VYAS GAYATRI (US)
TRABOLD THOMAS A (US)
DATTA REENA L (US)
| US20040151952A1 | 2004-08-05 | |||
| US6667553B2 | 2003-12-23 | |||
| US20050064275A1 | 2005-03-24 | |||
| US20040142184A1 | 2004-07-22 | |||
| US20040241520A1 | 2004-12-02 | |||
| US6586056B2 | 2003-07-01 | |||
| US5590383A | 1996-12-31 | |||
| US20050208360A1 | 2005-09-22 |
CLAIMS What is claimed is:
1. A process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition using a precursor gas, the precursor gas comprising a compound comprising at least one Si-O group, and at least one group including a saturated or unsaturated carbon chain.
2. A process as set forth in claim 1 further comprising pretreating the substrate, prior to depositing the first coating, to remove contaminants from the substrate.
3. A process as set forth in claim 1 further comprising pretreating the substrate, prior to depositing the first coating, to attach polar groups to the substrate.
4. A process as set forth in claim 3 wherein the polar groups comprises hydroxyl groups.
5. A process comprising pretreating the substrate, prior to depositing the first coating, comprising exposing the substrate to a plasma comprising oxygen.
6. A process comprising pretreating the substrate, prior to depositing the first coating, comprising exposing the substrate to a microwave generated plasma comprising oxygen.
7. A process as set forth in claim 6 wherein the exposure is for a period of up to 5 minutes.
8. A process as set forth in claim 6 wherein the exposure is for a period of 0.5 to 3 minutes.
9. A process as set forth in claim 1 wherein the plasma assisted chemical deposition is conducted at a pressure ranging from 0 to 500 Pa.
10. A process as set forth in claim 1 wherein the plasma assisted chemical deposition is conducted at a pressure ranging from 10 to 100 Pa.
11. A process as set forth in claim 1 wherein the plasma assisted chemical deposition is conducted at a pressure ranging from 30-100 Pa.
12. A process as set forth in claim 1 wherein the plasma is generated by microwave energy.
13. A process as set forth in claim 12 wherein the microwave energy ranges from 50 W to 10 kW.
14. A process as set forth in claim 12 wherein the microwave energy ranges from 100 W to 1 kW.
15. A process as set forth in claim 12 wherein the microwave energy ranges from 200 W to 300 W.
16. A process as set forth in claim 15 wherein the volume of the reactor is about 110 liters.
17. A process as set forth in claim 1 further comprising a carrier gas.
18. A process as set forth in claim 17 wherein the carrier gas comprises at least one of air, nitrogen, argon, alkyamines, alkysilanes, ammonia, carbon dioxide, chloride, chlorine dioxide, chlorohydrocarbons, nitrous oxide, oxygen, ozone, water vapor or mixtures thereof.
19. A process as set forth in claim 17 wherein the precursor to carrier gas volume flow ratio ranges from 4-16 percent.
20. A process as set forth in claim 17 wherein the precursor to carrier gas volume flow ratio ranges from 4-12 percent.
21. A process as set forth in claim 17 wherein the precursor to carrier gas volume flow ratio ranges from 8-10 percent.
22. A process as set forth in claim 17 wherein the carrier gas comprises oxygen.
23. A process as set forth in claim 22 wherein the precursor to carrier gas volume flow ratio ranges from 4-16 percent.
24. A process as set forth in claim 22 wherein the precursor to carrier gas volume flow ratio ranges from 4-12 percent.
25. A process as set forth in claim 22 wherein the precursor to carrier gas volume flow ratio ranges from 8-10 percent.
26. A process as set forth in claim 22 wherein the carrier gas comprises O2.
27. A process as set forth in claim 17 wherein the precursor gas flow rate ranges from 2-50 ml/minute and the carrier gas flow rate ranges from 20-625 ml/minute.
28. A process as set forth in claim 17 wherein the precursor gas flow rate ranges from 10-30 ml/minute and the carrier gas flow rate ranges from 100-375 ml/minute.
29. A process as set forth in claim 17 wherein the precursor gas flow rate ranges from 15-20 ml/minute and the carrier gas flow rate ranges from 150-250 ml/minute.
30. A process as set forth in claim 1 wherein the plasma is maintained at a steady state.
31. A process as set forth . in claim 12 wherein the microwave power is pulsed using microsecond to nanosecond pulses.
32. A process as set forth in claim 1 further comprising post- treating the first coating to add polar groups to the compound.
33. A process as set forth in claim 1 further comprising post- treating the first coating comprising exposing the first coating to a plasma comprising oxygen.
34. A process as set forth in claim 33 wherein the exposing is conducted for a period up to 5 minutes.
35. A process as set forth in claim 33 wherein the exposing is conducted for a period ranging from 0.5 to 3 minutes.
36. A process as set forth in claim 32 wherein the polar group comprises a hydroxyl group, halide, carboxyl, ketonic or an aldehyde function group.
37. A process as set forth in claim 1 wherein the carbon chain has between 1 to 4 carbon atoms.
38. A process as set forth in claim 1 wherein the coating further comprises an electrically conductive material.
39. A product as set forth in claim 38 wherein the electrically conductive material comprises at least one of Au, Ag, Ru, Rh, Pd, Re, Os, Ir, Pt, rare earth metals, alloys thereof, polymeric carbon or graphite.
40. A product as set forth in claim 1 wherein the component comprises a bipolar plate.
41. A product as set forth in claim 1 wherein the substrate comprises a metaj.
42. A product as set forth in claim 1 wherein the substrate comprises a polymeric composite material.
43. A product as set forth in claim 1 further comprising a second coating comprising an electrically conductive material and wherein the second coating overlies the substrate and the first coating overlies the second coating.
44. A product as set forth in claim 1 wherein the carbon chain is linear, branched or cyclic.
45. A process as set forth in claim 1 further comprising selectively depositing a mask over portions of the substrate leaving portions of the substrate unmasked and exposed prior to depositing a first coating over a fuel cell component.
46. A process as set forth in claim 45 wherein the mask is one of a hard mask, a washable mask, or a photoresist mask.
47. A process as set forth in claim 45 wherein the component is a bipolar plate having a plurality of lands and channels and wherein the mask is selectively deposited only over the lands.
48. A process as set forth in claim 1 wherein the component is a bipolar plate having a plurality of lands and channels and wherein the mask is selectively deposited only over portions of the bipolar plate prior to depositing the first coating over a fuel cell component, and thereafter removing the mask and any portion of the first coating overlying the mask.
49. A process as set forth in claim 1 wherein the component is a bipolar plate having a plurality of lands and channels and wherein the first coating is deposited over the lands and channels and selective portions of the first coating is thereafter removed.
50. A process as set forth in claim 1 wherein the component is a bipolar plate having a plurality of lands and channels and wherein the first coating is deposited over the lands and channels and the first coating over the lands is thereafter removed.
51. A process as set forth in claim 1 wherein the component is a bipolar plate having a plurality of lands and channels and wherein the first coating is deposited over the lands and channels, and further comprising selectively depositing a mask over portions of the first coating leaving portions of the first coating exposed, and thereafter removing the exposed portions of the first coating.
52. A process as set forth in claim 51 wherein the exposed portions are removed by etching.
53. A process as set forth in claim 1 wherein the mask is deposited only over the channels.
54. A process as set forth in claim 1 wherein the precursor gases comprising a material having the formula
R, R 4
R 2
- Si - O - Si - R 5
55. A process as set forth in claim 32 wherein the polar groups comprise at least one of a hydroxyl, carboxyl or aldehyde functional group.
56. A process as set forth in claim 1 wherein the precursor comprises hexamethyl disoloxane.
57. A process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition using a precursor gas, the precursor gas comprising a first compound comprising at least one of a silxoane or silanol.
58. A process as set forth in claim 57 wherein the plasma assisted chemical vapor deposition further comprising a second gas comprising oxygen.
59. A process as set forth in claim 58 wherein the coating comprises a second compound and further comprising treating the first coating to add polar groups to the second compound.
60. A process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition comprising flowing a silane gas, a gas comprising a compound comprising a carbon chain and a gas comprising oxygen.
61. A process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition comprising flowing a gas comprising a first compound comprising silicon, a second gas comprising a second compound comprising a carbon chain and a third gas comprising compound comprising oxygen.
62. A process comprising: depositing a coating over a fuel cell component using plasma assisted chemical vapor deposition flowing a precursor gas into a plasma reaction chamber and flowing a carrier gas into the plasma reaction chamber, wherein the molar flow rate ratio of the precursor to carrier gas ranges from about 4 to about 16 percent.
63. A process as set forth in claim 62 wherein the molar flow rate ratio of the precursor to carrier gas ranges from about 4 to about 12 percent.
64. A process as set forth in claim 62 wherein the molar flow rate ratio of the precursor to carrier gas ranges from about 8 to about 10 percent.
65. A process as set forth in claim 62 wherein the precursor gas comprises hexamethyl disiloxane and the carrier gas comprises oxygen.
66. A process as set forth in claim 62 further comprising post- treating the coating to add polar groups.
67. A process as set forth in claim 62 further comprising post- treating the coating comprising exposing the coating to a plasma comprising oxygen ions.
68. A process as set forth in claim 62 further comprising pre-treating the fuel cell component prior to the depositing comprising attaching polar groups to the fuel cell component.
69. A process comprising: depositing a coating on a fuel cell bipolar plate using plasma assisted chemical vapor deposition.
70. A process as set forth further comprising masking a portion of the bipolar plate prior to depositing.
71. A process as set forth in claim 69 wherein the using plasma assisted chemical vapor deposition comprises flowing a precursor gas into a plasma reaction chamber and wherein the precursor gas comprises at least one of carbon or silicon.
72. A process as set forth in claim 69 wherein the using plasma assisted chemical vapor deposition comprises flowing a precursor gas into a plasma reaction chamber and wherein the precursor gas comprises carbon and silicon.
73. A process as set forth in claim 72 further comprising flowing a carrier gas into the plasma reaction chamber, wherein the carrier gas comprises oxygen.
74. A process as set forth in claim 54 wherein at least one of Ri , R≥, R3, R4, Rs. or R 6 , is a carbon chain having at least one carbon atom. |
PROCESS FOR APPLICATION OF A HYDROPHILIC COATING TO FUEL
CELL BIPOLAR PLATES
TECHNICAL FIELD
[0001] The disclosure generally relates to making fuel cell components with a coating thereon.
BACKGROUND
[0002] Hydrogen is a very attractive fuel because it is clean and can be used to efficiently produce electricity in a fuel cell. The automotive industry expends significant resources in the development of hydrogen fuel cells as a source of power for vehicles. Such vehicles would be more efficient and generate fewer emissions than today's vehicles employing internal combustion engines.
[0003] A hydrogen fuel cell is an electro-chemical device that includes an anode and a cathode with an electrolyte therebetween. The anode receives hydrogen-rich gas or pure hydrogen and the cathode receives oxygen or air. The hydrogen gas is dissociated in the anode to generate free protons and electrons. The protons pass through the electrolyte to the cathode. The protons react with the oxygen and the electrons in the cathode to generate water. The electrons from the anode cannot pass through the electrolyte, and thus are directed through a load to perform work before being sent to the cathode. The work may be used to operate a vehicle, for example.
[0004] Proton exchange membrane fuel cells (PEMFC) are popular for vehicle applications. The PEMFC generally includes a solid-polymer- electrolyte proton-conducting membrane, such as a perfluorosulfonic acid membrane. The anode and cathode typically include finely divided catalytic particles, usually platinum (Pt), supported on carbon particles and mixed with an ionomer. The catalytic mixture is deposited on opposing sides of the membrane. The combination of the anode catalytic mixture, the cathode catalytic mixture and the membrane define a membrane electrode assembly (MEA). MEAs are relatively expensive to manufacture and require certain conditions for effective operation. These conditions include proper water management and humidification, and control of catalyst poisoning constituents, such as carbon monoxide (CO).
[0005] Several fuel cells are typically combined in a fuel cell stack to generate the desired power. For the automotive fuel cell stack mentioned above, the stack may include about two hundred or more bipolar plates. The fuel cell stack receives a cathode reactant gas, typically a flow of air forced through the stack by a compressor. Not all of the oxygen is consumed by the stack and some of the air is output as a cathode exhaust gas that may include liquid water as a stack by-product. The fuel cell stack also receives an anode hydrogen reactant gas that flows into the anode side of the stack.
[0006] The fuel cell stack includes a series of flow field or bipolar plates positioned between the several MEAs in the stack. The bipolar plates include an anode side and a cathode side for adjacent fuel cells in the stack.
Anode gas flow channels are provided on the anode side of the bipolar plates that allow the anode gas to flow to the anode side of the MEA. Cathode gas flow channels are provided on the cathode side of the bipolar plates that allow the cathode gas to flow to the cathode side of the MEA. The bipolar plates may also include flow channels for a cooling fluid.
[0007] The bipolar plates are typically made of a conductive material, such as stainless steel, titanium, aluminum, polymeric carbon composites, etc., so that they conduct the electricity generated by the fuel cells from one cell to the next cell and out of the stack. Metal bipolar plates typically produce a natural oxide on their outer surface that makes them resistant to corrosion. However, this oxide layer is not conductive, and thus increases the internal resistance of the fuel cell, reducing its electrical performance. Also, the oxide layer frequently makes the plates more hydrophobic. [0008] US Patent Application Publication No. 2003/0228512, assigned to the assignee of this application, the disclosure of which is and herein incorporated by reference, discloses a process for depositing a conductive outer layer on a flow field plate that prevents the plate from oxidizing and increasing its ohmic contact. US Patent No. 6,372,376, also assigned to the assignee of this application, discloses depositing an electrically conductive, oxidation resistant and acid resistant coating on a flow field plate. US Patent Application Publication No. 2004/0091768, also assigned to the assignee of this application, discloses depositing a graphite and carbon black coating on a flow field plate for making
the flow field plate corrosion resistant, electrically conductive and thermally conductive.
[0009] As is well understood in the art, the membranes within a fuel cell need to have a certain relative humidity so that the ionic resistance across the membrane is low enough to effectively conduct protons. During operation of the fuel cell, moisture from the MEAs and external humidification may enter the anode and cathode flow channels. At low cell power demands, typically below 0.2 A/cm 2 , water accumulates within the flow channels because the flow rate of the reactant gas is too low to force the water out of the channels. As the water accumulates, it forms droplets that continue to expand because of the hydrophobic nature of the plate material. The contact angle of the water droplets is generally about 90° in that the droplets form in the flow channels substantially perpendicular to the flow of the reactant gas. As the size of the droplets increases, the flow channel is closed off, and the reactant gas is diverted to other flow channels because the channels flow in parallel between common inlet and outlet manifolds. Because the reactant gas may not flow through a channel that is blocked with water, the reactant gas cannot force the water out of the channel. Those areas of the membrane that do not receive reactant gas as a result of the channel being blocked will not generate electricity, thus resulting in a non- homogenous current distribution and reducing the overall efficiency of the fuel cell. As more and more flow channels are blocked by water, the electricity produced by the fuel cell decreases, where a cell voltage potential less than 200 mV is considered a cell failure. Because the fuel cells are electrically coupled in
series, if one of the fuel cells stops performing, the entire fuel cell stack may stop performing.
[00010] It is usually possible to purge the accumulated water in the flow channels by periodically forcing the reactant gas through the flow channels at a higher flow rate. However, on the cathode side, this increases the parasitic power applied to the air compressor, thereby reducing overall system efficiency. Moreover, there are many reasons not to use the hydrogen fuel as a purge gas, including reduced economy, reduced system efficiency and increased system complexity for treating elevated concentrations of hydrogen in the exhaust gas stream.
[00011] Reducing accumulated water in the channels can also be accomplished by reducing inlet humidification. However, it is desirable to provide some relative humidity in the anode and cathode reactant gases so that the membrane in the fuel cells remains hydrated. A dry inlet gas has a drying effect on the membrane that could increase the cell's ionic resistance, and limit the membrane's long-term durability.
[00012] It has been proposed by the present inventors to make bipolar plates for a fuel cell hydrophilic to improve channel water transport. A hydrophilic plate causes water in the channels to spread along the surface in a process termed spontaneous wetting. The resulting thin film has less of a tendency to alter the flow distribution along the array of channels connected to the common inlet and outlet headers. If the plate material has sufficiently high surface energy, water transported through the diffusion media will contact the
channel walls and then, by capillary force, be transported into the bottom corners of the channel along its length. The physical requirements to support spontaneous wetting in the corners of a flow channel are described by the
Concus-Finn condition, β+— <90 9 , where β is the static contact angle formed
between a liquid surface and a solid surface and a is the channel corner angle. For a rectangular channel all = 45 °, which dictates that spontaneous wetting will occur when the static contact angle is less than 45°. For the roughly rectangular channels used in current fuel cell stack designs with composite bipolar plates, this sets an approximate upper limit on the contact angle needed to realize the beneficial effects of hydrophilic plate surfaces on channel water transport and low load stability.
SUMMARY OF EXEMPLARY EMBODIMENTS OF THE INVENTION
[00014] One embodiment of the invention includes a process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition using a precursor gas, the precursor gas comprising a compound comprising at least one Si-O group, and at least one group including a saturated or unsaturated carbon chain. [00015] Another embodiment of the invention includes a process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition using a precursor
gas, the precursor gas comprising a first compound comprising at least one of a sixolane or silanol.
[00016] Another embodiment of the invention includes a process comprising: depositing a first coating over a fuel cell component comprising a substrate using a plasma assisted chemical vapor deposition comprising flowing a silane gas, a gas comprising a compound comprising a carbon chain and a gas comprising oxygen.
[00017] Another embodiment of the invention includes a process comprising: depositing a coating over a fuel cell component using plasma assisted chemical vapor deposition including flowing a precursor gas into a plasma reaction chamber and flowing a carrier gas into the plasma reaction chamber, wherein the molar flow rate ratio of the precursor to carrier gas ranges from about 4 to about 16 percent.
[00018] Another embodiment of the invention includes a process comprising: depositing a coating on a fuel cell bipolar plate using plasma assisted chemical vapor deposition.
[00019] Other embodiments of the invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the exemplary embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[00020] The exemplary embodiments of the invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
[00021] Figure 1 is a graph of the result of Fourier-transform infrared spectra of a coating produced according to one embodiment of the invention using a gas ratio of precursor to carrier gas of 4 percent in a plasma enhanced chemical vapor deposition process.
[00022] Figure 2 is a graph of the result of Fourier-transform infrared spectra of a coating produced according to one embodiment of the invention using a gas ratio of precursor to carrier gas of 8 percent in a plasma enhanced chemical vapor deposition process.
[00023] Figure 3 is a graph of the result of Fourier-transform infrared spectra of a coating produced according to one embodiment of the invention using a gas ratio of precursor to carrier gas of 12 percent in a plasma enhanced chemical vapor deposition process.
[00024] Figure 4 illustrates a microscopic photo of a coating according to one embodiment of the invention wherein the coating is porous and include nanoparticles having a nodule shape.
[00025] Figure 5 is a cross-sectional view of a fuel cell in a fuel cell stack that includes bipolar plates having coating to make the plate hydrophilic, according to an embodiment of the invention;
[00026] Figure 6 is a broken-away, cross-sectional view of a bipolar plate for a fuel cell including a coating defined by islands separated by open areas, according to another embodiment of the invention;
[00027] Figure 7 is a broken-away, cross-sectional view of a bipolar plate for a fuel cell including a coating, where the coating has been removed at the lands between the flow channels in the plate, according to another embodiment of the invention;
[00028] Figure 8 is a broken-away, cross-sectional view of a bipolar plate for a fuel cell where a coating is deposited over another coating that is on the bipolar plate, according to one embodiment of the invention;
[00029] Figure 9 illustrates one embodiment of the invention including a process including first selectively forming a mask over the lands of a bipolar plate and thereafter depositing a coating over the bipolar plate including the mask;
[00030] Figure 10 illustrates one embodiment of the invention including a process wherein the mask over the lands is removed to leave the coating only overlying the channel of the bipolar plate;
[00031] Figure 11 illustrates one embodiment of the invention including a process including first depositing a coating including silicon over the bipolar plate, then selectively forming a mask over the channels of a bipolar plate, and thereafter the coating over the lands of the bipolar plate are etched back;
[00032] Figure 12 is a plan view of a system for depositing the various layers on the bipolar plates according to one embodiment of the invention; and
[00033] Figure 13 illustrates a plasma assisted chemical vapor deposition reaction chamber useful in a process according to one embodiment of the invention.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS [00034] The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
[00035] One embodiment of the invention includes a fuel cell component having a substrate, such as, but not limited to, a bipolar plate having a coating thereon. In one embodiment, the coating is hydrophilic and includes at least one Si-O group, at least one polar group and at least one group including a saturated or unsaturated carbon chain. In one embodiment of the invention, the polar group may include a hydroxyl or chloride. In one embodiment of the invention, the carbon chain may be saturated or unsaturated and may have between 1 to 4 carbon atoms. The coating may have addition elements or compounds, including, for example, Au, Ag, Ru, Rh, Pd, Re, Os, Ir, Pt, rare earth metals, alloys thereof, polymeric carbon or graphite to improve conductivity. [00036] In one embodiment of the invention, the coating includes a
Si-O group and an Si-R group wherein R includes a saturated or unsaturated
carbon chain, and wherein the molar ratio of Si-R groups to Si-O groups ranges from 1/8 to Vz, preferably % to 1/2. In another embodiment of the invention, the coating further includes hydroxyl groups to improve the hydrophilicity of the coating.
[00037] Another embodiment of the invention includes a fuel cell component having a component with a coating thereon, and wherein the coating is derived from a siloxane. The siloxane may be linear, branched or cyclic. In one embodiment the siloxane has the formula R 2 SiO and wherein R is an alkyl group.
[00038] Another embodiment of the invention includes a fuel cell component having a component with a coating thereon, and wherein the coating is derived from a material having the formula
R 3 Re wherein Ri, R 2 , R 3 , R 4 , R 5 , and Re, each may be H, O, Cl, or a saturated or unsaturated carbon chain having 1 to 4 carbon atoms, and wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , may be the same or different.
[0039] Another embodiment of the invention includes a product comprising a fuel cell component having a coating formed thereon and wherein the coating is formed by a process comprising plasma enhanced chemical vapor deposition of the coating from a precursor gas comprising a material having the formula
Ri R4
R 2
- Si - O - Si - R 5
wherein R 1 , R 2 , R3, R4, Rs, and R 6 , each may be H, O, Cl, or a saturated or unsaturated carbon chain having 1 to 4 carbon atoms, and wherein Ri , R 2 , R3, R 4 , R 5 , and Re, may be the same or different, and further comprising treating the plasma enhanced chemical deposition deposited coating to provide polar groups. In another embodiment of the invention, at least one of R-i, R 2 , R3, R 4 , Rs, or R 6 is a carbon chain with at least one carbon atom.
[00040] Another embodiment of the invention includes post-treating the plasma enhanced chemical deposition deposited coating comprising subjecting the plasma enhanced CVD deposited coating to a plasma comprising oxygen to produced hydroxyl groups in the plasma enhanced CVD deposited coating.
[00041] Another embodiment of the invention includes a fuel cell component having a coating thereon, wherein the coating includes nanopaticles having a size ranging from 1 to 100 nanometers, preferably 1-50, and most preferably 1-10 nanometers, and wherein the nanoparticles comprises a
compound comprising silicon, a saturated or unsaturated carbon chain and a polar group.
[00042] Another embodiment of the invention includes a fuel cell having a bipolar plate with a hydrophilic coating thereon, and a difussion media positioned adjacent the bipolar plate. The hydrophilic coating includes nodule shaped nanoparticles and the coating is sufficient porous so that fibers from a diffusion media position adjacent the coating on the bipolar plate extend though the coating to provide an electrical path through the coating from the bipolar plate to the diffusion media.
[00043] In one embodiment of the invention, the coating is a siloxane-like (SiO x ) material that is applied through a three-step process which enhances adhesion to the plate material and the material hydrophilicity through introduction of hydroxyl groups (i.e., Si-OH bonds). The Fourier-transform infrared (FTIR) spectrum of the optimized material is shown in Figure 1 , with the key functional bonds identified. Adjustment of the ratio of precursor and carrier gas flows affords control of the Si-CH3 content, shown in Figure 1 as a "shoulder" on the left-hand side of the main Si-O-Si peak. This aspect of the chemical structure controls the resulting coating morphology, with the preferred formulation achieved with a precursor gas hexamethyl disiloxane (HMDSO) volumetric flow of 8-10% of the carrier gas (oxygen) flow. The microscopic structure of the coating, illustrated in a scanning electron microscope (SEM) image in Figure 4, is rather discontinuous and comprised of distinct nodules. This porous structure affords penetration of the fibers of the gas diffusion medium (fibers approximately
7 μm mean diameter) through the coating to so that intimate contact can be made with the base bipolar plate material. The additional resistance introduced by the hydrophilic coating is approximately 10 mω cm 2 , has been achieved. This preferred material formulation has been used on bipolar plates run a stack for over 1000 hours. Measurements of the coating thickness acquired from one of the plates after 534 hours of operation indicated that the material loss was less than 20% within the cathode channels, where most of the product water is known to reside and have the most significant influence on the stack voltage stability at low load. It has been demonstrated than this material loss to zero coating thickness has survived for more than 5000 hours of fuel cell operation. [00044] Hydrophilic coating may also required on the anode side of the bipolar plates, because anode water accumulation is known to influence operational stability under some conditions, and is suspected to impact electrode and membrane durability through hydrogen starvation. However, it is expected that the rate of coating dissolution on the anode side will be faster than on the cathode side as a result of higher HF concentration. Therefore, the anode coating may be thicker than the cathode coating to achieve durability to the end of fuel cell life. In one embodiment of the invention, the mean anode coating thickness is approximately 15% greater than the mean cathode coating thickness. Although the plasma-enhanced CVD conditions were maintained constant throughout the coating process, the anode coating is naturally thicker because of fewer channels in the active area which lowers the total plate surface area. Post-mortem visual inspection of hydrophilically coated plates indicated
that the loss of SiOx material was most significant on the anode side, especially in the vicinity of the 90 Q bends upstream of the anode outlet header. Therefore, the preferred anode coating would be thicker than the cathode coating by more than 15%, which would likely require adjustment of the CVD coating parameters. [00045] A pre-treatment process is required to remove organic contaminants residing on the base plate material as a result of the plate manufacturing process or handling between the plate manufacture and coating processes. Additionally, the pre-treatment operation should be selected to attach polar groups to the base plate material to enhance the effectiveness of the subsequent deposition process. The pre-treatment process involves exposure to a microwave-generated oxygen plasma environment for 0 to 5 minutes, preferably: 0.5 to 3 minutes; and most preferably: 1 minute. [00046] In one embodiment of the invention, the precursor gas is preferably hexamethyl disiloxane (HMDSO), but can be selected from among inorganic or organic derivatives from siloxanes, silanols or silanes based chemistry, or other carbon and/or silicon containing gases and/or liquids. In one embodiment of the invention, the coating process involves micro-wave plasma- enhanced chemical vapor deposition (CVD) using hexamethyl disiloxane (HMDSO) precursor and pure oxygen as a carrier gas, which results in a siloxane-like (SiOx) coating. The microwave frequency may be fixed at 2.45 GHz. The process temperature may be relatively low, in the range of ambient to 45 Q C, so that any practical bipolar plate material can be coated without concerns of thermal damage or distortion. The actual application of the hydrophilic coating
material, and its resulting chemical and physical structure, is controlled by the six adjustable process parameters associated with the coating apparatus, in this case the PLASMAtech Model 110: operated at a pressure ranging from 0 to 500 Pa; preferably: 10 to 100 Pa; and most preferably: 30 Pa.; at a microwave power ranging from 50 W to 10 kW, preferably: 100 W to 1 kW, and most preferably: 200 to 300 W for a CVD reactor with volume of 110 liters. The precursor gas is preferably hexamethyl disiloxane (HMDSO), but can be selected from among inorganic or organic derivatives from siloxanes, silanols or silanes based chemistry, or other carbon and/or silicon containing gases and/or liquids as described above. The carrier gas is preferably oxygen, but may include at least one of nitrogen, nitrous oxide, argon, argon-oxygen, or their mixtures, or mixtures with other gases in appropriate ratios.
[00047] The ratio of precursor-to-carrier gas volumetric flow rate has a significant effect on the resulting chemical structure and morphology of the coated layer. In general, particularly with a siloxane-containing precursor, a small precursor-to-carrier ratio will result in a denser coating that approaches the chemical structure of pure Siθ 2 - As this ratio is increased, the organic content of the coating increases, which most likely reduces the hydrophilicity (i.e., increases static contact angle) but also increases the porosity of the coating structure. It is the balance of these characteristics that is critical for application in a fuel cell, to attain the required contact angle, while also minimizing the added electrical resistance.
[00048] The change in the chemical structure of the SiO x coating with variation of precursor-to-carrier gas ratio can be understood through changes observed in the Fourier-transform infrared (FTIR) spectra illustrated in Figures 1 through 3. In Figure 1 , for a gas ratio of 4-5%, the coating approaches the structure of pure quartz, with no apparent Si-CH 3 content. As the precursor flow is increased to 8-10% of the carrier flow, a small "shoulder" peak appears on the left side of the main Si-O-Si peak, representing a relatively low Si-CH 3 content (Figure 2). As the gas ratio is increased further to about 12-15%, the Si- CH 3 content clearly increases even more (Figure 3). Of these three gas flow combinations, it was determined that the 8-10% ratio provided the preferred characteristic of both very low static contact angle (< 10 9 ) and, by virtue of the discontinuous physical structure, added electrical resistance of only about 10 mω cm 2 .
[00049] In one embodiment of the invention, the precursor-to-carrier flow ratio of 2 to 16%, preferably: 4 to 12%, and most preferably: 8 to 10%. [00050] The absolute gas flow rates will be functions of the total reactor volume. For the PLASMAtech Model 110 used to produce the bipolar plate coatings described herein, the gas flow ranges (assuming a gas flow ratio of 8 to 10% as discussed above) are as follows: Applicable ranges: Precursor = 2 - 50 ml/min; Carrier = 20 - 625 ml/min, preferably: Precursor = 10 - 30 ml/min; Carrier = 100 - 375 ml/min, and most preferably: Precursor = 15 - 20 ml/min; Carrier = 150 - 250 ml/min.
[00051] The reactor time will dictate the thickness of the coated layer, but may also impact the coating morphology. The time may be selected to produce a coating that is thick enough to accommodate the rate of material dissolution in the dilute HF environment within the fuel cell to end-of-life. Conversely, the coating should be thin enough, with the preferred discontinuous morphology, to minimize the added electrical resistance. This combination of coating characteristics was optimized by using a reactor time of 4 minutes per side of the bipolar plates, to produce a coating with mean thickness of 80 - 100 nm. A scanning electron micrograph of the preferred coating is illustrated in Figure 4.
[00052] If the work piece to which the coating is to be applied is predominately planar, spatially uniform coating thickness can be achieved by using a steady-state plasma. However, if there are features on the work piece that are at different distances from the plasma source, as in the case of the bipolar plate channels, it is expected that there would be a variation in the plasma density and hence the resulting coating thickness. In one embodiment of the invention, for a steady-state microwave plasma, the coating thickness in the bottom of the channels (depth = 290 μm; width-to-depth aspect ratio = 1.9) is about 60% of the coating thickness on the lands. This coating thickness variation between lands and channel can be improved further by using microsecond to nanosecond pulses of the plasma power supply. Also, as the channel aspect ratio and/or absolute depth get smaller (as is currently being considered for future stack designs), the coating thickness non-uniformity would become even
more significant. These coating variations can be avoided by using micro to nano second pulses of the plasma power supply.
[00053] A post-treatment process may be required to introduce polar functional moieties (predominantly hydroxyl groups) onto the base SiO x structure, thereby further enhancing the material hydrophilicity. In one embodiment of the invention, this is done by exposing the SiO x films to a reactive oxygen plasma which would activate the SiO x coating by breaking organic bonds and forming hydroxyl, carboxyl and aldehyde functional groups. This activation by post - treatment also enhances the material porosity, which may further reduce the electrical resistance. In another embodiment, the coating is reacted with a chemical to produce the polar groups. In another embodiment, the polar groups are introduced by applying a thin layer of a hydrophilic coating. [00054] In one embodiment of the invention, the post-treatment process involves exposure to a microwave-generated oxygen plasma environment for 0 to 5 minutes, preferably: 0.5 to 3 minutes, and most preferably: 1.5 minutes.
[00055] Figure 5 is a cross-sectional view of a fuel cell 10 that is part of a fuel stack of the type discussed above. The fuel cell 10 includes a cathode side 12 and an anode side 14 separated by an electrolyte membrane 16. A cathode side diffusion media layer 20 is provided on the cathode side 12, and a cathode side catalyst layer 22 is provided between the membrane 16 and the diffusion media layer 20. Likewise, an anode side diffusion media layer 24 is provided on the anode side 14, and an anode side catalyst layer 26 is provided
between the membrane 16 and the diffusion media layer 24. The catalyst layers 22 and 26 and the membrane 16 define an MEA. The diffusion media layers 20 and 24 are porous layers that provide for input gas transport to and water transport from the MEA. Various techniques are known in the art for depositing the catalyst layers 22 and 26 on the diffusion media layers 20 and 24, respectively, or on the membrane 16. The fuel cell 10 may include additional layers and/or coatings, such as, but not limited to, microporous layers. [00056] A cathode side flow field plate or bipolar plate 18 is provided on the cathode side 12 and an anode side flow field plate or bipolar plate 30 is provided on the anode side 14. The bipolar plates 18 and 30 are provided between the fuel cells in the fuel cell stack. A hydrogen reactant gas flow from flow channels 28 in the bipolar plate 30 reacts with the catalyst layer 26 to dissociate the hydrogen ions and the electrons. Airflow from flow channels 32 in the bipolar plate 18 reacts with the catalyst layer 22. The hydrogen ions are able to propagate through the membrane 16 where they electro-chemically react with the oxygen in the airflow and the return electrons in the catalyst layer 22 to generate water as a by-product.
[00057] In this non-limiting embodiment, the bipolar plate 18 includes two sheets 34 and 36 that are stamped and welded together. The sheet 36 defines the flow channels 32 and the sheet 34 defines flow channels 38 for the anode side of an adjacent fuel cell to the fuel cell 10. Cooling fluid flow channels 40 are provided between the sheets 34 and 36, as shown. Likewise, the bipolar plate 30 includes a sheet 42 defining the flow channels 28, a sheet 44 defining
flow channels 46 for the cathode side of an adjacent fuel cell, and cooling fluid flow channels 48. In the embodiments discussed herein, the sheets 34, 36, 42 and 44 are made of an electrically conductive material, such as stainless steel, titanium, aluminum, polymeric carbon composites, etc.
[00058] According to one embodiment of the invention, the bipolar plates 18 and 30 include a coating 50 that makes the plates 18 and 30 hydrophilic. The hydrophilicity of the coating 50 causes the water within the flow channels 28 and 32 to form a film instead of water droplets so that the water does not significantly block the flow channels. Particularly, the hydrophilicity of the coating 50 decreases the contact angle of water accumulating within the flow channels 32, 38, 28 and 46, preferably below 40 9 , so that the reactant gas is still able to flow through the channels 28 and 32 at low loads. In one embodiment, the coating 50 is a thin film, for example, in the range of 5 to 50 nm, so that the conductivity of the sheets 34, 36, 42 and 44 still allows electricity to be effectively coupled out of the fuel cell 10.
[00059] According to another embodiment of the invention, the coating 50 is combined with a conductive material, such as ruthenium oxide or gold, that increases the conductivity of the coating 50. By making the bipolar plates 18 and 30 more conductive, the electrical contact resistance and the ohmic losses in the fuel cell 10 are reduced, thus increasing cell efficiency. Also, a reduction in compression force in the stack can be provided, addressing certain durability issues within the stack.
[00060] Before the coating 50 is deposited on the bipolar plates 18 and 30, the bipolar plates 18 and 30 may be cleaned by a suitable process, such as ion beam sputtering, to remove the resistive oxide film on the outside of the plates 18 and 30 that may have formed. The coating 50 material can be deposited on the bipolar plates 18 and 30 by any suitable technique including, but not limited to, physical vapor deposition processes, chemical vapor deposition (CVD) processes, thermal spraying processes, sol-gel, spraying, dipping, brushing, spinning on, or screen printing. Suitable examples of physical vapor deposition processes include electron beam evaporation, magnetron sputtering and pulsed plasma processes. Suitable chemical vapor deposition processes include plasma enhanced CVD and atomic layer deposition processes. CVD deposition processes may be more suitable for the thin film layers of the coating 50.
[00061] Figure 6 is a broken-away, cross-sectional view of a bipolar plate 60 including reactant gas flow channels 62 and lands 64 therebetween, according to another embodiment of the invention. The bipolar plate 60 is applicable to replace the bipolar plate 18 or 30 in the fuel cell 10. In this embodiment, a coating 50 is deposited as random islands 68 on the plate 60 so that the conductive material of plate 60 is exposed at areas 70 between the islands 68. The coating islands 68 provide the desired hydrophilicity of the plate 60, and the exposed areas 70 provide the desired conductivity of the plate 60. In this embodiment, the islands 68 may best be deposited by a physical vapor deposition process, such as electron beam evaporation, magnetron sputtering
and pulsed plasma processes. In one embodiment, the islands 68 are deposited to a thickness between 50 and 100 nm.
[00062] Figure 7 is a broken-away, cross sectional view of a bipolar plate 72 including reactant gas flow channels 74 and lands 76 therebetween, according to another embodiment of the invention. In this embodiment, a coating 78 is deposited on the bipolar plate 72. The coating 78 is then removed over the lands 76 by any suitable process, such as polishing or grinding, to expose the conductive material of the plate 72 at the lands 76. Therefore, the flow channels 74 include the hydrophilic coating, and the lands 76 are conductive so that electricity is conducted out of a fuel cell. In this embodiment, the coating 78 can be deposited thicker than the embodiments discussed above, such as 100 nm to 1//, because the plate 72 can be less conductive in the channels 74.
[00063] Figure 8 is broken-away, cross-sectional view of a bipolar plate 82 including reactant gas flow channels 74 and lands 76, according to another embodiment of the present invention. In this embodiment, the bipolar plate 82 has an electrically conductive protective layer 52 thereon. A coating 78 according to the present invention is provide overlying only the channels 74 of the bipolar plate 82.
[00064] Figure 9 illustrates one embodiment of a process according to the present invention including first selectively forming a mask 200 over the lands 76 of a bipolar plate 18 and thereafter depositing a coating 50, which may include silicon, over the bipolar plate18 including the mask 200. The mask 200
may be a hard physical mask, a viscous liquid or gel like material, or a removable material such as a photoresist. As shown in Figure 10, the mask 200 over the lands 76 is removed to leave the coating 50 only overlying the channel 74 of the bipolar plate 18.
[00065] Figure 11 illustrates one embodiment of the invention including a process including first depositing a coating 50 including silicon over the bipolar plate 18 including the lands 76 and channels 74, then selectively forming a mask 200, such as a photoresist or water soluble material, over the channels 74 of a bipolar plate, and thereafter the coating 50 over the lands 76 of the bipolar plate are etched back. The etch may be accomplished using a wet or dry etch process provide the etching does not damage the bipolar plate 18. In one embodiment the coating 50 over the lands may be remove by an argon plasma and thereafter any remaining portion of the mask is removed. [00066] Figure 12 is a plan view of a system 100 for depositing the various layers on the bipolar plates discussed above. The system 100 is intended to represent any of the techniques mentioned above, including, but not limited to, blasting, physical vapor deposition processes, chemical vapor deposition processes, thermal spraying processes and sol-gel. In the system 100, an electron gun 102 heats a material 104 that causes the material 104 to be vaporized and deposited on a substrate 106, representing the bipolar plate, to form a coating 108 thereon. In another process, the system 100 includes an ion gun 110 that directs a beam of ions to a sputtering surface 112 that releases material, such as a metal oxide, to deposit the coating 108. In another
embodiment, the coating 50 may be applied by spraying, dipping, brushing, spinning on, or screen printing.
[00067] Figure 13 illustrates one embodiment of a plasma assisted chemical vapor deposition reactor 400 useful in a process according to the present invention. The reactor 400 includes a plurality of walls 402 and a ceiling 404. A plurality of gas charging ports 406, 408, 410 may be provided through the walls 402 or ceiling 404 for charging reaction and carrier gases into the reactor chamber 412. A liquid charging dispenser 414 may also be provided. The reactor may include a microwave generating means 416 and an Rf generating means 418 to produce a plasma in the reactor chamber 412. A chuck 420 may be provided to support a fuel cell component such as a bipolar plate. [00068] In another embodiment of the invention a coating having Si-
O and Si-R (where R is a saturated or unsaturated carbon chain) groups are selectively deposited on a flat substrate such as a foil of stainless steel and there after formed, for example by stamping, into a bipolar plate having a gas flow field including a plurality of lands and channels, and wherein the coating is deposited in the channels.
[00069] In another embodiment of the invention, a coating having Si-
O and Si-R (where R is a saturated or unsaturated carbon chain) groups may be formed on a substrate using a variety of chemistries including material comprising Si and materials including carbon. For example, the coating may be produced using plasma assisted CVD with silane (SiH 4 ), oxygen and a carbon based gas of liquid. In another embodiment, the coating may be produced using
plasma assisted CVD with TEOS which is tetraethyloxysilate or tetraethoxysilane (Si(C 2 H 5 O^), or MTEOS which is methyltriethoxysilane, and oxygen or ozone, and optionally a carbon based gas of liquid. [00070] The term "plasma assisted chemical vapor deposition" means chemical vapor deposition using a plasma and includes plasma enhanced CVD and high density plasma CVD. When the terms "over", "overlying", "overlies" or the like are used herein with respect to the relative position of layers to each other, such shall mean that the layers are in direct contact with each other or that another layer or layers may be interposed between the layers. [00071] The description of the invention is merely exemplary in nature and, thus, variations thereof are not to be regarded as a departure from the spirit and scope of the invention.