The DMFC relies upon the
oxidation of
methanol on a
catalyst layer to form
carbon dioxide. Water is consumed at the
anode and produced at the
cathode.
Protons (H+) are transported across the proton exchange membrane - often made from
Nafion - to the cathode where they react with
oxygen to produce water.
Electrons are transported through an external circuit from anode to cathode, providing power to connected devices. The
half-reactions are: Methanol and water are adsorbed on a catalyst usually made of
platinum and
ruthenium particles, and lose protons until carbon dioxide is formed. As water is consumed at the
anode in the reaction, pure methanol cannot be used without provision of water via either passive transport such as back
diffusion (
osmosis), or
active transport such as pumping. The need for water limits the energy density of the fuel. Platinum is used as a catalyst for both half-reactions. This contributes to the loss of cell voltage potential, as any methanol that is present in the cathode chamber will oxidize. If another catalyst could be found for the reduction of oxygen, the problem of methanol crossover would likely be significantly lessened. Furthermore, platinum is very expensive and contributes to the high cost per kilowatt of these cells. During the methanol oxidation reaction
carbon monoxide (CO) is formed, which strongly adsorbs onto the platinum catalyst, reducing the number of available reaction sites and thus the performance of the cell. The addition of other metals, such as
ruthenium or
gold, to the platinum catalyst tends to ameliorate this problem. In the case of platinum-ruthenium catalysts, the oxophilic nature of ruthenium is believed to promote the formation of
hydroxyl radicals on its surface, which can then react with carbon monoxide adsorbed on the platinum atoms. The water in the fuel cell is oxidized to a hydroxy radical via the following reaction: H2O → OH• + H+ + e−. The hydroxy radical then oxidizes
carbon monoxide to produce
carbon dioxide, which is released from the surface as a gas: CO + OH• → CO2 + H+ + e−. Using these OH groups in the half reactions, they are also expressed as:
Cross-over current Methanol on the anodic side is usually in a weak solution (from 1M to 3M), because methanol in high concentrations has the tendency to diffuse through the membrane to the cathode, where its concentration is about zero because it is rapidly consumed by oxygen. Low concentrations help in reducing the cross-over, but also limit the maximum attainable current. The practical realization is usually that a solution loop enters the anode, exits, is refilled with methanol, and returns to the anode again. Alternatively, fuel cells with optimized structures can be directly fed with high concentration methanol solutions or even pure methanol.
Water drag The water in the anodic loop is lost because of the anodic reaction, but mostly because of the associated water drag: every proton formed at the anode drags a number of water molecules to the cathode. Depending on the temperature and membrane type, this number can be between 2 and 6. == Ancillary units ==