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# Proton exchange membrane fuel cell

Proton exchange membrane fuel cells, also known as polymer electrolyte membrane fuel cells (PEMFC), are a type of fuel cell being developed for transport applications as well as for stationary and portable applications. Their distinguishing features include lower temperature/pressure ranges and a special polymer electrolyte membrane.

## Science

### Reactions

For more details on this topic, see Fuel cell.

A proton exchange membrane fuel cell transforms the chemical energy liberated during the electrochemical reaction of hydrogen and oxygen to electrical energy, as opposed to the direct combustion of hydrogen and oxygen gases to produce thermal energy.

A stream of hydrogen is delivered to the anode side of the membrane-electrode assembly (MEA). At the anode side it is catalytically split into protons and electrons. This oxidation half-cell reaction is represented by:

 $\mathrm{H}_2 \rightarrow \mathrm{2H}^+ + \mathrm{2e}^-$ Eo = 0VSHE $\left ( 1 \right )$

The newly formed protons permeate through the polymer electrolyte membrane to the cathode side. The electrons travel along an external load circuit to the cathode side of the MEA, thus creating the current output of the fuel cell.

Meanwhile, a stream of oxygen is delivered to the cathode side of the MEA. At the cathode side oxygen molecules react with the protons permeating through the polymer electrolyte membrane and the electrons arriving through the external circuit to form water molecules. This reduction half-cell reaction is represented by:

 $\mathrm{4H}^+ + \mathrm{4e}^- + \mathrm{O}_2 \rightarrow \mathrm{2H}_2\mathrm{O}$ Eo = 1.229VSHE $\left ( 2 \right )$

PEM Fuel Cell

### Polymer electrolyte membrane

To function, the membrane must conduct hydrogen ions (protons) but not electrons as this would in effect "short circuit" the fuel cell. The membrane must also not allow either gas to pass to the other side of the cell, a problem known as gas crossover. Finally, the membrane must be resistant to the reducing environment at the cathode as well as the harsh oxidative environment at the anode.

Unfortunately, while the splitting of the hydrogen molecule is relatively easy by using a platinum catalyst, splitting the stronger oxygen molecule is more difficult, and this causes significant electric losses. An appropriate catalyst material for this process has not been discovered, and platinum is the best option. Another significant source of losses is the resistance of the membrane to proton flow, which is minimized by making it as thin as possible, on the order of 50 μm.

The PEMFC is a prime candidate for vehicle and other mobile applications of all sizes down to mobile phones, because of its compactness. However, the water management is crucial to performance: too much water will flood the membrane, too little will dry it; in both cases, power output will drop. Water management is a very difficult subject in PEM systems. A wide variety of solutions for managing the water exist including integration of electroosmotic pumps. Furthermore, the platinum catalyst on the membrane is easily poisoned by carbon monoxide (no more than one part per million is usually acceptable) and the membrane is sensitive to things like metal ions, which can be introduced by corrosion of metallic bipolar plates, metallic components in the fuel cell system or from contaminants in the fuel / oxidant.

PEM systems that use reformed methanol were proposed, as in Daimler Chrysler Necar 5; reforming methanol, i.e. making it react to obtain hydrogen, is however a very complicated process, that requires also purification from the carbon monoxide the reaction produces. A platinum-ruthenium catalyst is necessary as some carbon monoxide will unavoidably reach the membrane. The level should not exceed 10 parts per million. Furthermore, the start-up times of such a reformer reactor are of about half an hour. Alternatively, methanol, and some other biofuels can be fed to a PEM fuel cell directly without being reformed, thus making a direct methanol fuel cell (DMFC). These devices operate with limited success.

The most commonly used membrane is Nafion® by DuPont®, which relies on liquid water humidification of the membrane to transport protons. This implies that it is not feasible to use temperatures above 80–90˚C, since the membrane would dry. Other, more recent membrane types, based on Polybenzimidazole (PBI) OR phosphoric acid, can reach up to 220˚C without using any water management: higher temperature allow for better efficiencies, power densities, ease of cooling (because of larger allowable temperature differences), reduced sensitivity to carbon monoxide poisoning and better controllability (because of absence of water management issues in the membrane); however, these recent types are not as common and most research labs and papers still use Nafion. Companies producing PBI membranes include Celanese and PEMEAS, and there is an EU research project regarding these membranes.

Efficiencies of PEMs are in the range of 40-60% Higher Heating Value of Hydrogen (HHV).

## History

Before the invention of PEM fuel cells, existing fuel cell types such as solid-oxide fuel cells were only applied in extreme conditions. Such fuel cells also required very expensive materials and could only be used for stationary applications due to their size. These issues were addressed by the PEM fuel cell. The PEM fuel cell was invented in the early 1960s by Willard Thomas Grubb and Lee Niedrach of General Electric.[1] Initially, sulfonated polystyrene membranes were used for electrolytes, but they were replaced in 1966 by Nafion ionomer, which proved to be superior in performance and durability to sulfonated polystyrene.

PEM fuel cells were used in the NASA Gemini series of spacecraft, but they were replaced by Alkaline fuel cells in the Apollo program and in the Space shuttle.

Parallel with Pratt & Whitney Aircraft, General Electric developed the first proton exchange membrane fuel cells (PEMFCs) for the Gemini space missions in the early 1960s. The first mission to utilize PEMFCs was Gemini V. However, the Apollo space missions and subsequent Apollo-Soyuz, Skylab and Space Shuttle missions utilized fuel cells based on Bacon's design, developed by Pratt & Whitney Aircraft.

Extremely expensive materials were used and the fuel cells required very pure hydrogen and oxygen. Early fuel cells tended to require inconveniently high operating temperatures that were a problem in many applications. However, fuel cells were seen to be desirable due to the large amounts of fuel available (hydrogen & oxygen).

Despite their success in space programs, fuel cell systems were limited to space missions and other special applications, where high cost could be tolerated. It was not until the late 1980s and early 1990s that fuel cells became a real option for wider application base. Several pivotal innovations, e.g. low platinum catalyst loading and thin film electrodes drove the cost of fuel cells down, making development of PEMFC systems more or less realistic. However, there is significant debate as to whether hydrogen fuel cells will be a realistic technology for use in automobiles or other vehicles for many decades. (See The Hype about Hydrogen.)

## Market

Manufacturers of PEM systems include:

• Demirdokum
• Electrochem
• ReliOn, Inc.
• Ballard Power Systems
• UTC Power (also known as UTC Fuel Cells)
• PEMEAS USA
• E-TEK Inc
• DuPont Fuel Cells
• 3M
• Johnson Matthey
• WL Gore
• Hydrogenics
• Lynntech
• NedStack
• Giner
• Plug Power
• Atlantic Fuel Cell.
• NuVant Systems Inc.
• Vestel Elektronik

Manufacturers of PEM stacks and components include:

• DuPont Fuel Cells
• PEMcoat bipolar plate coatings
• [1]
• H2 ECOnomy