Fuel cells generate electricity based upon an electrochemical reaction. Various components of the fuel cell used in the process of generating electricity include conductive material such as graphite. Various types of graphite such as spheroidal graphite and flake graphite have been proposed for use in fuel cell components. The selection of the type of graphite depends, in part, on the desired properties of the resulting component.
There are tradeoffs associated with graphite selection as described in
U.S. Pat. No. 5,558,955. For example, flake graphite has been recognized as having a low corrosion rate in phosphoric acid fuel cells. Additionally, flake graphite has a relatively high packing density, which minimizes the amount of fluoropolymer required. Reducing fluoropolymer requirements reduces cost and reduces the coefficient of thermal expansion, which is an additional benefit. On the other hand, flake graphite tends to be primarily oriented within the plane of a plate as a result of the manufacturing process typically used for making fuel cell plates. This orientation of flake graphite results in a thru-plane conductivity that is typically lower than desired. Additionally, the in-plane conductivity of such plates tends to be higher than desired. The conductivities affect the number of cells that can be included in a cell stack assembly having a single coolant system and affect the temperature drop in an acid condensation zone, which has an effect on the rate of acid loss and the useful life of the fuel cell. U.S. Pat. Nos. 4,345,008; 4,414,291 and 8,318,362 describe how electrolyte condensation zones operate in phosphoric acid fuel cells. The disclosures of those documents are incorporated by reference.
An illustrative fuel cell separator plate includes a polymer and flake graphite particles having a length along a planar direction and a thickness along a generally perpendicular direction. The flake graphite particles have an aspect ratio of length to thickness that is less than ten. In some example embodiments the aspect ratio is between 5.0 and 7.5.
An exemplary method of making a fuel cell separator plate comprises configuring a mixture of flake graphite and a polymer into a desired shape of at least a portion of the fuel cell separator plate. The flake graphite particles have a length along a planar direction and a thickness along a generally perpendicular direction. The flake graphite particles have an aspect ratio of length to thickness that is less than ten. In some example embodiments, the aspect ratio is between 5.0 and 7.5.
The various features and advantages of disclosed examples will become apparent to those skilled in the art from the following detailed description. The drawings that accompany the detailed description can be briefly described as follows.
In the illustrated example, the separator plate 22 is a bipolar plate that includes channels for directing a reactant, such as hydrogen, toward the electrode assembly. The separator plate 30 also includes channels that facilitate directing a reactant, such as oxygen, toward the membrane electrode assembly. The electrochemical reaction between the hydrogen and oxygen at the electrode assembly 26 is used for producing electricity in a known manner.
The example plate 30 comprises flake graphite and a polymer, such as a fluoropolymer. The flake graphite tends to be oriented in the plate 30 with the generally planar surface of each flake parallel to the plane of the plate. That orientation of the flake graphite has an influence on the thru-plane conductivity and the in-plane conductivity of the plate. This is a result of the anisotropic conductivity characteristics of graphite combined with the influence of contact resistance between particles. Contact resistance between graphite flakes is a significant contributor to thermal resistance in the FEP-graphite (fluorinated ethylene propylene-graphite) composites.
One feature of the flake graphite used in embodiments of this invention is that it has an aspect ratio of the length L to the thickness T that is less than 10. The aspect ratio in some examples is between 5 and 7.5. Such an aspect ratio is significantly smaller than flake graphite that has typically been proposed for use in fuel cell plates. The published U.S. Patent Application No. 20110177419 is representative of the applicable prior art for fuel cell separator plates. The flake graphite identified in that document is grade SGC 2900 supplied by the Superior Graphite Company. That flake graphite has a nominal length of 350 microns and a nominal thickness of 20 microns for an L/T aspect ratio of about 17.5.
The smaller aspect ratio of the flake graphite included in the disclosed example embodiment reduces the in-plane thermal conductivity of a fuel cell separator plate, such as the bipolar plate 30. Lowering the aspect ratio of the graphite increases the number of graphite flakes by a factor of 4-5 and results in a substantially lower in-plane thermal conductivity.
Reducing the in-plane thermal conductivity is useful for decreasing the in-plane heat flow, which is required for maintaining a desired cell exit temperature. Using flake particles having larger aspect ratios compared to those included in the disclosed example tends to result in an in-plane conductivity that is too high resulting in an inability to achieve a desired cell exit temperature and a reduction in the lifetime of the fuel cell.
The temperature difference between the hot cell and the cold cell within the acid condensation zone is a function of the heat-flow in the thru-plane direction within the condensation zone. The heat flux is primarily due to in-plane conduction through the separator plate from the catalyzed area into the condensation zone. Thus reducing the in-plane conductivity of the separator plate will lower the temperature of the hot cell at the exit of the condensation zone which will result in an increased cell life due to lower rates of acid evaporation.
Table 1 indicates differences in in-plane thermal conductivity characteristics of separator plates made from thermally purified flake graphite obtained from the Superior Graphite Company with particle lengths of 170 and 350 microns, respectively. The graphite particles had a nominal thickness of 20 microns. A mixture of about 85% flake graphite and 15% fluorinated ethylene propylene (FEP) obtained from Dyneon Fluoropolymers was used to form the plates. The in-plane thermal conductivity of these plates was measured by Material Innovations Inc. at 150° C. Plates made with graphite with a flake dimension of 100 microns were not available at the time these measurements were made so the in-plane thermal conductivity of such a plate was projected by extrapolating the available data. Table 1 shows the measured and projected in-plane thermal conductivity data as a function of the length of the graphite flake. As can be appreciated from Table 1, a lower L/T aspect ratio results in a lower in-plane thermal conductivity.
One of the reasons why the smaller aspect ratio of the disclosed example reduces in-plane thermal conductivity is that the lower aspect ratio increases the number of graphite flakes over a given surface area. This increase is by a factor of at least four and up to greater than ten in some examples. The increase is proportional to the square of the length of the surface area. Increasing the number of graphite flakes for a given surface area changes the contact resistance between graphite flakes, which affects the in-plane thermal conductivity in a desirable manner.
It is known that decreasing the thickness of the graphite flakes below 20 microns will decrease the thru-plane thermal conductivity of the separator plate, which is undesirable. For example, flake graphite with a thickness of about 10 microns will have a thru-plane thermal conductivity that is 40-60% of that of graphite with a particle thickness of 20 microns. Increasing the thickness of the graphite flakes will increase the thru-plane thermal conductivity which is desirable.
The disclosed examples allow for making a monolithic separator plate having more isotropic thermal conductivities (e.g., in-plane and thru-plane). The disclosed examples also provide additional fuel cell design flexibility. The disclosed examples provide the ability to increase the useful lifetime of a fuel cell.
The preceding description is illustrative rather than limiting in nature. Variations and modifications to the disclosed examples may become apparent to those skilled in the art that do not necessarily depart from the essence of this invention. The scope of legal protection given to this invention can only be determined by studying the following claims.
Filing Document | Filing Date | Country | Kind |
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PCT/US14/18849 | 2/27/2014 | WO | 00 |