Fuel cell stack with enhanced freeze-thaw durability

Abstract

The present invention provides a fuel cell stack with enhanced freeze-thaw durability. In particular, the fuel cell stack includes a gas diffusion layer between a membrane-electrode assembly and a bipolar plate. The gas diffusion layer has a structure that reduces contact resistance in a fuel cell and is cut at a certain angle such that the machine direction (high stiffness direction) of GDL roll is not in parallel with the major flow field direction of the bipolar plate, resulting in an increased GDL stiffness in a width direction perpendicular to a major flow field direction of a bipolar plate.

Claims

1. A method of manufacturing a fuel cell stack with enhanced freeze-thaw durability, the fuel cell stack comprising a plurality of fuel cells, each of the fuel cells comprising a polymer electrolyte membrane, catalyst layers, compressible gas diffusion layers and bipolar plates, wherein the compressible gas diffusion layer (GDL) is attached to an outer surface of each of catalyst layers coated on both sides of the polymer electrolyte membrane, the bipolar plate is attached to an outer surface of each of the gas diffusion layers and is composed of a major flow field and a minor flow field, and the gas diffusion layer has a width direction perpendicular to a major flow field direction of the bipolar plate and a length direction which is in parallel with the major flow field direction of the bipolar plate, the method comprising: providing a rolled compressible GDL material having a dual layer structure including a microporous layer and a macroporous substrate which is formed of carbon fiber felt, or carbon fiber paper, wherein a machine direction of the rolled compressible GDL material is directed to an inherent high stiffness direction of the compressible GDL and a cross-machine direction thereof is directed to a low stiffness direction of the compressible GDL, wherein the machine direction has a higher stiffness than the cross machine direction, cutting the rolled compressible GDL material to form the compressible GDL at a certain angle (θ), wherein during the cutting, the certain angle is formed between the machine direction of the compressible GDL material and the major flow field direction of the bipolar plate such that the inherent high stiffness direction of the compressible GDL is not in parallel with the length direction of the compressible GDL, and assembling the compressible GDL with the bipolar plate such that the certain angle is formed between the inherent high stiffness direction of the compressible GDL and the major flow field direction of the bipolar plate.

2. The method of claim 1, wherein the compressible GDL is cut from the rolled compressible GDL material at the certain angle of 60°≦θ≦90° such that an angle between the inherent high stiffness direction of the compressible GDL and the major flow field direction of the bipolar plate is in a range of 60°≦θ≦90°.

3. The method of claim 1, wherein the compressible GDL is cut from the rolled compressible GDL material at the certain angle of 90° such that an angle between the inherent high stiffness direction of the compressible GDL and the major flow field direction of the bipolar plate is 90 degrees.

4. The method of claim 1, wherein the compressible GDL has a Taber bending stiffness of the machine direction (high stiffness direction) of the gas diffusion layer roll that ranges from 20 gf.Math.cm to 150 gf.Math.cm.

5. The method of claim 1, wherein the compressible GDL has a Taber bending stiffness of the machine direction (high stiffness direction) of the gas diffusion layer roll that ranges from 50 gf.Math.cm to 100 gf.Math.cm.

6. A method of manufacturing a compressible gas diffusion layer (GDL) for a fuel cell with enhanced freeze-thaw durability, the method comprising: providing a rolled compressible GDL material having a dual layer structure including a microporous layer and a macroporous substrate which is formed of carbon fiber felt, or carbon fiber paper, wherein a machine direction of the rolled compressible GDL material is directed to an inherent high stiffness direction of the compressible GDL and a cross-machine direction thereof is directed to a low stiffness direction of the compressible GDL, wherein the machine direction has a higher stiffness than the cross machine direction, cutting the rolled compressible GDL material to form the compressible GDL at a certain angle, wherein during the cutting, the certain angle is formed between the machine direction of the compressible GDL material and a major flow field direction of the bipolar plate, such that the inherent high stiffness direction of the compressible GDL is arranged in one direction and the inherent high stiffness direction of the compressible GDL is not parallel with the length direction of the compressible GDL, wherein the certain angle (θ) is 60°≦θ<90° degrees.

7. A method of manufacturing a fuel cell stack with enhanced freeze-thaw durability, the fuel cell stack comprising a plurality of fuel cells, each of the fuel cells comprising a polymer electrolyte membrane, catalyst layers, compressible gas diffusion layers and bipolar plates, wherein the compressible gas diffusion layer (GDL) is attached to an outer surface of each of catalyst layers coated on both sides of the polymer electrolyte membrane, the bipolar plate is attached to an outer surface of each of the gas diffusion layers and is composed of a major flow field and a minor flow field, and the gas diffusion layer has a width direction perpendicular to a major flow field direction of the bipolar plate and a length direction which is in parallel with the major flow field direction of the bipolar plate, the method comprising, cutting a rolled compressible GDL material to form the compressible GDL at an angle in a range of 60°≦θ<90° with respect to the major flow field direction of the bipolar plate, wherein the machine direction of the rolled compressible GDL material is directed to an inherent stiffness direction of the formed compressible GDL, and assembling the compressible GDL with the bipolar plate such that the angle is formed between the inherent stiffness direction of the compressible GDL and the major flow field direction of the bipolar plate and the inherent stiffness direction of the compressible GDL is at the angle 60°≦θ<90° with respect to the length direction of the compressible GDL, and at a same time, with respect to the major flow field direction of the bipolar plate in the fuel cell stack, to thereby reduce contact resistance at interfaces in a fuel cell and increase a stiffness in a width direction perpendicular to the major flow field direction of the bipolar plate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other features of the present invention will now be described in detail with reference to certain exemplary embodiments thereof illustrated the accompanying drawings which are given hereinbelow by way of illustration only, and thus are not limitative of the present invention, and wherein:

(2) FIG. 1 is a diagram illustrating intrusion of a GDL into a main flow field of a bipolar plate by bipolar plate land compression when fuel cells are assembled to each other in a typical stack;

(3) FIG. 2 is a diagram illustrating a method (90° GDL) of cutting the sheet of a GDL according to an exemplary embodiment of the present invention, compared to a method (0° GDL) of cutting the sheet of a GDL according to a related art;

(4) FIG. 3 is a diagram illustrating (a) an arrangement of a GDL's MD (high stiffness direction) and a major flow field direction of the bipolar plate in a 0° GDL-applied stack according to related art and (b) an arrangement of a GDL's MD (high stiffness direction) and a major flow field direction of the bipolar plate in a 90° GDL-applied stack according to an exemplary embodiment of the present invention;

(5) FIG. 4 is a scanning electron microscope (SEM) photograph (500×) illustrating a macro-porous substrate of the GDL used in an exemplary embodiment of the present invention and in the related art;

(6) FIG. 5 is a graph illustrating the electrochemical performances before and after 1000 freeze-thaw cycles of the 0° GDL-applied stack according to a related art and the 90° GDL-applied stack according to an exemplary embodiment of the present invention;

(7) FIG. 6 is graphs illustrating the cell voltage decay as a function of number of freeze-thaw cycles of the 0° GDL-applied stack according to a related art and the 90° GDL-applied stack according to an exemplary embodiment of the present invention, in which graph (a) shows a result at a current density of 800 mA/cm.sup.2 and graph (b) shows a result at a current density of 1,400 mA/cm.sup.2;

(8) FIG. 7 is a graph illustrating the high frequency resistances before and after 1000 freeze-thaw cycles of the 0° GDL-applied stack according to a related art and the 90° GDL-applied stack according to an exemplary embodiment of the present invention;

(9) FIG. 8 is graphs illustrating the increase of high frequency resistance as a function of number of freeze-thaw cycles of the 0° GDL-applied stack according to a related art and the 90° GDL-applied stack according to an exemplary embodiment of the present invention, in which graph (a) shows a result at a current density of 800 mA/cm.sup.2 and graph (b) shows a result at a current density of 1,400 mA/cm.sup.2.

(10) Reference numerals set forth in the Drawings includes reference to the following elements as further discussed below:

(11) TABLE-US-00001 100: MEA 106: GDL 200: bipolar plate 202: bipolar plate channel 204: bipolar plate land

(12) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.

(13) In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.

DETAILED DESCRIPTION

(14) Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.

(15) It is understood that the term “vehicle” or “vehicular” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g. fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.

(16) Hereinafter, exemplary embodiment of the present invention will be described in detail with reference to the accompanying drawings.

(17) The present invention provides a fuel cell stack with enhanced freeze-thaw durability by reducing generation of ice in a fuel cell through application of a GDL that can minimize contact resistance in the cell under a fuel cell freeze-thaw cycle condition.

(18) The inherent anisotropic characteristics of a gas diffusion layer may be used to reduce the contact resistance in a fuel cell.

(19) In a conventional manufacturing process, in a GDL including carbon fiber felt or carbon fiber paper that is widely used for a fuel cell vehicle as a macro-porous substrate, the carbon fiber may be preferentially oriented in one direction (i.e., MD) to have mechanical properties such as bending stiffness and tensile stress greater than those in the other direction (i.e., cross-machine direction (CMD), also called as transverse direction (TD)). Accordingly, the MD of fabrics of a GDL roll may usually be a high stiffness direction, and the CMD may be a low stiffness direction.

(20) In the fuel cell stack according to the exemplary embodiment of the present invention, an angular range between the MD (high stiffness direction) of the GDL roll and the major flow field direction of the bipolar plate may be greater than about 0 degrees, and equal to or smaller than about 90 degrees. More preferably, the GDL roll may be cut such that the angular range becomes greater than about 25 degrees, and equal to or smaller than about 90 degrees.

(21) More specifically, as shown in a related art of FIG. 3A, when a GDL roll is cut, it may be cut such that the MD of the GDL runs parallel to the major flow field direction of the bipolar plate. However, as shown in an embodiment of FIG. 3B, a GDL may be cut such that the MD of the GDL does not run parallel to the major flow field direction of the bipolar plate. Accordingly, the stiffness of the GDL may increase in the width (W) direction that crosses the major flow field direction of the bipolar plate.

(22) It has been described as an example that the cutting of the GDL roll is performed such that the MD of GDL roll and the major flow field direction of the bipolar plate cross each other at an angle equal to or smaller than about 90 degrees. For example, the GDL roll may be cut such that the two directions cross each other at an angle of about 30 degrees, 45 degrees, and 60 degrees in order to increase the freeze-thaw durability of the fuel cell stack.

(23) Thus, the GDL intrusion into gas channels of the bipolar plate can be reduced and an unnecessary gap in which water is frozen into ice can be reduced at an interface between the GDL and the MEA or the GDL and the bipolar plate. Accordingly, the freeze-thaw durability of the fuel cell stack can be improved.

(24) The Taber bending stiffness of the MD (high stiffness direction) of the GDL roll may range from about 20 g.sub.f.Math.cm to about 150 g.sub.f.Math.cm, and in some instances from about 50 g.sub.f.Math.cm to about 100 g.sub.f.Math.cm. If the Taber bending stiffness is smaller than about 20 g.sub.f.Math.cm, the stiffness is too small for the GDL to be used for a fuel cell vehicle. If the Taber bending stiffness is greater than 150 g.sub.f.Math.cm, the GDL becomes so stiff that the GDL cannot be stored in a roll form, thus causing a reduction in the mass-productivity of GDL.

(25) Also, the macro-porous substrate of the GDL mounted in the stack according to an exemplary embodiment of the present invention may be configured with carbon fiber felt, carbon fiber paper, or a combination thereof. Thus, since the MD (high stiffness direction) of the GDL and the major flow field direction of the bipolar plate are not parallel to each other, and carbon fiber felt or carbon fiber paper is used as a macro-porous substrate of the GDL, the contact resistance of the fuel cell can be reduced, and the interface between components of the fuel cell can be suitably maintained, thereby minimizing ice generation.

(26) That is, the decrease in performance of the fuel cell due to increase in the contact resistance can be reduced by decreasing the contact resistance between the GDL and the bipolar plate land, or between the GDL and the MEA. Also, since the interface between the GDL and MEA, or between the GDL and the bipolar plate can be suitably maintained, a gap in which generated water is frozen into ice may be significantly reduced, thereby improving the freeze-thaw durability.

(27) The fundamental characteristics of the carbon fiber felt-type GDL used in the present embodiment will be described in Table 1 below. The macro-porous substrate may be configured with typical carbon fiber felt as shown in FIG. 4 that is a magnified view of about 500× by a scanning electron microscope. It can be seen that the carbon fibers are irregularly entangled.

(28) As described in Table 1 below, the bending stiffness of the GDL has been measured with respect to MD and CMD at a bending angle of 15 degrees using a Taber Industries Stiffness Tester.

(29) TABLE-US-00002 TABLE 1 Type of Macro- Weight Bending Stiffness Porous Thickness per Unit [Taber Stiffness Unit, g.sub.f .Math. cm] Substrate [μm] Area [gm.sup.−2] MD CMD Carbon Fiber 426 ± 10 135 ± 2 64.87 ± 6.97 12.62 ± 0.38 Felt

(30) Hereinafter, an embodiment and a test example of the present invention will be described in further detail.

Embodiment

(31) As an embodiment of the present, a GDL roll was cut such that the MD (high stiffness direction) of the GDL roll is perpendicular to the major flow field direction of the bipolar plate (cutting angle of about 90 degrees). The GDLs were assembled into a 5-cell stack together with overall components such as MEAs, metallic bipolar plates, end plates and other assembly members.

Comparative Example

(32) As a comparative example, a GDL roll was cut such that the MD (high stiffness direction) of the roll runs parallel to the major flow field direction of the bipolar plate (cutting angle of about 0 degree). The GDLs were assembled into a 5-cell stack together with overall components such as MEAs, metallic bipolar plates, end plates and other assembly members.

Test Example

(33) Electrochemical performance of the GDLs according to the embodiment and the comparative example was tested. That is, the electrochemical performance of fuel cell stacks including the GDLs according to the exemplary embodiment and the comparative example was compared by measuring the current-voltage (I-V) polarization characteristics based on a 5-cell stack. A typical commercialized tester was used as a tester for measuring electrochemical cell performance.

(34) In this case, the test of the electrochemical performance of the fuel cell stacks having the GDLs according to the illustrative embodiment of the present invention and the comparative example were performed under the following conditions. Temperature at the inlet of the fuel cell=65° C., Hydrogen anode/air cathode relative humidity (RH)=50%/50%, Hydrogen anode/air cathode stoichiometric ratio (S.R.)=1.5/2.0

(35) A freeze-thaw cycle condition applied to the exemplary embodiment of the present invention and the comparative example includes putting a five-cell stack into an environmental chamber in which the temperature is adjustable, repeating 1,000 cycles at chamber temperatures between −25° C. and 15° C., and measuring and comparing the electrochemical performance and high frequency resistance (HFR) of a stack for every 50 cycles. Here, the HFR that was measured may be a factor representing contact resistance in the cell. If the HFR increases, an interface between components is damaged or deformed, and contact becomes poor. In this instance, the HFR was measured by a typical commercialized tester under a condition of amplitude of about 5 A and frequency of about 1 kHz.

(36) Test results of the electrochemical performance of the fuel cell stacks including the GDLs according to the illustrative embodiment of the present invention and the comparative example are shown in FIGS. 5 through 8.

(37) The electrochemical performance of the stacks having the GDLs according to the present embodiment (90° GDL) and the related art (0° GDL) was compared with each other after completion of 1,000 freeze-thaw cycles. As shown in FIG. 5, the electrochemical performance of the stacks of the embodiment and the comparative example were both reduced. On the contrary, the stack including the GDL according to the present embodiment showed a greater increase in electrochemical performance than the stack including the GDL according to the related art after both 0 freeze-thaw cycles and 1,000 freeze-thaw cycles. Further, the same was true for the performance decay rate.

(38) For the quantitative evaluation of the electrochemical performance decay rate of the stacks as a function of the number of the freeze-thaw cycles, a medium current density of about 800 mA/cm.sup.2 and a high current density of about 1,400 mA/cm.sup.2 were selected as representative fuel cell operation conditions. Cell voltage drops at the above current densities were compared to each other. As shown in FIG. 6A, when the current density was 800 mA/cm.sup.2, the cell voltage of the stack including the GDL according to the related art (0° GDL) decreased at a rate of about −38 μV/cycle, but the cell voltage of the stack including the GDL according to the present embodiment (90° GDL) decreased at a rate of about −27 μV/cycle. Accordingly, it can be seen that the performance of the cell stack according to the present invention was more gradually decreased than that of the cell stack according to the related art.

(39) As shown in FIG. 6B, when the current density was 1,400 mA/cm.sup.2, the cell performance decay rate increased. The cell voltage of the stack including the GDL according to the related art decreased at a rate of about −109 μV/cycle, but the cell voltage of the stack including the GDL according to the present embodiment decreased at a rate of about −66 μV/cycle. Accordingly, it can be seen that the performance of the cell stack according to the present invention was more gradually decreased at the high current density as well.

(40) When changes in the contact resistance in the cell of the fuel cell stack were compared to each other, the HFRs with respect to the stack according to the comparative example of the related art and the stack according to the present embodiment were compared to one another after 1,000 freeze-thaw cycles were completed. As shown in FIG. 7, the HFRs increased in both the stack according to the present invention and the stack according to the related art after 1,000 freeze-thaw cycles.

(41) However, the HFR with respect to the stack according to the present embodiment was smaller than the stack according to the stack according to the related art after both 0 cycles and 1,000 cycles. This means that the contact state between components in the stack cell of the present embodiment is greater than that in the stack cell according to the related art. Accordingly, it is very unlikely that ice may be generated at interfaces between components in the stack according to the present embodiment at a sub-zero temperature, and thus the cells may be less damaged under freezing conditions.

(42) Additionally, the HFR increase rates as a function of the number of the freeze-thaw cycles were quantitatively measured. As shown in FIG. 8A, when the current density was 800 mA/cm.sup.2, the HFR of the stack according to the related art increased at a rate of about 43 μΩcm.sup.2/cycle, but the HFR of the stack according to the present embodiment increased at a rate of 34 μΩcm.sup.2/cycle. Accordingly, it can be seen that the HFR of the stack according to the present embodiment increased more gradually than that of the stack according to the related art.

(43) As shown in FIG. 8B, when the current density is about 1,400 mA/cm.sup.2, the HFR increase rate increases in both stacks. The HFR of the stack according to the related art increased at a rate of about 50 μΩcm.sup.2/cycle, but the HFR of the stack according to the present invention increased at a rate of about 38 μΩcm.sup.2/cycle. Accordingly, it can be seen that the HFR of the stack according to the present embodiment increased more gradually at the high current density.

(44) For reference, the decay rate of the cell voltage and the increase rate of the HFR after 1,000 freeze-thaw cycles are summarized as shown in Table 2 below.

(45) TABLE-US-00003 TABLE 2 Cell Voltage Decay Rate HFR Increase Rate [μV/cycle] [μΩ cm.sup.2/cycle] 800 1,400 800 1,400 Type of Stack mAcm.sup.−2 mAcm.sup.−2 mAcm.sup.−2 mAcm.sup.−2 0° GDL Stack −38 −109 43 50 according to Related Art 90° GDL Stack −27 −66 34 38 according to Present Invention

(46) As described above, compared to the stack including the GDL (the MD of the GDL roll is parallel to the major flow field direction of the bipolar plate (cutting angle is 0 degree)) according to the related art, the stack including the GDL (the MD of the GDL roll is perpendicular to the major flow field direction of the bipolar plate (cutting angle is 90 degrees) according to the present embodiment has higher electrochemical performance, slower performance decay rate, smaller contact resistance in the cell, and a slower contact resistance increase rate during the freeze-thaw cycle. Accordingly, since the probability that ice is generated at interfaces in the cell is low, the freeze-thaw durability can be improved.

(47) According to an embodiment of the present invention, the fuel cell stack with the GDL in which its stiffness in a width direction perpendicular to a major flow field direction of a bipolar plate is increased by cutting a rolled GDL material at a certain angle such that a MD (high stiffness direction) of GDL roll is not in parallel with the major flow field direction of the bipolar plate can have enhanced durability under freeze/thaw cycling conditions. Also, the freeze-thaw durability may be improved by reducing generation of ice at interfaces in the fuel cell.

(48) The invention has been described in detail with reference to embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.