 °C. Although N-Heterocyles can optimize the unfavorable thermodynamic properties of cycloalkanes, a lot of issues remain unsolved, such as high cost, high toxicity and kinetic barriers etc.

The imidazolium ionic liquids such alkyl(aryl)-3-methylimidazolium N-bis(trifluoromethanesulfonyl)imidate salts can reversibly add 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.

Formic acid

Formic acid is a highly effective hydrogen storage material, although its H2 density is low. 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. 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. 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. 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 flammable.

Carbohydrates

Carbohydrates (polymeric C₆H₁₀O₅) release H₂ in a 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 powder. Carbohydrate is the most abundant renewable bioresource in the world.

Polysaccharides(C₆H₁₀O₅) has a reaction of C₆H₁₀O₅ + 7H2O → 12H2 +6CO2. As a result, hydrogen storage density in polysaccharides is 14.8 mass%. Carbonhydrates are much less costly than other carriers. Hydrogen generation from carbonhydrates can be implemented at mild conditions of 30~80 °C and about 1 atm, the process does not need any costly high pressure reactor, and high purity hydrogen mixed with CO2 is generated, making extra product purification unnecessary. Under the mild reaction conditions, separation of gaseous products and aqueous reaction is easy and nearly no cost. Moreover, renewable corbonhydrates are nearly inflammable and not toxic at all. Carbonhydrates may be an appealing hydrogen carrier.

Compared to other hydrogen carriers, carbonhydrates are very appealing due to their low cost, renewable source, high purity hydrogen generated, and so on.

Ammonia and related compounds

Ammonia

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. Since there is no carbon in ammonia, no carbon by-products are produced; thereby making this possibility a "carbon neutral" option for the future. 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 suitable alternative fuel because it has 18.6 MJ/kg energy density at NTP and carbon-free combustion byproducts.

Ammonia has several challenges to widespread adaption as a hydrogen storage material. Ammonia is a toxic gas with a potent odor at standard temperature and pressure. Additionally, advances in the efficiency and scalability of ammonia decomposition are needed for commercial viability, as fuel cell membranes are highly sensitive to residual ammonia and current decomposition techniques have low yield rates. A variety of transition metals can be used to catalyze the ammonia decomposition reaction, the most effective being ruthenium. This catalysis works through chemisorption, where the adsorption energy of N₂ is less than the reaction energy of dissociation. Hydrogen purification can be achieved in several ways. Hydrogen can be separated from unreacted ammonia using a permeable, hydrogen-selective membrane. It can also be purified through the adsorption of ammonia, which can be selectively trapped due to its polarity.

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.

positive and negative attributes of Ammonia ·pro's:High theoretical energy density, Wide spread availability, Large scale commercial production, Benign decomposition pathway to H2 and N2 ·con's:Toxicity, Corrosive, High decomposition temperature leading to efficiency loss

Hydrazine

Hydrazine breaks down in the cell to form nitrogen and hydrogen Silicon hydrides and germanium hydrides are also candidates of hydrogen storage materials, as they can subject to energetically favored reaction to form covalently bonded dimers with loss of a hydrogen molecule.

Chemical hydrides

Chemical hydride is a irreversible hydrogen storage material. The reaction of hydrogen releasing from chemical hydrides are usually exothermic, which makes regeneration of the fuel energy-intensive. NaBH₄ + 2H₂O → NaBO₂ + 4H₂ + 300 kJ. The chemical reaction gives potential for high density storage, but current systems produce much lower effective density. The NaBH4 has a theoritical effective density of 10.8 wt.%, however there is only 1.1 wt.% of effective density in reality. Examples of chemical hydride reactions: NaBH₄ (20~35% solution, stabilized with 1~3% NaOH) + 2H₂O (from fuel cell exhaust) → NaBO₂ (Borax in NaOH) + 4H2. 2LiH + 2H₂O → 2LiOH + 2H₂.

A leading chemical hydride is NH₃BH₃, which is a waxy solid at room temperature with a melting point of 90 °C. Hydrogen will be released from NH₃BH₃ around 90 °C because of thermal decomposition. NH₃BH₃ is a promising material for hydrogen storing because it has one of the highest theoretical hydrogen weight percentages at 19.6% and also the highest hydrogen volume density at 151 kg H₂ per volume. Hydrogen release from NH₃BH₃ occurs stepwise, where the onset temperature for the first equivalent is 90 °C, the temperature for second equivalent is 150 °C. The remaining hydrogen will be released at the temperature higher than 150 °C.

Amine boranes

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.

Physical storage

In this case hydrogen remains in physical forms, i.e., as gas, supercritical fluid, adsorbate, or molecular inclusions. Theoretical limitations and experimental results are considered concerning the volumetric and gravimetric capacity of glass microvessels, microporous, and nanoporous media, as well as safety and refilling-time demands.

Porous or layered carbon

Activated carbons are highly porous amorphous carbon materials with high apparent surface area. Hydrogen physisorption can be increased in these materials by increasing the apparent surface area and optimizing pore diameter to around 7 Å. These materials are of particular interest due to the fact that they can be made from waste materials, such as cigarette butts which have shown great potential as precursor materials for high-capacity hydrogen storage materials.

Graphene can store hydrogen efficiently. The H₂ adds to the double bonds giving graphane. The hydrogen is released upon heating to 450 °C.

Carbon nanotubes

Hydrogen carriers based on nanostructured carbon (such as carbon buckyballs and nanotubes) have been proposed. However, hydrogen content amounts up to ≈3.0-7.0 wt% at 77K which is far from the value set by US Department of Energy (6 wt% at nearly ambient conditions).

To realize carbon materials as effective hydrogen storage technologies, carbon nanotubes (CNTs) have been doped with MgH₂. The metal hydride has proven to have a theoretical storage capacity (7.6 wt%) that fulfills the United States Department of Energy requirement of 6 wt%, but has limited practical applications due to its high release temperature. The proposed mechanism involves the creation of fast diffusion channels by CNTs within the MgH₂ lattice. Fullerene is other carbonaceous nanomaterials that has been tested for hydrogen storage in this center. Fullerene molecules are composed of a C₆₀ close-caged structure, that allows for hydrogenation of the double bonded carbons leading to a theoretical C₆₀H₆₀ isomer with a hydrogen content of 7.7 wt%. However, the release temperature in these systems is high (600 °C).

Metal-organic frameworks

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.

Factors influencing hydrogen storage ability

Temperature, pressure and composition of MOFs can influence their hydrogen storage ability. The adsorption capacity of MOFs is lower at higher temperature and higher at lower temperatures. With the rising of temperature, physisorption decreases and chemisorption increases. For MOF-519 and MOF-520, the isosteric heat of adsorption decreased with pressure increase. For MOF-5, both gravimetric and volumetric hydrogen uptake increased with increase in pressure. The total capacity may not be consistent with the usable capacity under pressure swing conditions. For instance, MOF-5 and IRMOF-20, which have the highest total volumetric capacity, show the least usable volumetric capacity. Absorption capacity can be increased by modification of structure. For example, the hydrogen uptake of PCN-68 is higher than PCN-61. Porous aromatic frameworks (PAF-1), which is known as a high surface area material, can achieve a higher surface area by doping.

Modification of MOFs

There are many different ways to modify MOFs, such as MOF catalysts, MOF hybrids, MOF with metal centers and doping. MOF catalysts have high surface area, porosity and hydrogen storage capacity. However, the active metal centers are low. MOF hybrids have enhanced surface area, porosity, loading capacity and hydrogen storage capacity. Nevertheless, they are not stable and lack active centers. Doping in MOFs can increase hydrogen storage capacity, but there might be steric effect and inert metals have inadequate stability. There might be formation of interconnected pores and low corrosion resistance in MOFs with metal centers, while they might have good binding energy and enhanced stability. These advantages and disadvantages for different kinds of modified MOFs show that MOF hybrids are more promising because of the good controllability in selection of materials for high surface area, porosity and stability.

In 2006, chemists achieved hydrogen storage concentrations of up to 7.5 wt% in MOF-74 at a low temperature of 77 K. In 2009, researchers reached 10 wt% at 77 bar (1,117 psi) and 77 K with MOF NOTT-112. Most articles about hydrogen storage in MOFs report hydrogen uptake capacity at a temperature of 77K and a pressure of 1 bar because these conditions are commonly available and the binding energy between hydrogen and the MOF at this temperature is large compared to the thermal vibration energy. Varying several factors such as surface area, pore size, catenation, ligand structure, and sample purity can result in different amounts of hydrogen uptake in MOFs.

In 2020, researchers reported that NU-1501-Al, an ultraporous metal–organic framework (MOF) based on metal trinuclear clusters, yielded "impressive gravimetric and volumetric storage performances for hydrogen and methane", with a hydrogen delivery capacity of 14.0% w/w, 46.2 g/litre.

Cryo-compressed

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 ).

Furthermore, another study has shown that cryo-compressed exhibits interesting cost advantages: ownership cost (price per mile) and storage system cost (price per vehicle) are actually the lowest when compared to any other technology (see third row in slide 13 of ). For example, a cryo-compressed hydrogen 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.

Like liquid storage, cryo-compressed uses cold hydrogen (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 an hydrogen-fueled engine of Toyota Prius. Research is still underway to study and demonstrate the full potential of the technology.

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.

Clathrate hydrates

H₂ caged in a clathrate hydrate was first reported in 2002, but requires very high pressures to be stable. In 2004, researchers 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. These clathrates have a theoretical maximum hydrogen densities of around 5 wt% and 40 kg/m³.

Glass capillary arrays

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. The C.En technology has achieved the United States Department of Energy (DOE) 2010 targets for on-board hydrogen storage systems. DOE 2015 targets can be achieved using flexible glass capillaries and cryo-compressed method of hydrogen storage.

Glass microspheres

Hollow glass microspheres (HGM) can be utilized for controlled storage and release of hydrogen. HGMs with a diameter of 1 to 100 μm, a density of 1.0 to 2.0 gm/cc and a porous wall with openings of 10 to 1000 angstroms are considered for hydrogen storage. The advantages of HGMs for hydrogen storage are that they are nontoxic, light, cheap, recyclable, reversible, easily handled at atmospheric conditions, capable of being stored in a tank, and the hydrogen within is non-explosive. Each of these HGMs is capable of containing hydrogen up to 150 MPa without the heaviness and bulk of a large pressurized tank. All of these qualities are favorable in vehicular applications. Beyond these advantages, HGMs are seen as a possible hydrogen solution due to hydrogen diffusivity having a large temperature dependence. At room temperature, the diffusivity is very low, and the hydrogen is trapped in the HGM. The disadvantage of HGMs is that to fill and outgas hydrogen effectively the temperature must be at least 300 °C which significantly increases the operational cost of HGM in hydrogen storage. The high temperature can be partly attributed to glass being an insulator and having a low thermal conductivity; this hinders hydrogen diffusivity and therefore requiring a higher temperature to achieve the desired output.

To make this technology more economically viable for commercial use, research is being done to increase the efficiency of hydrogen diffusion through the HGMs. One study done by Dalai et al. sought to increase the thermal conductivity of the HGM through doping the glass with cobalt. In doing so they increased the thermal conductivity from 0.0072 to 0.198 W/m-K at 10 wt% Co. Increases in hydrogen adsorption though were only seen up to 2 wt% Co (0.103 W/m-K) as the metal oxide began to cover pores in the glass shell. This study concluded with a hydrogen storage capacity of 3.31 wt% with 2 wt% Co at 200 °C and 10 bar.

A study done by Rapp and Shelby sought to increase the hydrogen release rate through photo-induced outgassing in doped HGMs in comparison to conventional heating methods. The glass was doped with optically active metals to interact with the high-intensity infrared light. The study found that 0.5 wt% Fe₃O₄ doped 7070 borosilicate glass had hydrogen release increase proportionally to the infrared lamp intensity. In addition to the improvements to diffusivity by infrared alone, reactions between the hydrogen and iron-doped glass increased the Fe²⁺/Fe³⁺ ratio which increased infrared absorption therefore further increasing the hydrogen yield.

As of 2020, the progress made in studying HGMs has increased its efficiency but it still falls short of Department of Energy targets for this technology. The operation temperatures for both hydrogen adsorption and release are the largest barrier to commercialization.

Photo-Chemical storage

A method of storing hydrogen in light-activated hydrides has been developed. Hydrogen is stored in a layered nanophotonic structure deposited on a disk or a nano-graphite film; the hydrogen is released when laser light is applied. The photonic release process selectively releases protium but not deuterium. Consequently, after sustained used the material accumulates deuterium. After about 150 cycles, the material can be processed to extract deuterium for commercial use.

Stationary hydrogen storage

Unlike mobile applications, hydrogen density is not a huge problem for stationary applications. As for mobile applications, stationary applications can use established technology:

Compressed hydrogen (CGH₂) in a hydrogen tank
Liquid hydrogen in a (LH₂) cryogenic hydrogen tank
Slush hydrogen in a cryogenic hydrogen tank

Underground hydrogen storage

'Available storage technologies, their capacity and discharge time.'

Underground hydrogen storage is the practice of hydrogen storage in caverns, salt domes and depleted oil and gas fields. Large quantities of gaseous hydrogen have been stored in caverns by ICI for many years without any difficulties. The storage of large quantities of liquid hydrogen underground can function as grid energy storage. The round-trip efficiency is approximately 40% (vs. 75-80% for pumped-hydro (PHES)), and the cost is slightly higher than pumped hydro, if only a limited number of hours of storage is required. Another study referenced by a European staff working paper found that for large scale storage, the cheapest option is hydrogen at €140/MWh for 2,000 hours of storage using an electrolyser, salt cavern storage and combined-cycle power plant. The European project Hyunder indicated in 2013 that for the storage of wind and solar energy an additional 85 caverns are required as it cannot be covered by PHES and CAES systems. A German case study on storage of hydrogen in salt caverns found that if the German power surplus (7% of total variable renewable generation by 2025 and 20% by 2050) would be converted to hydrogen and stored underground, these quantities would require some 15 caverns of 500,000 cubic metres each by 2025 and some 60 caverns by 2050 – corresponding to approximately one third of the number of gas caverns currently operated in Germany. In the US, Sandia Labs are conducting research into the storage of hydrogen in depleted oil and gas fields, which could easily absorb large amounts of renewably produced hydrogen as there are some 2.7 million depleted wells in existence.

Power to gas

Power to gas is a technology which converts electrical power to a gas fuel. There are two methods: the first is to use the electricity for water splitting and inject the resulting hydrogen into the natural gas grid; the second, less efficient method is used to convert carbon dioxide and hydrogen to methane, (see natural gas) using electrolysis and the Sabatier reaction. A third option is to combine the hydrogen via electrolysis with a source of carbon (either carbon dioxide or carbon monoxide from biogas, from industrial processes or via direct air-captured carbon dioxide) via biomethanation, where biomethanogens (archaea) consume carbon dioxide and hydrogen and produce methane within an anaerobic environment. This process is highly efficient, as the archaea are self-replicating and only require low-grade (60 °C) heat to perform the reaction.

Another process has also been achieved by SoCalGas to convert the carbon dioxide in raw biogas to methane in a single electrochemical step, representing a simpler method of converting excess renewable electricity into storable natural gas.

The UK has completed surveys and is preparing to start injecting hydrogen into the gas grid as the grid previously carried 'town gas' which is a 50% hydrogen-methane gas formed from coal. Auditors KPMG found that converting the UK to hydrogen gas could be £150bn to £200bn cheaper than rewiring British homes to use electric heating powered by lower-carbon sources.

Excess power or off peak power generated by wind generators or solar arrays can then be used for load balancing in the energy grid. Using the existing natural gas system for hydrogen, Fuel cell maker Hydrogenics and natural gas distributor Enbridge have teamed up to develop such a power to gas system in Canada.

Pipeline storage of hydrogen where a natural gas network is used for the storage of hydrogen. Before switching to natural gas, the German gas networks were operated using towngas, which for the most part (60-65%) consisted of hydrogen. The storage capacity of the German natural gas network is more than 200,000 GW·h which is enough for several months of energy requirement. By comparison, the capacity of all German pumped storage power plants amounts to only about 40 GW·h. The transport of energy through a gas network is done with much less loss (<0.1%) than in a power network (8%). The use of the existing natural gas pipelines for hydrogen was studied by NaturalHy

Automotive onboard hydrogen storage

Portability is one of the biggest challenges in the automotive industry, where high density storage systems are problematic due to safety concerns. High-pressure tanks weigh much more than the hydrogen they can hold. For example, in the 2014 Toyota Mirai, a full tank contains only 5.7% hydrogen, the rest of the weight being the tank.

The US Department of Energy has set targets for onboard hydrogen storage for light vehicles. The list of requirements include parameters related to gravimetric and volumetric capacity, operability, durability and cost. These targets have been set as the goal for a multiyear research plan expected to offer an alternative to fossil fuels. The FreedomCAR Partnership, which was established under U.S. President George W. Bush, set targets for hydrogen vehicle fuel systems. The 2005 targets were not reached. The targets were revised in 2009 to reflect new data on system efficiencies obtained from fleets of test cars. In 2017 the 2020 and ultimate targets were lowered, with the ultimate targets set to 65 g H₂ per kg total system weight, and 50 g H₂ per litre of system.

FreedomCAR targets for on-board hydrogen storage assuming storage of 5 kg of hydrogen. (Now out of date.)

It is important to note that these targets are for the hydrogen storage system, not the hydrogen storage material such as a hydride. 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 having the potential 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.

The target for fuel cell powered vehicles is to provide a driving range of over 300 miles. A long-term goal set by the US Fuel Cell Technology Office involves the use of nanomaterials to improve maximum range.

Fuel cells and storage

Due to its clean-burning characteristics, hydrogen is a clean fuel alternative for the automotive industry. Hydrogen-based fuel could significantly reduce the emissions of greenhouse gases such as CO₂, SO₂ and NO_x. Three problems for the use of hydrogen fuel cells (HFC) are efficiency, size, and safe onboard storage of the gas. Other major disadvantages of this emerging technology involve cost, operability and durability issues, which still need to be improved from the existing systems. To address these challenges, the use of nanomaterials has been proposed as an alternative option to the traditional hydrogen storage systems. The use of nanomaterials could provide a higher density system and increase the driving range towards the target set by the DOE at 300 miles. Carbonaceous materials such as carbon nanotube and metal hydrides are the main focus of research. They are currently being considered for onboard storage systems due to their versatility, multi-functionality, mechanical properties and low cost with respect to other alternatives.

Other advantages of nanomaterials in fuel cells

The introduction of nanomaterials in onboard hydrogen storage systems may be a major turning point in the automotive industry. However, storage is not the only aspect of the fuel cell to which nanomaterials may contribute. Different studies have shown that the transport and catalytic properties of Nafion membranes used in HFCs can be enhanced with TiO₂/SnO₂ nanoparticles. The increased performance is caused by an improvement in hydrogen splitting kinetics due to catalytic activity of the nanoparticles. Furthermore, this system exhibits faster transport of protons across the cell which makes HFCs with nanoparticle composite membranes a promising alternative.

Another application of nanomaterials in water splitting has been introduced by a research group at Manchester Metropolitan University in the UK using screen-printed electrodes consisting of a graphene-like material. Similar systems have been developed using photoelectrochemical techniques.

Hydrogen storage now and in the future

The Hydrogen Storage Materials research field is vast, having tens of thousands of published papers. According to Papers in the 2000 to 2015 period collected from Web of Science and processed in VantagePoint^® bibliometric software, a scientometric review of research in hydrogen storage materials was constituted. According to the literature, hydrogen energy went through

a hype-cycle type of development in the 2000's. Research in Hydrogen Storage Materials grew at increasing rates from 2000 to 2010. Afterwards, growth continued but at decreasing rates, and a plateau was reached in 2015. Looking at individual country output, there is a division between countries that after 2010 inflected to a constant or slightly declining production, such as the European Union countries, the US and Japan, and those whose production continued growing until 2015, such as China and South Korea. The countries with most publications were China, the EU and the USA, followed by Japan. China kept the leading position throughout the entire period, and had a higher share of hydrogen storage materials publications in its total research output.

Among materials classes, Metal-Organic Frameworks were the most researched materials, followed by Simple Hydrides. Three typical behaviors were identified: 1) New materials, researched mainly after 2004, such as MOFs and Borohydrides; 2) Classic materials, present through the entire period with growing number of papers, such as Simple Hydrides, and 3) Materials with stagnant or declining research through the end of the period, such as AB5 alloys and Carbon Nanotubes.

However, current physisorption technologies are still far from being commercialized. The experimental studies are executed for small samples less than 100 g. The described technologies require high pressure and/or low temperatures as a rule. Therefore, we consider these techniques at their current state of the art not as a separate novel technology but as a type of valuable add-on to current compression and liquefaction methods.

Physisorption processes are reversible since no activation energy is involved and the interaction energy is very low. In materials such as metal–organic frameworks, porous carbons, zeolites, clathrates, and organic polymers, hydrogen is physisorbed on the surface of the pores. In these classes of materials, the hydrogen storage capacity mainly depends on the surface area and pore volume. The main limitation of use of these sorbents as H2 storage materials is weak van der Waals interaction energy between hydrogen and the surface of the sorbents. Therefore, many of the physisorption based materials have high storage capacities at liquid nitrogen temperature and high pressures, but their capacities become very low at ambient temperature and pressure.

LOHC, liquid organic hydrogen storage systems is a promising technique for future hydrogen storage. LOHC are organic compounds that can absorb and release hydrogen through chemical reactions. These compounds are characterized by the fact that they can be loaded and un-loaded with considerable amounts of hydrogen in a cyclic process. In principle, every unsaturated compound (organic molecules with C-C double or triple bonds) can take up hydrogen during hydrogenation. This technique ensures that the release of compounds into the atmosphere are entirely avoided in hydrogen storage. Therefore, LOHCs is an attractive way to provide wind and solar energy for mobility applications in the form of liquid energy carrying molecules of similar energy storage densities and manageability as today's fossil fuels.

Fuel cell

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Fuel_cell

Demonstration model of a direct-methanol fuel cell (black layered cube) in its enclosure.

Scheme of a proton-conducting fuel cell

A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requiring a continuous source of fuel and oxygen (usually from air) to sustain the chemical reaction, whereas in a battery the chemical energy usually comes from metals and their ions or oxides that are commonly already present in the battery, except in flow batteries. Fuel cells can produce electricity continuously for as long as fuel and oxygen are supplied.

The first fuel cells were invented by Sir William Grove in 1838. The first commercial use of fuel cells came more than a century later following the invention of the hydrogen–oxygen fuel cell by Francis Thomas Bacon in 1932. The alkaline fuel cell, also known as the Bacon fuel cell after its inventor, has been used in NASA space programs since the mid-1960s to generate power for satellites and space capsules. Since then, fuel cells have been used in many other applications. Fuel cells are used for primary and backup power for commercial, industrial and residential buildings and in remote or inaccessible areas. They are also used to power fuel cell vehicles, including forklifts, automobiles, buses, boats, motorcycles and submarines.

There are many types of fuel cells, but they all consist of an anode, a cathode, and an electrolyte that allows ions, often positively charged hydrogen ions (protons), to move between the two sides of the fuel cell. At the anode a catalyst causes the fuel to undergo oxidation reactions that generate ions (often positively charged hydrogen ions) and electrons. The ions move from the anode to the cathode through the electrolyte. At the same time, electrons flow from the anode to the cathode through an external circuit, producing direct current electricity. At the cathode, another catalyst causes ions, electrons, and oxygen to react, forming water and possibly other products. Fuel cells are classified by the type of electrolyte they use and by the difference in startup time ranging from 1 second for proton-exchange membrane fuel cells (PEM fuel cells, or PEMFC) to 10 minutes for solid oxide fuel cells (SOFC). A related technology is flow batteries, in which the fuel can be regenerated by recharging. Individual fuel cells produce relatively small electrical potentials, about 0.7 volts, so cells are "stacked", or placed in series, to create sufficient voltage to meet an application's requirements. In addition to electricity, fuel cells produce water, heat and, depending on the fuel source, very small amounts of nitrogen dioxide and other emissions. The energy efficiency of a fuel cell is generally between 40 and 60%; however, if waste heat is captured in a cogeneration scheme, efficiencies of up to 85% can be obtained.

History

Sketch of Sir William Grove's 1839 fuel cell

The first references to hydrogen fuel cells appeared in 1838. In a letter dated October 1838 but published in the December 1838 edition of The London and Edinburgh Philosophical Magazine and Journal of Science, Welsh physicist and barrister Sir William Grove wrote about the development of his first crude fuel cells. He used a combination of sheet iron, copper and porcelain plates, and a solution of sulphate of copper and dilute acid. In a letter to the same publication written in December 1838 but published in June 1839, German physicist Christian Friedrich Schönbein discussed the first crude fuel cell that he had invented. His letter discussed current generated from hydrogen and oxygen dissolved in water. Grove later sketched his design, in 1842, in the same journal. The fuel cell he made used similar materials to today's phosphoric acid fuel cell.

In 1932, Francis Thomas Bacon invented a fuel cell which derived power from hydrogen and oxygen. This was used by NASA to power lights, air-conditioning and communications.

The Brits who bolstered the Moon landings, BBC Archives.

In 1932, English engineer Francis Thomas Bacon successfully developed a 5 kW stationary fuel cell. The alkaline fuel cell (AFC), also known as the Bacon fuel cell after its inventor, is one of the most developed fuel cell technologies, which NASA has used since the mid-1960s.

In 1955, W. Thomas Grubb, a chemist working for the General Electric Company (GE), further modified the original fuel cell design by using a sulphonated polystyrene ion-exchange membrane as the electrolyte. Three years later another GE chemist, Leonard Niedrach, devised a way of depositing platinum onto the membrane, which served as catalyst for the necessary hydrogen oxidation and oxygen reduction reactions. This became known as the "Grubb-Niedrach fuel cell". GE went on to develop this technology with NASA and McDonnell Aircraft, leading to its use during Project Gemini. This was the first commercial use of a fuel cell. In 1959, a team led by Harry Ihrig built a 15 kW fuel cell tractor for Allis-Chalmers, which was demonstrated across the U.S. at state fairs. This system used potassium hydroxide as the electrolyte and compressed hydrogen and oxygen as the reactants. Later in 1959, Bacon and his colleagues demonstrated a practical five-kilowatt unit capable of powering a welding machine. In the 1960s, Pratt & Whitney licensed Bacon's U.S. patents for use in the U.S. space program to supply electricity and drinking water (hydrogen and oxygen being readily available from the spacecraft tanks). In 1991, the first hydrogen fuel cell automobile was developed by Roger Billings.

UTC Power was the first company to manufacture and commercialize a large, stationary fuel cell system for use as a co-generation power plant in hospitals, universities and large office buildings.

In recognition of the fuel cell industry and America's role in fuel cell development, the US Senate recognized 8 October 2015 as National Hydrogen and Fuel Cell Day, passing S. RES 217. The date was chosen in recognition of the atomic weight of hydrogen (1.008).

Types of fuel cells; design

Fuel cells come in many varieties; however, they all work in the same general manner. They are made up of three adjacent segments: the anode, the electrolyte, and the cathode. Two chemical reactions occur at the interfaces of the three different segments. The net result of the two reactions is that fuel is consumed, water or carbon dioxide is created, and an electric current is created, which can be used to power electrical devices, normally referred to as the load.

At the anode a catalyst oxidizes the fuel, usually hydrogen, turning the fuel into a positively charged ion and a negatively charged electron. The electrolyte is a substance specifically designed so ions can pass through it, but the electrons cannot. The freed electrons travel through a wire creating the electric current. The ions travel through the electrolyte to the cathode. Once reaching the cathode, the ions are reunited with the electrons and the two react with a third chemical, usually oxygen, to create water or carbon dioxide.

A block diagram of a fuel cell

Design features in a fuel cell include:

The electrolyte substance, which usually defines the type of fuel cell, and can be made from a number of substances like potassium hydroxide, salt carbonates, and phosphoric acid.
The fuel that is used. The most common fuel is hydrogen.
The anode catalyst, usually fine platinum powder, breaks down the fuel into electrons and ions.
The cathode catalyst, often nickel, converts ions into waste chemicals, with water being the most common type of waste.
Gas diffusion layers that are designed to resist oxidization.

A typical fuel cell produces a voltage from 0.6 to 0.7 V at full rated load. Voltage decreases as current increases, due to several factors:

Activation loss
Ohmic loss (voltage drop due to resistance of the cell components and interconnections)
Mass transport loss (depletion of reactants at catalyst sites under high loads, causing rapid loss of voltage).

To deliver the desired amount of energy, the fuel cells can be combined in series to yield higher voltage, and in parallel to allow a higher current to be supplied. Such a design is called a fuel cell stack. The cell surface area can also be increased, to allow higher current from each cell.

Proton-exchange membrane fuel cells (PEMFCs)

Construction of a high-temperature PEMFC: Bipolar plate as electrode with in-milled gas channel structure, fabricated from conductive composites (enhanced with graphite, carbon black, carbon fiber, and/or carbon nanotubes for more conductivity); Porous carbon papers; reactive layer, usually on the polymer membrane applied; polymer membrane.

Condensation of water produced by a PEMFC on the air channel wall. The gold wire around the cell ensures the collection of electric current.

SEM micrograph of a PEMFC MEA cross-section with a non-precious metal catalyst cathode and Pt/C anode. False colors applied for clarity.

In the archetypical hydrogen–oxide proton-exchange membrane fuel cell design, a proton-conducting polymer membrane (typically nafion) contains the electrolyte solution that separates the anode and cathode sides. This was called a solid polymer electrolyte fuel cell (SPEFC) in the early 1970s, before the proton-exchange mechanism was well understood. (Notice that the synonyms polymer electrolyte membrane and 'proton-exchange mechanism result in the same acronym.)

On the anode side, hydrogen diffuses to the anode catalyst where it later dissociates into protons and electrons. These protons often react with oxidants causing them to become what are commonly referred to as multi-facilitated proton membranes. The protons are conducted through the membrane to the cathode, but the electrons are forced to travel in an external circuit (supplying power) because the membrane is electrically insulating. On the cathode catalyst, oxygen molecules react with the electrons (which have traveled through the external circuit) and protons to form water.

In addition to this pure hydrogen type, there are hydrocarbon fuels for fuel cells, including diesel, methanol (see: direct-methanol fuel cells and indirect methanol fuel cells) and chemical hydrides. The waste products with these types of fuel are carbon dioxide and water. When hydrogen is used, the CO₂ is released when methane from natural gas is combined with steam, in a process called steam methane reforming, to produce the hydrogen. This can take place in a different location to the fuel cell, potentially allowing the hydrogen fuel cell to be used indoors—for example, in fork lifts.

The different components of a PEMFC are

bipolar plates,
electrodes,
catalyst,
membrane, and
the necessary hardware such as current collectors and gaskets.

The materials used for different parts of the fuel cells differ by type. The bipolar plates may be made of different types of materials, such as, metal, coated metal, graphite, flexible graphite, C–C composite, carbon–polymer composites etc. The membrane electrode assembly (MEA) is referred to as the heart of the PEMFC and is usually made of a proton-exchange membrane sandwiched between two catalyst-coated carbon papers. Platinum and/or similar type of noble metals are usually used as the catalyst for PEMFC, and these can be contaminated by carbon monoxide, necessitating a relatively pure hydrogen fuel. The electrolyte could be a polymer membrane.

Proton-exchange membrane fuel cell design issues

Cost: In 2013, the Department of Energy estimated that 80-kW automotive fuel cell system costs of US$67 per kilowatt could be achieved, assuming volume production of 100,000 automotive units per year and US$55 per kilowatt could be achieved, assuming volume production of 500,000 units per year. Many companies are working on techniques to reduce cost in a variety of ways including reducing the amount of platinum needed in each individual cell. Ballard Power Systems has experimented with a catalyst enhanced with carbon silk, which allows a 30% reduction (1.0–0.7 mg/cm²) in platinum usage without reduction in performance. Monash University, Melbourne uses PEDOT as a cathode. A 2011-published study documented the first metal-free electrocatalyst using relatively inexpensive doped carbon nanotubes, which are less than 1% the cost of platinum and are of equal or superior performance. A recently published article demonstrated how the environmental burdens change when using carbon nanotubes as carbon substrate for platinum.
Water and air management (in PEMFCs): In this type of fuel cell, the membrane must be hydrated, requiring water to be evaporated at precisely the same rate that it is produced. If water is evaporated too quickly, the membrane dries, resistance across it increases, and eventually it will crack, creating a gas "short circuit" where hydrogen and oxygen combine directly, generating heat that will damage the fuel cell. If the water is evaporated too slowly, the electrodes will flood, preventing the reactants from reaching the catalyst and stopping the reaction. Methods to manage water in cells are being developed like electroosmotic pumps focusing on flow control. Just as in a combustion engine, a steady ratio between the reactant and oxygen is necessary to keep the fuel cell operating efficiently.
Temperature management: The same temperature must be maintained throughout the cell in order to prevent destruction of the cell through thermal loading. This is particularly challenging as the 2H₂ + O₂ → 2H₂O reaction is highly exothermic, so a large quantity of heat is generated within the fuel cell.
Durability, service life, and special requirements for some type of cells: Stationary fuel cell applications typically require more than 40,000 hours of reliable operation at a temperature of −35 °C to 40 °C (−31 °F to 104 °F), while automotive fuel cells require a 5,000-hour lifespan (the equivalent of 240,000 km (150,000 mi)) under extreme temperatures. Current service life is 2,500 hours (about 75,000 miles). Automotive engines must also be able to start reliably at −30 °C (−22 °F) and have a high power-to-volume ratio (typically 2.5 kW/L).
Limited carbon monoxide tolerance of some (non-PEDOT) cathodes.

Phosphoric acid fuel cell (PAFC)

Phosphoric acid fuel cells (PAFC) were first designed and introduced in 1961 by G. V. Elmore and H. A. Tanner. In these cells phosphoric acid is used as a non-conductive electrolyte to pass positive hydrogen ions from the anode to the cathode. These cells commonly work in temperatures of 150 to 200 degrees Celsius. This high temperature will cause heat and energy loss if the heat is not removed and used properly. This heat can be used to produce steam for air conditioning systems or any other thermal energy consuming system. Using this heat in cogeneration can enhance the efficiency of phosphoric acid fuel cells from 40 to 50% to about 80%. Phosphoric acid, the electrolyte used in PAFCs, is a non-conductive liquid acid which forces electrons to travel from anode to cathode through an external electrical circuit. Since the hydrogen ion production rate on the anode is small, platinum is used as catalyst to increase this ionization rate. A key disadvantage of these cells is the use of an acidic electrolyte. This increases the corrosion or oxidation of components exposed to phosphoric acid.

Solid acid fuel cell (SAFC)

Solid acid fuel cells (SAFCs) are characterized by the use of a solid acid material as the electrolyte. At low temperatures, solid acids have an ordered molecular structure like most salts. At warmer temperatures (between 140 and 150 °C for CsHSO₄), some solid acids undergo a phase transition to become highly disordered "superprotonic" structures, which increases conductivity by several orders of magnitude. The first proof-of-concept SAFCs were developed in 2000 using cesium hydrogen sulfate (CsHSO₄). Current SAFC systems use cesium dihydrogen phosphate (CsH₂PO₄) and have demonstrated lifetimes in the thousands of hours.

Alkaline fuel cell (AFC)

The alkaline fuel cell or hydrogen-oxygen fuel cell was designed and first demonstrated publicly by Francis Thomas Bacon in 1959. It was used as a primary source of electrical energy in the Apollo space program. The cell consists of two porous carbon electrodes impregnated with a suitable catalyst such as Pt, Ag, CoO, etc. The space between the two electrodes is filled with a concentrated solution of KOH or NaOH which serves as an electrolyte. H₂ gas and O₂ gas are bubbled into the electrolyte through the porous carbon electrodes. Thus the overall reaction involves the combination of hydrogen gas and oxygen gas to form water. The cell runs continuously until the reactant's supply is exhausted. This type of cell operates efficiently in the temperature range 343–413 K and provides a potential of about 0.9 V. AAEMFC is a type of AFC which employs a solid polymer electrolyte instead of aqueous potassium hydroxide (KOH) and it is superior to aqueous AFC.

High-temperature fuel cells

Solid oxide fuel cell

Solid oxide fuel cells (SOFCs) use a solid material, most commonly a ceramic material called yttria-stabilized zirconia (YSZ), as the electrolyte. Because SOFCs are made entirely of solid materials, they are not limited to the flat plane configuration of other types of fuel cells and are often designed as rolled tubes. They require high operating temperatures (800–1000 °C) and can be run on a variety of fuels including natural gas.

SOFCs are unique since in those, negatively charged oxygen ions travel from the cathode (positive side of the fuel cell) to the anode (negative side of the fuel cell) instead of positively charged hydrogen ions travelling from the anode to the cathode, as is the case in all other types of fuel cells. Oxygen gas is fed through the cathode, where it absorbs electrons to create oxygen ions. The oxygen ions then travel through the electrolyte to react with hydrogen gas at the anode. The reaction at the anode produces electricity and water as by-products. Carbon dioxide may also be a by-product depending on the fuel, but the carbon emissions from an SOFC system are less than those from a fossil fuel combustion plant. The chemical reactions for the SOFC system can be expressed as follows:

Anode reaction: 2H₂ + 2O²⁻ → 2H₂O + 4e⁻

Cathode reaction: O₂ + 4e⁻ → 2O²⁻

Overall cell reaction: 2H₂ + O₂ → 2H₂O

SOFC systems can run on fuels other than pure hydrogen gas. However, since hydrogen is necessary for the reactions listed above, the fuel selected must contain hydrogen atoms. For the fuel cell to operate, the fuel must be converted into pure hydrogen gas. SOFCs are capable of internally reforming light hydrocarbons such as methane (natural gas), propane and butane. These fuel cells are at an early stage of development.

Challenges exist in SOFC systems due to their high operating temperatures. One such challenge is the potential for carbon dust to build up on the anode, which slows down the internal reforming process. Research to address this "carbon coking" issue at the University of Pennsylvania has shown that the use of copper-based cermet (heat-resistant materials made of ceramic and metal) can reduce coking and the loss of performance. Another disadvantage of SOFC systems is slow start-up time, making SOFCs less useful for mobile applications. Despite these disadvantages, a high operating temperature provides an advantage by removing the need for a precious metal catalyst like platinum, thereby reducing cost. Additionally, waste heat from SOFC systems may be captured and reused, increasing the theoretical overall efficiency to as high as 80–85%.

The high operating temperature is largely due to the physical properties of the YSZ electrolyte. As temperature decreases, so does the ionic conductivity of YSZ. Therefore, to obtain optimum performance of the fuel cell, a high operating temperature is required. According to their website, Ceres Power, a UK SOFC fuel cell manufacturer, has developed a method of reducing the operating temperature of their SOFC system to 500–600 degrees Celsius. They replaced the commonly used YSZ electrolyte with a CGO (cerium gadolinium oxide) electrolyte. The lower operating temperature allows them to use stainless steel instead of ceramic as the cell substrate, which reduces cost and start-up time of the system.

Molten-carbonate fuel cell (MCFC)

Molten carbonate fuel cells (MCFCs) require a high operating temperature, 650 °C (1,200 °F), similar to SOFCs. MCFCs use lithium potassium carbonate salt as an electrolyte, and this salt liquefies at high temperatures, allowing for the movement of charge within the cell – in this case, negative carbonate ions.

Like SOFCs, MCFCs are capable of converting fossil fuel to a hydrogen-rich gas in the anode, eliminating the need to produce hydrogen externally. The reforming process creates CO₂ emissions. MCFC-compatible fuels include natural gas, biogas and gas produced from coal. The hydrogen in the gas reacts with carbonate ions from the electrolyte to produce water, carbon dioxide, electrons and small amounts of other chemicals. The electrons travel through an external circuit creating electricity and return to the cathode. There, oxygen from the air and carbon dioxide recycled from the anode react with the electrons to form carbonate ions that replenish the electrolyte, completing the circuit. The chemical reactions for an MCFC system can be expressed as follows:

Anode reaction: CO₃²⁻ + H₂ → H₂O + CO₂ + 2e⁻

Cathode reaction: CO₂ + ½O₂ + 2e⁻ → CO₃²⁻

Overall cell reaction: H₂ + ½O₂ → H₂O

As with SOFCs, MCFC disadvantages include slow start-up times because of their high operating temperature. This makes MCFC systems not suitable for mobile applications, and this technology will most likely be used for stationary fuel cell purposes. The main challenge of MCFC technology is the cells' short life span. The high-temperature and carbonate electrolyte lead to corrosion of the anode and cathode. These factors accelerate the degradation of MCFC components, decreasing the durability and cell life. Researchers are addressing this problem by exploring corrosion-resistant materials for components as well as fuel cell designs that may increase cell life without decreasing performance.

MCFCs hold several advantages over other fuel cell technologies, including their resistance to impurities. They are not prone to "carbon coking", which refers to carbon build-up on the anode that results in reduced performance by slowing down the internal fuel reforming process. Therefore, carbon-rich fuels like gases made from coal are compatible with the system. The United States Department of Energy claims that coal, itself, might even be a fuel option in the future, assuming the system can be made resistant to impurities such as sulfur and particulates that result from converting coal into hydrogen. MCFCs also have relatively high efficiencies. They can reach a fuel-to-electricity efficiency of 50%, considerably higher than the 37–42% efficiency of a phosphoric acid fuel cell plant. Efficiencies can be as high as 65% when the fuel cell is paired with a turbine, and 85% if heat is captured and used in a combined heat and power (CHP) system.

FuelCell Energy, a Connecticut-based fuel cell manufacturer, develops and sells MCFC fuel cells. The company says that their MCFC products range from 300 kW to 2.8 MW systems that achieve 47% electrical efficiency and can utilize CHP technology to obtain higher overall efficiencies. One product, the DFC-ERG, is combined with a gas turbine and, according to the company, it achieves an electrical efficiency of 65%.

Electric storage fuel cell

The electric storage fuel cell is a conventional battery chargeable by electric power input, using the conventional electro-chemical effect. However, the battery further includes hydrogen (and oxygen) inputs for alternatively charging the battery chemically.

Comparison of fuel cell types

Anode: The electrode at which oxidation (a loss of electrons) takes place. For fuel cells and other galvanic cells, the anode is the negative terminal; for electrolytic cells (where electrolysis occurs), the anode is the positive terminal.
Aqueous solution: Of, relating to, or resembling water; Made from, with, or by water.
Catalyst: A chemical substance that increases the rate of a reaction without being consumed; after the reaction, it can potentially be recovered from the reaction mixture and is chemically unchanged. The catalyst lowers the activation energy required, allowing the reaction to proceed more quickly or at a lower temperature. In a fuel cell, the catalyst facilitates the reaction of oxygen and hydrogen. It is usually made of platinum powder very thinly coated onto carbon paper or cloth. The catalyst is rough and porous so the maximum surface area of the platinum can be exposed to the hydrogen or oxygen. The platinum-coated side of the catalyst faces the membrane in the fuel cell.
Cathode: The electrode at which reduction (a gain of electrons) occurs. For fuel cells and other galvanic cells, the cathode is the positive terminal; for electrolytic cells (where electrolysis occurs), the cathode is the negative terminal.
Electrolyte: A substance that conducts charged ions from one electrode to the other in a fuel cell, battery, or electrolyzer.
Fuel cell stack: Individual fuel cells connected in a series. Fuel cells are stacked to increase voltage.
Matrix: something within or from which something else originates, develops, or takes form.
Membrane: The separating layer in a fuel cell that acts as electrolyte (an ion-exchanger) as well as a barrier film separating the gases in the anode and cathode compartments of the fuel cell.
Molten carbonate fuel cell (MCFC): A type of fuel cell that contains a molten carbonate electrolyte. Carbonate ions (CO₃²⁻) are transported from the cathode to the anode. Operating temperatures are typically near 650 °C.
Phosphoric acid fuel cell (PAFC): A type of fuel cell in which the electrolyte consists of concentrated phosphoric acid (H₃PO₄). Protons (H+) are transported from the anode to the cathode. The operating temperature range is generally 160–220 °C.
Proton-exchange membrane fuel cell (PEM): A fuel cell incorporating a solid polymer membrane used as its electrolyte. Protons (H+) are transported from the anode to the cathode. The operating temperature range is generally 60–100 °C for Low Temperature Proton-exchange membrane fuel cell (LT-PEMFC). PEM fuel cell with operating temperature of 120-200 °C is called High Temperature Proton-exchange membrane fuel cell (HT-PEMFC).
Solid oxide fuel cell (SOFC): A type of fuel cell in which the electrolyte is a solid, nonporous metal oxide, typically zirconium oxide (ZrO₂) treated with Y₂O₃, and O²⁻ is transported from the cathode to the anode. Any CO in the reformate gas is oxidized to CO₂ at the anode. Temperatures of operation are typically 800–1,000 °C.
Solution: An act or the process by which a solid, liquid, or gaseous substance is homogeneously mixed with a liquid or sometimes a gas or solid.; A homogeneous mixture formed by this process; especially : a single-phase liquid system.; The condition of being dissolved.

Efficiency of leading fuel cell types

Theoretical maximum efficiency

The energy efficiency of a system or device that converts energy is measured by the ratio of the amount of useful energy put out by the system ("output energy") to the total amount of energy that is put in ("input energy") or by useful output energy as a percentage of the total input energy. In the case of fuel cells, useful output energy is measured in electrical energy produced by the system. Input energy is the energy stored in the fuel. According to the U.S. Department of Energy, fuel cells are generally between 40 and 60% energy efficient. This is higher than some other systems for energy generation. For example, the typical internal combustion engine of a car is about 25% energy efficient. In combined heat and power (CHP) systems, the heat produced by the fuel cell is captured and put to use, increasing the efficiency of the system to up to 85–90%.

The theoretical maximum efficiency of any type of power generation system is never reached in practice, and it does not consider other steps in power generation, such as production, transportation and storage of fuel and conversion of the electricity into mechanical power. However, this calculation allows the comparison of different types of power generation. The theoretical maximum efficiency of a fuel cell approaches 100%, while the theoretical maximum efficiency of internal combustion engines is approximately 58%.

In practice

In a fuel cell vehicle the tank-to-wheel efficiency is greater than 45% at low loads and shows average values of about 36% when a driving cycle like the NEDC (New European Driving Cycle) is used as test procedure. The comparable NEDC value for a Diesel vehicle is 22%. In 2008 Honda released a demonstration fuel cell electric vehicle (the Honda FCX Clarity) with fuel stack claiming a 60% tank-to-wheel efficiency.

It is also important to take losses due to fuel production, transportation, and storage into account. Fuel cell vehicles running on compressed hydrogen may have a power-plant-to-wheel efficiency of 22% if the hydrogen is stored as high-pressure gas, and 17% if it is stored as liquid hydrogen.^[70] Fuel cells cannot store energy like a battery, except as hydrogen, but in some applications, such as stand-alone power plants based on discontinuous sources such as solar or wind power, they are combined with electrolyzers and storage systems to form an energy storage system. As of 2019, 90% of hydrogen was used for oil refining, chemicals and fertilizer production, and 98% of hydrogen is produced by steam methane reforming, which emits carbon dioxide. The overall efficiency (electricity to hydrogen and back to electricity) of such plants (known as round-trip efficiency), using pure hydrogen and pure oxygen can be "from 35 up to 50 percent", depending on gas density and other conditions. The electrolyzer/fuel cell system can store indefinite quantities of hydrogen, and is therefore suited for long-term storage.

Solid-oxide fuel cells produce heat from the recombination of the oxygen and hydrogen. The ceramic can run as hot as 800 degrees Celsius. This heat can be captured and used to heat water in a micro combined heat and power (m-CHP) application. When the heat is captured, total efficiency can reach 80–90% at the unit, but does not consider production and distribution losses. CHP units are being developed today for the European home market.

Professor Jeremy P. Meyers, in the Electrochemical Society journal Interface in 2008, wrote, "While fuel cells are efficient relative to combustion engines, they are not as efficient as batteries, primarily due to the inefficiency of the oxygen reduction reaction (and ... the oxygen evolution reaction, should the hydrogen be formed by electrolysis of water).... [T]hey make the most sense for operation disconnected from the grid, or when fuel can be provided continuously. For applications that require frequent and relatively rapid start-ups ... where zero emissions are a requirement, as in enclosed spaces such as warehouses, and where hydrogen is considered an acceptable reactant, a [PEM fuel cell] is becoming an increasingly attractive choice [if exchanging batteries is inconvenient]". In 2013 military organizations were evaluating fuel cells to determine if they could significantly reduce the battery weight carried by soldiers.

Applications

Type 212 submarine with fuel cell propulsion of the German Navy in dry dock

Power

Stationary fuel cells are used for commercial, industrial and residential primary and backup power generation. Fuel cells are very useful as power sources in remote locations, such as spacecraft, remote weather stations, large parks, communications centers, rural locations including research stations, and in certain military applications. A fuel cell system running on hydrogen can be compact and lightweight, and have no major moving parts. Because fuel cells have no moving parts and do not involve combustion, in ideal conditions they can achieve up to 99.9999% reliability. This equates to less than one minute of downtime in a six-year period.

Since fuel cell electrolyzer systems do not store fuel in themselves, but rather rely on external storage units, they can be successfully applied in large-scale energy storage, rural areas being one example. There are many different types of stationary fuel cells so efficiencies vary, but most are between 40% and 60% energy efficient. However, when the fuel cell's waste heat is used to heat a building in a cogeneration system this efficiency can increase to 85%. This is significantly more efficient than traditional coal power plants, which are only about one third energy efficient. Assuming production at scale, fuel cells could save 20–40% on energy costs when used in cogeneration systems. Fuel cells are also much cleaner than traditional power generation; a fuel cell power plant using natural gas as a hydrogen source would create less than one ounce of pollution (other than CO₂) for every 1,000 kW·h produced, compared to 25 pounds of pollutants generated by conventional combustion systems. Fuel Cells also produce 97% less nitrogen oxide emissions than conventional coal-fired power plants.

One such pilot program is operating on Stuart Island in Washington State. There the Stuart Island Energy Initiative has built a complete, closed-loop system: Solar panels power an electrolyzer, which makes hydrogen. The hydrogen is stored in a 500-U.S.-gallon (1,900 L) tank at 200 pounds per square inch (1,400 kPa), and runs a ReliOn fuel cell to provide full electric back-up to the off-the-grid residence. Another closed system loop was unveiled in late 2011 in Hempstead, NY.

Fuel cells can be used with low-quality gas from landfills or waste-water treatment plants to generate power and lower methane emissions. A 2.8 MW fuel cell plant in California is said to be the largest of the type. Small-scale (sub-5kWhr) fuel cells are being developed for use in residential off-grid deployment.

Cogeneration

Combined heat and power (CHP) fuel cell systems, including micro combined heat and power (MicroCHP) systems are used to generate both electricity and heat for homes (see home fuel cell), office building and factories. The system generates constant electric power (selling excess power back to the grid when it is not consumed), and at the same time produces hot air and water from the waste heat. As the result CHP systems have the potential to save primary energy as they can make use of waste heat which is generally rejected by thermal energy conversion systems. A typical capacity range of home fuel cell is 1–3 kW_el, 4–8 kW_th. CHP systems linked to absorption chillers use their waste heat for refrigeration.

The waste heat from fuel cells can be diverted during the summer directly into the ground providing further cooling while the waste heat during winter can be pumped directly into the building. The University of Minnesota owns the patent rights to this type of system.

Co-generation systems can reach 85% efficiency (40–60% electric and the remainder as thermal). Phosphoric-acid fuel cells (PAFC) comprise the largest segment of existing CHP products worldwide and can provide combined efficiencies close to 90%. Molten carbonate (MCFC) and solid-oxide fuel cells (SOFC) are also used for combined heat and power generation and have electrical energy efficiencies around 60%. Disadvantages of co-generation systems include slow ramping up and down rates, high cost and short lifetime. Also their need to have a hot water storage tank to smooth out the thermal heat production was a serious disadvantage in the domestic market place where space in domestic properties is at a great premium.

Delta-ee consultants stated in 2013 that with 64% of global sales the fuel cell micro-combined heat and power passed the conventional systems in sales in 2012. The Japanese ENE FARM project will pass 100,000 FC mCHP systems in 2014, 34.213 PEMFC and 2.224 SOFC were installed in the period 2012–2014, 30,000 units on LNG and 6,000 on LPG.

Fuel cell electric vehicles (FCEVs)

Configuration of components in a fuel cell car

Toyota Mirai

Element One fuel cell vehicle

Automobiles

By year-end 2019, about 18,000 FCEVs had been leased or sold worldwide. Three fuel cell electric vehicles have been introduced for commercial lease and sale: the Honda Clarity, Toyota Mirai and the Hyundai ix35 FCEV. Additional demonstration models include the Honda FCX Clarity, and Mercedes-Benz F-Cell. As of June 2011 demonstration FCEVs had driven more than 4,800,000 km (3,000,000 mi), with more than 27,000 refuelings. Fuel cell electric vehicles feature an average range of 314 miles between refuelings. They can be refueled in less than 5 minutes. The U.S. Department of Energy's Fuel Cell Technology Program states that, as of 2011, fuel cells achieved 53–59% efficiency at one-quarter power and 42–53% vehicle efficiency at full power, and a durability of over 120,000 km (75,000 mi) with less than 10% degradation. In a 2017 Well-to-Wheels simulation analysis that "did not address the economics and market constraints", General Motors and its partners estimated that per mile traveled, a fuel cell electric vehicle running on compressed gaseous hydrogen produced from natural gas could use about 40% less energy and emit 45% less greenhouse gasses than an internal combustion vehicle.

In 2015, Toyota introduced its first fuel cell vehicle, the Mirai, at a price of $57,000. Hyundai introduced the limited production Hyundai ix35 FCEV under a lease agreement. In 2016, Honda started leasing the Honda Clarity Fuel Cell. In 2020, Toyota introduced the second generation of its Mirai brand, improving fuel efficiency and expanding range compared to the original Sedan 2014 model.

Criticism

Some commentators believe that hydrogen fuel cell cars will never become economically competitive with other technologies or that it will take decades for them to become profitable. Elon Musk, CEO of battery-electric vehicle maker Tesla Motors, stated in 2015 that fuel cells for use in cars will never be commercially viable because of the inefficiency of producing, transporting and storing hydrogen and the flammability of the gas, among other reasons.

In 2012, Lux Research, Inc. issued a report that stated: "The dream of a hydrogen economy ... is no nearer". It concluded that "Capital cost ... will limit adoption to a mere 5.9 GW" by 2030, providing "a nearly insurmountable barrier to adoption, except in niche applications". The analysis concluded that, by 2030, PEM stationary market will reach $1 billion, while the vehicle market, including forklifts, will reach a total of $2 billion. Other analyses cite the lack of an extensive hydrogen infrastructure in the U.S. as an ongoing challenge to Fuel Cell Electric Vehicle commercialization.

In 2014, Joseph Romm, the author of The Hype About Hydrogen (2005), said that FCVs still had not overcome the high fueling cost, lack of fuel-delivery infrastructure, and pollution caused by producing hydrogen. "It would take several miracles to overcome all of those problems simultaneously in the coming decades." He concluded that renewable energy cannot economically be used to make hydrogen for an FCV fleet "either now or in the future." Greentech Media's analyst reached similar conclusions in 2014. In 2015, Clean Technica listed some of the disadvantages of hydrogen fuel cell vehicles. So did Car Throttle.

A 2019 video by Real Engineering noted that, notwithstanding the introduction of vehicles that run on hydrogen, using hydrogen as a fuel for cars does not help to reduce carbon emissions from transportation. The 95% of hydrogen still produced from fossil fuels releases carbon dioxide, and producing hydrogen from water is an energy-consuming process. Storing hydrogen requires more energy either to cool it down to the liquid state or to put it into tanks under high pressure, and delivering the hydrogen to fueling stations requires more energy and may release more carbon. The hydrogen needed to move a FCV a kilometer costs approximately 8 times as much as the electricity needed to move a BEV the same distance. A 2020 assessment concluded that hydrogen vehicles are still only 38% efficient, while battery EVs are 80% efficient.

Buses

Toyota FCHV-BUS at the Expo 2005

As of August 2011, there were about 100 fuel cell buses in service around the world. Most of these were manufactured by UTC Power, Toyota, Ballard, Hydrogenics, and Proton Motor. UTC buses had driven more than 970,000 km (600,000 mi) by 2011. Fuel cell buses have from 39% to 141% higher fuel economy than diesel buses and natural gas buses.

As of 2019, the NREL was evaluating several current and planned fuel cell bus projects in the U.S.

Trucks

In December 2020, Toyota and Hino Motors, together with Seven-Eleven (Japan), FamilyMart and Lawson announced that they have agreed to jointly consider introducing light-duty fuel cell electric trucks (light-duty FCETs). Lawson started testing for low temperature delivery at the end of July 2021 in Tokyo, using a Hino Dutro in which the Toyota Mirai fuel cell is implemented. FamilyMart started testing in Okazaki city.

In August 2021, Toyota announced their plan to make fuel cell modules at its Kentucky auto-assembly plant for use in zero-emission big rigs and heavy-duty commercial vehicles. They plan to begin assembling the electrochemical devices in 2023.

Forklifts

A fuel cell forklift (also called a fuel cell lift truck) is a fuel cell-powered industrial forklift truck used to lift and transport materials. In 2013 there were over 4,000 fuel cell forklifts used in material handling in the US, of which 500 received funding from DOE (2012). Fuel cell fleets are operated by various companies, including Sysco Foods, FedEx Freight, GENCO (at Wegmans, Coca-Cola, Kimberly Clark, and Whole Foods), and H-E-B Grocers. Europe demonstrated 30 fuel cell forklifts with Hylift and extended it with HyLIFT-EUROPE to 200 units, with other projects in France and Austria. Pike Research projected in 2011 that fuel cell-powered forklifts would be the largest driver of hydrogen fuel demand by 2020.

Most companies in Europe and the US do not use petroleum-powered forklifts, as these vehicles work indoors where emissions must be controlled and instead use electric forklifts. Fuel cell-powered forklifts can provide benefits over battery-powered forklifts as they can be refueled in 3 minutes and they can be used in refrigerated warehouses, where their performance is not degraded by lower temperatures. The FC units are often designed as drop-in replacements.

Motorcycles and bicycles

In 2005, a British manufacturer of hydrogen-powered fuel cells, Intelligent Energy (IE), produced the first working hydrogen-run motorcycle called the ENV (Emission Neutral Vehicle). The motorcycle holds enough fuel to run for four hours, and to travel 160 km (100 mi) in an urban area, at a top speed of 80 km/h (50 mph). In 2004 Honda developed a fuel cell motorcycle that utilized the Honda FC Stack.

Other examples of motorbikes and bicycles that use hydrogen fuel cells include the Taiwanese company APFCT's scooter using the fueling system from Italy's Acta SpA and the Suzuki Burgman scooter with an IE fuel cell that received EU Whole Vehicle Type Approval in 2011. Suzuki Motor Corp. and IE have announced a joint venture to accelerate the commercialization of zero-emission vehicles.

Airplanes

In 2003, the world's first propeller-driven airplane to be powered entirely by a fuel cell was flown. The fuel cell was a stack design that allowed the fuel cell to be integrated with the plane's aerodynamic surfaces. Fuel cell-powered unmanned aerial vehicles (UAV) include a Horizon fuel cell UAV that set the record distance flown for a small UAV in 2007. Boeing researchers and industry partners throughout Europe conducted experimental flight tests in February 2008 of a manned airplane powered only by a fuel cell and lightweight batteries. The fuel cell demonstrator airplane, as it was called, used a proton-exchange membrane (PEM) fuel cell/lithium-ion battery hybrid system to power an electric motor, which was coupled to a conventional propeller.

In 2009, the Naval Research Laboratory's (NRL's) Ion Tiger utilized a hydrogen-powered fuel cell and flew for 23 hours and 17 minutes. Fuel cells are also being tested and considered to provide auxiliary power in aircraft, replacing fossil fuel generators that were previously used to start the engines and power on board electrical needs, while reducing carbon emissions. In 2016 a Raptor E1 drone made a successful test flight using a fuel cell that was lighter than the lithium-ion battery it replaced. The flight lasted 10 minutes at an altitude of 80 metres (260 ft), although the fuel cell reportedly had enough fuel to fly for two hours. The fuel was contained in approximately 100 solid 1 square centimetre (0.16 sq in) pellets composed of a proprietary chemical within an unpressurized cartridge. The pellets are physically robust and operate at temperatures as warm as 50 °C (122 °F). The cell was from Arcola Energy.

Lockheed Martin Skunk Works Stalker is an electric UAV powered by solid oxide fuel cell.

Boats

The world's first certified fuel cell boat (HYDRA), in Leipzig/Germany

The world's first fuel cell boat HYDRA used an AFC system with 6.5 kW net output. Amsterdam introduced fuel cell-powered boats that ferry people around the city's canals.

Submarines

The Type 212 submarines of the German and Italian navies use fuel cells to remain submerged for weeks without the need to surface.

The U212A is a non-nuclear submarine developed by German naval shipyard Howaldtswerke Deutsche Werft. The system consists of nine PEM fuel cells, providing between 30 kW and 50 kW each. The ship is silent, giving it an advantage in the detection of other submarines. A naval paper has theorized about the possibility of a nuclear-fuel cell hybrid whereby the fuel cell is used when silent operations are required and then replenished from the Nuclear reactor (and water).

Portable power systems

Portable fuel cell systems are generally classified as weighing under 10 kg and providing power of less than 5 kW. The potential market size for smaller fuel cells is quite large with an up to 40% per annum potential growth rate and a market size of around $10 billion, leading a great deal of research to be devoted to the development of portable power cells. Within this market two groups have been identified. The first is the microfuel cell market, in the 1-50 W range for power smaller electronic devices. The second is the 1-5 kW range of generators for larger scale power generation (e.g. military outposts, remote oil fields).

Microfuel cells are primarily aimed at penetrating the market for phones and laptops. This can be primarily attributed to the advantageous energy density provided by fuel cells over a lithium-ion battery, for the entire system. For a battery, this system includes the charger as well as the battery itself. For the fuel cell this system would include the cell, the necessary fuel and peripheral attachments. Taking the full system into consideration, fuel cells have been shown to provide 530Wh/kg compared to 44 Wh/kg for lithium ion batteries. However, while the weight of fuel cell systems offer a distinct advantage the current costs are not in their favor. while a battery system will generally cost around $1.20 per Wh, fuel cell systems cost around $5 per Wh, putting them at a significant disadvantage.

As power demands for cell phones increase, fuel cells could become much more attractive options for larger power generation. The demand for longer on time on phones and computers is something often demanded by consumers so fuel cells could start to make strides into laptop and cell phone markets. The price will continue to go down as developments in fuel cells continues to accelerate. Current strategies for improving micro fuel cells is through the use of carbon nanotubes. It was shown by Girishkumar et al. that depositing nanotubes on electrode surfaces allows for substantially greater surface area increasing the oxygen reduction rate.

Fuel cells for use in larger scale operations also show much promise. Portable power systems that use fuel cells can be used in the leisure sector (i.e. RVs, cabins, marine), the industrial sector (i.e. power for remote locations including gas/oil wellsites, communication towers, security, weather stations), and in the military sector. SFC Energy is a German manufacturer of direct methanol fuel cells for a variety of portable power systems. Ensol Systems Inc. is an integrator of portable power systems, using the SFC Energy DMFC. The key advantage of fuel cells in this market is the great power generation per weight. While fuel cells can be expensive, for remote locations that require dependable energy fuel cells hold great power. For a 72-h excursion the comparison in weight is substantial, with a fuel cell only weighing 15 pounds compared to 29 pounds of batteries needed for the same energy.

Other applications

Providing power for base stations or cell sites
Distributed generation
Emergency power systems are a type of fuel cell system, which may include lighting, generators and other apparatus, to provide backup resources in a crisis or when regular systems fail. They find uses in a wide variety of settings from residential homes to hospitals, scientific laboratories, data centers.
Telecommunication equipment and modern naval ships.
An uninterrupted power supply (UPS) provides emergency power and, depending on the topology, provide line regulation as well to connected equipment by supplying power from a separate source when utility power is not available. Unlike a standby generator, it can provide instant protection from a momentary power interruption.
Base load power plants
Solar Hydrogen Fuel Cell Water Heating
Hybrid vehicles, pairing the fuel cell with either an ICE or a battery.
Notebook computers for applications where AC charging may not be readily available.
Portable charging docks for small electronics (e.g. a belt clip that charges a cell phone or PDA).
Smartphones, laptops and tablets.
Small heating appliances
Food preservation, achieved by exhausting the oxygen and automatically maintaining oxygen exhaustion in a shipping container, containing, for example, fresh fish.
Breathalyzers, where the amount of voltage generated by a fuel cell is used to determine the concentration of fuel (alcohol) in the sample.
Carbon monoxide detector, electrochemical sensor.

Fueling stations

Hydrogen fueling station.

According to FuelCellsWorks, an industry group, at the end of 2019, 330 hydrogen refueling stations were open to the public worldwide. As of June 2020, there were 178 publicly available hydrogen stations in operation in Asia. 114 of these were in Japan. There were at least 177 stations in Europe, and about half of these were in Germany. There were 44 publicly accessible stations in the US, 42 of which were located in California.

A hydrogen fueling station costs between $1 million and $4 million to build.

Markets and economics

In 2012, fuel cell industry revenues exceeded $1 billion market value worldwide, with Asian pacific countries shipping more than 3/4 of the fuel cell systems worldwide. However, as of January 2014, no public company in the industry had yet become profitable. There were 140,000 fuel cell stacks shipped globally in 2010, up from 11,000 shipments in 2007, and from 2011 to 2012 worldwide fuel cell shipments had an annual growth rate of 85%. Tanaka Kikinzoku expanded its manufacturing facilities in 2011. Approximately 50% of fuel cell shipments in 2010 were stationary fuel cells, up from about a third in 2009, and the four dominant producers in the Fuel Cell Industry were the United States, Germany, Japan and South Korea. The Department of Energy Solid State Energy Conversion Alliance found that, as of January 2011, stationary fuel cells generated power at approximately $724 to $775 per kilowatt installed. In 2011, Bloom Energy, a major fuel cell supplier, said that its fuel cells generated power at 9–11 cents per kilowatt-hour, including the price of fuel, maintenance, and hardware.

Industry groups predict that there are sufficient platinum resources for future demand, and in 2007, research at Brookhaven National Laboratory suggested that platinum could be replaced by a gold-palladium coating, which may be less susceptible to poisoning and thereby improve fuel cell lifetime. Another method would use iron and sulphur instead of platinum. This would lower the cost of a fuel cell (as the platinum in a regular fuel cell costs around US$1,500, and the same amount of iron costs only around US$1.50). The concept was being developed by a coalition of the John Innes Centre and the University of Milan-Bicocca. PEDOT cathodes are immune to monoxide poisoning.

In 2016, Samsung "decided to drop fuel cell-related business projects, as the outlook of the market isn't good".

Research and development

2005: Georgia Institute of Technology researchers used triazole to raise the operating temperature of PEM fuel cells from below 100 °C to over 125 °C, claiming this will require less carbon-monoxide purification of the hydrogen fuel.
2008: Monash University, Melbourne used PEDOT as a cathode.
2009: Researchers at the University of Dayton, in Ohio, showed that arrays of vertically grown carbon nanotubes could be used as the catalyst in fuel cells. The same year, a nickel bisdiphosphine-based catalyst for fuel cells was demonstrated.
2013: British firm ACAL Energy developed a fuel cell that it said can run for 10,000 hours in simulated driving conditions. It asserted that the cost of fuel cell construction can be reduced to $40/kW (roughly $9,000 for 300 HP).
2014: Researchers in Imperial College London developed a new method for regeneration of hydrogen sulfide contaminated PEFCs. They recovered 95–100% of the original performance of a hydrogen sulfide contaminated PEFC. They were successful in rejuvenating a SO₂ contaminated PEFC too. This regeneration method is applicable to multiple cell stacks.

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