Fuel Cells - A Perspective
by Tom Biegler
With their promise of environmentally benign power, fuel cells are widely promoted as the electricity generators of the future. Technological advances over several decades have demonstrated that they can certainly be made to work but their central claim of exceptionally high efficiency does not always stand up to scientific scrutiny. Expectations that fuel cells will be simple and cheap seem unrealistic. Fuel cells attract great public and commercial interest. Their ability to turn a fuel’s energy into electricity without flame or combustion has immediate popular appeal. The mass media regularly carry items about fuel cell powered cars and their role in a future hydrogen economy. There is also a huge amount of information on the internet: a Google search on ‘fuel cell’ gives more hits (3.7 million) than ‘internal combustion engine’. What more can this article add? Unfortunately, fuel cell publicity conveys expectations and hopes that are often based on uncritical interpretations of the underlying science. The aim here is to use that science to analyse how the technology has developed and what can realistically be delivered by fuel cells. The fuel cell concept has been around since 1839 when Sir William Grove, a Welsh judge and gentleman scientist, first demonstrated the principle. It was little more than a scientific curiosity until the needs of the early US space missions for a ‘long-life battery’ drove an intensive development effort that allowed the 1960s Apollo and Gemini missions to be equipped with fuel cells. More recently, concerns about global warming and greenhouse gas abatement have dominated the fuel cell and energy agenda. Their reputation for efficiency and energy savings has helped fuel cells gain prominence for applications such as transportation and distributed power generation and for converting hydrogen energy to electricity, in ‘hydrogen economy’ scenarios. Also, new niche applications in portable consumer electronics such as notebook computers and mobile phones have emerged. Fuel cell development is big business. In excess of $US2 billion has been invested in fuel cell development over the past decade, and a large part of it has come from governments. Fuel Cell Basic As in batteries, two electrochemical half-reactions occur in a fuel cell. One is the oxidation of the fuel, typically one of the familiar combustible gaseous or liquid materials such as hydrocarbons, natural gas, alcohols, carbon monoxide or hydrogen. The other is the reduction of oxygen. The sum of these two half-reactions equates to the overall combustion of the fuel and the electrical energy generated is related to the energy of combustion. Many types of fuel cell have been designed and developed. An elementary laboratory demonstration of the fuel cell concept makes a good starting point for understanding how these sometimes strikingly different designs have come about. An H-shaped glass vessel contains sulfuric acid. In each arm hangs a platinum electrode. Hydrogen is bubbled into one arm and oxygen or air into the other. A meter connected between the electrodes detects an electrical current. As the current drawn from the cell is increased, the voltage between the electrodes falls. The cell temperature rises slightly as the experiment proceeds. From this simple school experiment, one can deduce that hydrogen is oxidised at one electrode, oxygen reduced at the other, and current flows through the acid by ionic conduction. The overall reaction is equivalent to the burning of hydrogen to produce water. The experiment also embodies the critical elements of fuel cells that determine practical designs. Platinum is used here because of its catalytic properties. The electrochemical reactions in fuel cells have high activation energies. But platinum is expensive and must be used sparingly. Some fuel cells aim for high electrode activity with cheaper materials, by operating at elevated temperatures. Most fuels are less electrochemically reactive than hydrogen. Hydrocarbons such as methane do not oxidise directly at useful rates even at a catalytic electrode. They need some form of pre-treatment. The injection of gases and liquids into fuel cells means that flow and pressure controls are required. Also, electrode structures designed to create thin liquid films and hence short gas diffusion paths help to increase reaction rates of sparingly soluble gases like hydrogen and oxygen. In this elementary cell, the H-shape keeps the two gases and reaction zones apart and prevents chemical short circuiting, but its internal resistance is high and the cell produces little power for its size. Technology for a practical cell must have electrodes and separators compactly arranged with low resistance. The drop in voltage with increasing current reflects energy and efficiency losses. These occur both at the electrode surfaces and within the cell. They can be minimised but not eliminated. Heat is produced, which means that fuel cell temperature needs to be managed. This little fuel cell generates water, as well as electricity. When a fuel contains carbon, the cell makes carbon dioxide. A fuel cell must have a way of handling these chemical products. Major Types of Fuel Cell In the scaling up, engineering and commercial development of fuel cells, there are some common issues. Electrochemical reactions are heterogeneous. They take place at a surface, not in a three-dimensional chamber or vessel, so scale-up requires the replication of interfaces and the creation of multiple arrays of surfaces. To maximise surface area and activity, electrode surface coatings are often in a highly dispersed state. This makes them potentially unstable due to sintering and recrystallisation processes. Catalytic electrodes can be vulnerable to poisoning. Chemically aggressive conditions create engineering problems. Like the well-established electrochemical processes, such as zinc electrowinning or chlorine production, fuel cell operating conditions (eg fuel and air supply rate, temperature, hydrodynamic conditions within the stack) need to be controlled within a pre-determined optimal range. Alkaline Fuel Cell (AFC) Phosphoric Acid Fuel Cell (PAFC) Proton Exchange Membrane Fuel Cell (PEMFC) Direct Methanol Fuel Cell (DMFC) Molten Carbonate Fuel Cell (MCFC) Solid Oxide Fuel Cell (SOFC) Commercialisation Status of Cell Technologies The PAFC is the most commercially advanced technology, aimed at medium-scale power generation. UTC Fuel Cells offers a version of a 200 kW-rated PAFC system (PureCell™ 200, formerly PA25) that has been available for over a decade. They claim worldwide installation of more than 250 units, accumulating over six million hours of operational experience. PAFC commercialisation was given a kick-start in the mid-1990s when the US government offered a one-third subsidy to stimulate sales and lower production costs. The PEMFC is favoured for transportation because of its high power density, moderate operating temperature, quick start-up and rapid response to changes in system demand. The leading developer is Ballard Power Systems Inc, reputed to have 98 percent of the transport demonstration market. Ballard’s brochures describe a 68 kW light duty engine for the automobile market and a 190 kW engine for buses and trucks, as well as a 1.2 kW module for small applications. Smaller PEMFCs are being developed for the portable market. PEMFCs of up to 250 kW capacity have been field-trialled for stationary power generation. The DMFC has made a comeback (CSIRO worked on this type in the 1960s) because of the market need in consumer electronics. The high energy content of methanol is the attraction. It is claimed that a notebook computer could run for 10 hours on 100 millilitres of methanol fuel. Platinum-based catalysts are needed. Technical challenges include lowering catalyst usage and preventing methanol and water ‘crossover’ through the membrane. Models are said to be close to market release. High operating temperatures and slow start-up mean that both the MCFC and SOFC lend themselves to power generation in larger, continuously operating installations in the tens of kW to several MW range. One of the main developers of the MCFC, FuelCell Energy Inc, describes models of 250 kW, 1 MW and 2 MW capacities. An operating life of 16,000 hours for a recent demonstration unit has been reported. The SOFC has had a 40 year development history since Westinghouse (now Siemens Westinghouse) first produced its tubular design, aimed at avoiding the problems of sealing a conventional battery-type structure that would comprise arrays of flat plates. The tubular concept has been demonstrated with 100 and 220 kW units. Australia’s Ceramic Fuel Cells Ltd is one of the developers of a flat-plate SOFC design. The Future of Fuel Cells Efficiency Thermodynamic theory does indeed say that the electrical energy from a fuel cell relates to the free energy of the process. The ‘thermodynamic’ theoretical efficiency, defined as the ratio of reaction free energy to enthalpy, can be 80 percent or above. But electrochemical kinetic theory says that this ratio is an upper limit, only reached at equilibrium when the current is zero. The efficiency in practice must be smaller. Many factors can contribute to efficiency losses:
These factors have a ‘theoretical’ basis just as sound as the thermodynamic analysis of fuel cell efficiency. They cannot simply be dismissed as temporary practical impediments, waiting to be overcome by further development. What are fuel cell efficiencies in practice? Data from independent field trials are hard to come by and care is needed in evaluating efficiency figures and ensuring that they are comparable. It is not always made clear how fuel utilisation and energy losses in peripherals have been taken into account. Efficiencies might include waste heat usage (as in combined heat and power generation, perhaps of no potential value to a customer) or energy recovered from unburnt fuel. Often efficiency is based on the ‘lower heating value’ (LHV) of the fuel which, depending on the fuel, gives a figure some 10-18 percent higher than with its higher heating value. The most extensive data come from the US Department of Defence, which conducted field trials of 30 PAFCs and 76 PEMFCs installed at defence sites. Average electrical efficiencies were 31.6 percent for the PAFC and 23.4 percent for the PEMFC. Data for the MCFC all seem to come from the manufacturers and are in the range 47-52 percent (LHV). The Siemens Westinghouse tubular SOFC has a reported efficiency of 46 percent (LHV) in their 100 and 200 kW demonstration units. FuelCell Energy reports two slightly different published efficiencies of 29 percent and 31percent for its latest 2.1 kW flat-plate SOFC. None of these figures is strictly independent. So, while some good efficiencies have been reported for the larger high-temperature cells, these rather sparse results suggest that widely held expectations of 60- 80 percent efficiency are too optimistic. There is a need for more efficiency data, with independent verification. Inescapable energy losses incurred in electrochemical operations are not unique to fuel cells. Even the simple process of storing electrical energy in a rechargeable battery (e.g. the common lead/acid car battery) results in significant losses, with energy recovery efficiency (kWh out vs. kWh in) typically only 60 -70 percent. Perhaps the efficiency results for fuel cells should not surprise. Simplicity Stationary fuel cell power generators are large. The 200 kW commercial PAFC occupies 48 m³ and weighs 18 tonnes. A 250 kW MCFC occupies 72 m³. The reality is that the fuel cell is not a simple device. To be fair, the primary goal in much fuel cell development to date has been to get them working. Making them simpler and smaller comes later. But, given how they work, simplicity is probably not a reasonable expectation. Cost The best cost data concern the PAFC. The price for a 200 kW unit in the early 1990s was $US 600,000. Government subsidies did not help cost reduction efforts and it is believed that prices even increased, by a further 50 percent. Ballard PEMFC fuel cells have recently been advertised for restricted purchase by educational institutions only. The 1.2 kW Nexa is $US 6495; a 1kW ac generator based on the same module sells for the same price. A German 250 kW MCFC has a reported price tag of €2.4 million. ‘Project costs’ for demonstration installations, rather than prices, have been reported for a few other fuel cells, for example, a 250 kW SOFC in Hannover at €6.2 million and a 250 kW PEMFC in Berlin at €3.5 million. While it obviously comprises more than just a fuel cell, the latest Mercedes-Benz F-Cell car has a recently reported price of $1.4 million. No doubt these scant early-stage prices and project costs represent upper limits to ultimate fuel cell costs. Engineering improvements, economies of scale and new ideas will bring costs down. The Solid State Energy Conversion Alliance, a part US-government-funded consortium, aims to reduce the mass-produced cost of an SOFC to $US 400/kW by 2010, seemingly a decrease of some two orders of magnitude. The challenge is huge, and the present evidence provides little encouragement that fuel cells are going to be cheap. Fuel Cells and the Hydrogen Economy Unfortunately, misconceptions about the hydrogen economy abound, mainly to do with the notion that hydrogen is an ‘abundant fuel’ that can replace fossil fuels. Hydrogen does not occur naturally and can never be a primary fuel. It needs to be manufactured using other sources of energy. While much hydrogen could be produced from coal, the claims of ‘abundance’ are usually referring to its presence in water, which of course is irrelevant to its potential as a common energy transmitter. Fuel cells for converting reticulated hydrogen into electricity occupy a firm place in hydrogen economy scenarios because of their reputation for intrinsically high efficiency. As already explained, that reputation still needs to be substantiated. Conclusions Cost reduction is a big issue for fuel cells. They are not in principle especially simple devices. Better engineering and mass production will presumably bring costs down, but because of their inherent complexity there is no reason to expect them to be cheap. It is fair to conclude that predictions of fuel cells as commonplace components of energy systems (including a hydrogen economy) need to be treated with caution, at least until major improvements eventuate. However, one type, the direct methanol fuel cell, is aimed at a clear existing market in consumer electronics where a long operating cycle, not efficiency, is the objective. The first genuinely commercial fuel cell product is therefore likely to be a DMFC. Acknowledgement
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