Patent Application
20080023320
A method for manufacturing a separator according to the present invention will be described in detail below with reference to the accompanying drawings.
A separator produced by a manufacturing method according to a first embodiment will first be described based on
The fuel cell 10 shown in
The MEA 12 comprises positive and negative electrode layers 15 and 16 disposed on both sides of an electrolyte membrane 14, a positive-side diffusion layer 17 disposed outside of the positive-electrode layer 15, and a negative-side diffusion layer 18 disposed outside of the negative-electrode layer 16.
The positive-electrode layer 15 and the positive-side diffusion layer 17 are sometimes collectively referred to as “a positive-electrode layer,” and the negative-electrode layer 16 and the negative-side diffusion layer 18 are sometimes collectively referred to as “a positive-electrode layer”.
In the titanium separators 13, oxide films 66 (see
Each of the separators 13 is provided with a plurality of grooves 24 on the surfaces 21, 21 by forming the surfaces 21, 21 into a concavoconvex shape.
The separators 13 are brought into contact with the two surfaces 12a, 12b of the MEA 12, whereby the grooves 24 are blocked off at the two surfaces 12a, 12b of the MEA 12 to form a plurality of gas-conducting channels 25 or a plurality of water-conducting channels 25.
A plurality of convexities 26 on the surfaces 21, 21 of the separators 13 is in contact with the two surfaces 12a, 12b of the MEA 12. It is preferable to thereby minimize the contact resistance (i.e., the electrical resistance) of the convexities 26 (i.e., the surface 21) of the separators 12.
It is also preferable to minimize strain in the separators 12 in order to make the convexities 26 (i.e., the surface 21) on the separators 12 to properly contact the two surfaces 12a, 12b of the MEA 12.
Following is a description of a manufacturing method designed to minimize the contact resistance on the surface 21 of the separators 13 and the strain in the separators 12.
An apparatus for manufacturing a separator according to the invention is first described based on
The apparatus 30 for manufacturing a fuel cell separator shown in
A negative pole 35a of a DC power supply 35 is connected to a support part 33 of the mounting base 32. A positive pole 35b of the DC power supply 35 is connected to the container 31.
A gas source 37 is connected to the interior of the container 31 via a supply channel 38. A first on/off valve 39 is provided midway in the supply channel 38.
A vacuum pump 42 is connected to the interior of the container 31 via a discharge channel 41. A second on/off valve 43 is provided midway in the discharge channel 41.
A heater 45 is disposed on the outside of a wall part 31a of the container 31. A non-contact temperature sensor 46 is disposed so as to face the wall part 31a of the container 31. A gas pressure sensor 47 is disposed in the base 31b of the container 31.
A control unit 48 controls the DC power supply 35, the gas source 37, the vacuum pump 42, and the heater 45 on the basis of detection signals from the temperature sensor 46 and the gas pressure sensor 47.
The mounting base 32 comprises the support part 33 and a mounting plate 34 installed on top of the support part 33. The separator blanks 51 are placed vertically on the mounting plate 34 at prescribed intervals.
The gas source 37 supplies nitrogen (N2) gas (nitriding gas) 55 (see
The nitrogen gas 55 and hydrogen gas 56 may, for example, be in a proportion at which the nitrogen gas/hydrogen gas ratio is 7:3.
The separator manufacturing apparatus 30 is configured so as to generate a glow discharge between the container 31 and the mounting base 32 by placing the separator blanks 51 vertically on the mounting plate 34 at prescribed intervals, supplying the nitrogen gas 55 and hydrogen gas 56 from the gas source 37 into the container 31, and applying a prescribed voltage between the container 31 and the mounting base 32 from the DC power supply 35.
A method for manufacturing a fuel cell separator according to the invention is next described based on
In
In
As shown in
The second on/off valve 43 is subsequently opened and the vacuum pump 42 is driven. The second on/off valve 43 is closed and the vacuum pump 42 is stopped, after which the second on/off valve 43 is opened and the nitrogen gas 55 and hydrogen gas 56 are supplied from the gas source 37 into the container 31 as indicated by arrows a.
The nitrogen gas 55 and hydrogen gas 56 are supplied so that the nitrogen gas 55 and hydrogen gas 56 in the container 31 are in a proportion at which the nitrogen gas/hydrogen gas ratio is, for example, 7:3.
Both a reducing atmosphere and a nitriding atmosphere are thereby created inside the container 31.
The pressure inside the container 31 is detected by the gas pressure sensor 47 and confirmed to be, for example, 67 to 1,333 Pa (0.5 to 10 Torr). The second on/off valve 43 is closed.
The container is heated by the heater 45 so that the treatment temperature reaches 350 to 500° C. The separator blanks 51 are heated to a range of 350 and 500° C.
In this state, a prescribed voltage is applied between the container 31 and the mounting base 32 from the DC power supply 35, whereby a glow discharge is generated between the container 31 and the mounting base 32.
In
The ionized hydrogen ions 56 are moved toward the surface 21 of each of the separator blanks 51 as indicated by arrows b.
The ionized nitrogen ions 55 are moved toward the surface 21 of each of the separator blanks 51 as indicated by arrows c.
In
Sputtering causes the hydrogen ions 56 to react with oxygen 65 in the surface 21 of the separator blank 51 to create water vapor.
The oxide film 66 is removed from the surface 21 of the separator blank 51 by removing the oxygen 65 from the surface 21 as indicated by arrows d.
The nitrogen ions 55 are moved toward the surface 21 of the separator blank 51 as indicated by arrows c, whereby the nitrogen ions 55 are caused to collide with the surface 21 of the separator blank 51, and plasma nitriding is performed.
At this point, the oxide film 66 is removed from the surface 21 of the separator blank 51 by sputtering. The nitrogen 55 is thereby diffused more readily in the surface 21 of the separator blank 51 when the nitrogen ions 55 are caused to collide with the surface 21 of the separator blank 51 by plasma nitriding.
In
The separator 13 is obtained by completing plasma nitriding. The separator 13 is provided with a titanium nitride film 71 obtained by adequately diffusing the nitrogen 55 in the surface 21. The surface 21 of the separator 13 is thereby made less likely to oxidize.
The titanium nitride film 71 preferably has a thickness t2 of 0.1 to 3.0 μm. The titanium nitride film 71 is too thin to minimize the oxide film (natural oxide film) 66 when the film thickness t2 is less than 0.1 μm. The film thickness t2 is set to 0.1 μm or greater to minimize the oxide film (natural oxide film) 66.
On the other hand, when the film thickness t2 exceeds 3.0 μm, the titanium nitride film 71 is too thick to secure the toughness that is necessary for the separator. In addition, too much time is required to perform plasma nitriding, and it is more difficult to achieve increased productivity. The film thickness t2 is therefore set to 3.0 μm or less to provide the separator with the desired brittleness and to ensure the desired productivity.
In
The surface 21 of the separator 13 is less likely to oxidize, and formation of the oxide film (natural oxide film) 66 can be inhibited because the titanium nitride film 71 is formed on the surface 21 of the separator 13. The oxide film 66 is thereby kept extremely thin and stable at a thickness t3 of 0 to 1 nm.
The treatment temperature, i.e., the heating temperature of the separator blank 51 (see
The reason that the heating temperature (treatment temperature) was reduced to a range of 350 to 500° C. during the plasma nitriding treatment will be described herein.
The heating temperature is too low and the nitrogen 55 cannot be adequately diffused in the surface 21 of the separator 13 when the heating temperature is less than 350° C. The heating temperature was therefore set at 350° C. or greater to allow the nitrogen 55 to be adequately diffused in the surface 21 of the separator 13.
The heating temperature is too high and strain may develop in the separator 13 when the heating temperature exceeds 500° C. The heating temperature was therefore set at 500° C. or less to prevent strain from developing in the separator 13.
An example in which a separator produced by the method for manufacturing a fuel cell separator is used in a fuel cell will be next described based on
In
A surface 21 (specifically convexities 26) of one of the separators 13 is brought into contact with the side 12a of the MEA 12, and a surface 21 (specifically convexities 26) of the other separator 13 is brought into contact with the other side 12b of the MEA 12.
The heating temperature of a separator blank 51 (see
The surfaces 21, 21 (convexities 26) of the separators 13 can thereby form uniform contact with the two sides 12a, 12b of the MEA.
In
The reasons for setting the treatment temperature of plasma nitriding to a range of 350 to 500° C. will be described based on Table 1, comparative examples 1 through 7 shown as a graph in
The treatment temperature has minimal effect on the sputtering treatment, and the treatment temperature needs to be considered only for the plasma nitriding treatment.
The titanium separators of comparative examples 1 through 7 and examples 1 through 4 are as described below:
Comparative example 1 is an example in which the titanium separators were subjected neither to sputtering nor to plasma nitriding.
Comparative example 2 is an example in which a container was filled 100% with nitrogen gas, and the titanium separators were subjected to plasma nitriding at a treatment temperature of 350° C. The treatment time was five hours.
Comparative example 3 is an example in which the container was filled 100% with nitrogen gas, and the titanium separators were subjected to plasma nitriding at a treatment temperature of 400° C. The treatment time was five hours.
Comparative example 4 is an example in which the container was filled 100% with nitrogen gas, and the titanium separators were subjected to plasma nitriding at a treatment temperature of 500° C. The treatment time was five hours.
Comparative example 5 is an example in which the container was filled 100% with nitrogen gas, and the titanium separators were subjected to plasma nitriding at a treatment temperature of 800° C. The treatment time was five hours.
Comparative example 6 is an example in which the container was filled 70% with nitrogen gas and 30% with hydrogen gas, and the titanium separators were subjected to sputtering and plasma nitriding at a treatment temperature of 250° C. The treatment time was five hours.
Comparative example 7 is an example in which the container was filled 70% with nitrogen gas and 30% with hydrogen gas, and the titanium separators were subjected to sputtering and plasma nitriding at a treatment temperature of 800° C. The treatment time was five hours.
Example 1 is an example in which the container was filled 70% with nitrogen gas and 30% with hydrogen gas, and the titanium separators were subjected to sputtering and plasma nitriding at a treatment temperature of 350° C. The treatment time was five hours.
Example 2 is an example in which the container was filled 70% with nitrogen gas and 30% with hydrogen gas, and the titanium separators were subjected to sputtering and plasma nitriding at a treatment temperature of 370° C. The treatment time was five hours.
Example 3 is an example in which the container was filled 70% with nitrogen gas and 30% with hydrogen gas, and the titanium separators were subjected to sputtering and plasma nitriding at a treatment temperature of 400° C. The treatment time was five hours.
Example 4 is an example in which the container was filled 70% with nitrogen gas and 30% with hydrogen gas, and the titanium separators were subjected to sputtering and plasma nitriding at a treatment temperature of 500° C. The treatment time was five hours.
Both the strain and the contact resistance (mΩ·cm2) of the separators of comparative examples 1 through 7 and examples 1 through 4 were evaluated, and overall evaluations were made based on both of the evaluations.
Evaluation criteria for the strain were set in such a way that cases in which the strain was identified as beyond the allowable limits as a result of visual inspection of the strain in the titanium separators were evaluated as “×,” cases in which the strain was identified as within the allowable limits were evaluated as “Δ”, and cases in which the strain was minimal were evaluated as “◯.” The evaluations “◯” and “Δ” were “good,” and the evaluation “×” is “poor.”
Evaluation criteria for the contact resistance were set in such a way that cases in which the contact resistance of the separators exceeded 16.9 mΩ·cm2 were evaluated as “poor,” and cases in which the contact resistance was 16.9 mΩ·cm2 or less were evaluated as “good.”
The reasons for setting the evaluation criterion for the contact resistance at 16.9 mΩ·cm2 will be described below.
Performing plasma nitriding on the surfaces of a titanium separator is believed to minimize the contact resistance of the separator.
As described in the background art, the plasma nitriding process requires a heating temperature to be approximately 700° C. for oxygen to properly diffuse in a separator surface.
Contact resistance obtained by performing the plasma nitriding process at a heating temperature of 700° C. can therefore be chosen as the criterion for the contact resistance. However, the conditions were set more rigorously in this case, and the contact resistance obtained by performing the plasma nitriding process at a heating temperature of 800° C., i.e., the contact resistance of 16.9 mΩ·cm2 obtained by performing the plasma nitriding process under the conditions in comparative example 5, was chosen as the evaluation criterion.
Thus, the overall evaluations were “◯” (“good”) in cases in which the evaluation criterion for the strain was “good” and in which the evaluation criterion for the contact resistance was also “good.” The overall evaluations of all other cases were “×” (“poor”).
Conditions for measuring contact resistance are as described below.
The positive-side diffusion layer 17 and the negative-side diffusion layer 18 shown in
One separator 13 was sandwiched between two sheets of carbon paper, and contact resistance was measured when a contact pressure of 10 kgf/cm2 was applied by sandwiching the separator 13. The evaluation of good or poor was made based on the measured contact resistance.
In other words, a contact resistance of 16.9 mΩ·cm2 was a value achieved when the sheets of carbon paper were brought into contact with both sides of the separator 13.
The fuel cell element 11 shown in
The evaluation results are described below.
Comparative example 1: The strain was minimal, and the evaluation of the strain was “◯.” The contact resistance was 197 mΩ·cm2, which was greater than the evaluation criterion (16.9 mΩ·cm2), and the evaluation of the contact resistance was therefore “×.” The overall evaluation was “×” (“poor”) because the evaluation of the contact resistance was “×.”
Comparative example 2: The strain was minimal, and the evaluation of the strain was therefore “◯.” The contact resistance was 93.4 mΩ·cm2, which was greater than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “×.” The overall evaluation was “×” because the evaluation of the contact resistance was “×.”
Comparative example 3: The strain was minimal, and the evaluation of the strain was therefore “◯.” The contact resistance was 67.45 mΩ·cm2, which was greater than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “×.” The total evaluation was “×” because the evaluation of the contact resistance was “×.”
Comparative example 4: The strain was within the allowable range, and the evaluation of the strain was therefore “Δ.” The contact resistance was 22 mΩ·cm2, which was greater than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “×.” The total evaluation was “×” because the evaluation of the contact resistance was “×.”
Comparative example 5: The strain exceeded the allowable range, and the evaluation of the strain was therefore “×.” The evaluation was based on contact resistance (16.9 mΩ·cm2), and the evaluation of the contact resistance was therefore “◯.” The total evaluation was “×” because the evaluation of the strain was “×.”
Comparative example 6: The strain was minimal, and the evaluation of the strain was therefore “◯.” The contact resistance was 54.5 mΩ·cm2, which was greater than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “×.” The overall evaluation was “×” because the evaluation of the contact resistance was “×.”
Comparative example 7: The strain exceeded the allowable range, and the evaluation of the strain was therefore “×.” The contact resistance was 5.03 mΩ·cm2, which is less than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “◯.” The overall evaluation was “×” because the evaluation of the strain is “×.”
Example 1: The strain was minimal, and the evaluation of the strain was therefore “◯.” The contact resistance was 14.65 mΩ·cm2, which is less than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “◯.” The overall evaluation was “◯” (“good”) because the evaluations of the strain and contact resistance were “◯.”
Example 2: The strain was minimal, and the evaluation of the strain was therefore “◯.” The contact resistance was 9.87 mΩ·cm2, which is less than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “◯.” The overall evaluation was “◯” because the evaluations of the strain and contact resistance were “◯.”
Example 3: The strain was minimal, and the evaluation of the strain was therefore “◯.” The contact resistance was 5.38 mΩ·cm2, which is less than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “◯.” The overall evaluation was “◯” because the evaluations of the strain and contact resistance were “◯.”
Example 4: The strain was within the allowable range, and the evaluation of the strain was therefore “Δ.” The contact resistance was 5.35 mΩ·cm2, which is less than 16.9 mΩ·cm2, and the evaluation of the contact resistance was therefore “◯.” The overall evaluation was “◯” because the evaluations of the strain and contact resistance were “Δ” and “◯.”
Graph g1 represents a relationship between the contact resistance and the treatment temperatures of comparative examples 2 through 5, and graph g2 represents a relationship between the contact resistance and the treatment temperatures of comparative examples 6 and 7, and examples 1 through 4.
It follows from graphs g1 and g2 that it is in examples 1 through 4 and comparative example 7 that the contact resistance could be reduced to or below the evaluation criterion (16.9 mΩ·cm2) of comparative example 5.
In comparative example 7, the treatment temperature is high at 800° C., and the strain in the separator therefore exceeds the allowable range. As a result, it is understood that examples 1 through 4 are cases in which the contact resistance can be reduced to the evaluation criterion (16.9 mΩ·cm2) or less, and the strain in the separator can be properly minimized.
The treatment temperature of example 1 is 350° C., the treatment temperature of example 2 is 370° C., the treatment temperature of example 3 is 400° C., and the treatment temperature of example 4 is 500° C. It is thereby understood that contact resistance can be reduced to a desirable value by setting the treatment temperature of plasma nitriding to a range of 350 to 500° C.
It is also understood from Table 1 that the strain in the separator can be minimized by setting the treatment temperature of plasma nitriding to the range of 350 to 500° C.
A method for manufacturing a separator according to the second embodiment of the invention is described next based on
As shown in
As shown in
In
The second on/off valve 43 is subsequently opened and the vacuum pump 42 is actuated. The second on/off valve 43 is closed and the vacuum pump 42 is stopped, after which the second on/off valve 43 is opened and hydrogen gas 56 is supplied from the gas source 37 into the container 31 as indicated by arrows e. A reducing atmosphere is thereby created in the container 31. In this state, a prescribed voltage is applied between the container 31 and the mounting base 32 from the DC power supply 35, whereby a glow discharge is generated between the container 31 and the mounting base 32.
In
Sputtering causes the hydrogen ions 56 to react with oxygen 65 in the surface 21 to create water vapor. The oxide film 66 is removed from the surface 21 of the separator blank 51 by removing the oxygen 65 from the surface 21 as indicated by arrows g.
In
The second on/off valve 43 is closed and the vacuum pump 42 is stopped, after which the second on/off valve 43 is opened and the nitrogen gas 55 is supplied from the gas source 37 into the container 31 as indicated by the arrows h. A nitriding atmosphere is thereby created in the container 31.
The pressure inside the container 31 is detected by the gas pressure sensor 47 and confirmed to be, for example, 67 to 1333 Pa (0.5 to 10 Torr). The second on/off valve 43 is closed.
The container is heated by the heater 45 so that the treatment temperature reaches 350 to 500° C. The separator blank 51 is heated to a range of 350 to 500° C.
In this state, a prescribed voltage is applied between the container 31 and the mounting base 32 from the DC power supply 35, whereby a glow discharge is generated between the container 31 and the mounting base 32.
In
At this point, an oxide film 66 is removed from the surface 21 of the separator blank 51 by sputtering as described with reference to
In
The separator 13 is obtained by completing the plasma nitriding treatment. The separator 13 is provided with a titanium nitride film 71 obtained by adequately diffusing the nitrogen 55 in the surface 21. The surface 21 of the separator 13 will be less likely to oxidize as a result.
The titanium nitride film 71 preferably has a thickness t2 of 0.1 to 3.0 μm, in a manner similar to that of the first embodiment.
If the film thickness t2 is less than 0.1 μm, the titanium nitride film 71 will be too thin to minimize the oxide film (natural oxide film) 66. The film thickness t2 is set to 0.1 μm or greater to minimize the oxide film (natural oxide film) 66.
On the other hand, if the film thickness t2 exceeds 3.0 μm, the titanium nitride film 71 will be too thick to ensure the toughness required of the separator. In addition, too much time is required to perform plasma nitriding, and complications are encountered in achieving increased productivity. The film thickness t2 is therefore set to 3.0 μm or less, to ensure the toughness for the separator and productivity.
In
The titanium nitride film 71 will be formed on the surface 21 of the separator 13; therefore, oxidation on the surface 21 of the separator 13 will tend not to occur, and it will be possible to prevent the oxide film 66 (natural oxide film) from forming. Accordingly, the oxide film 66 will be stably held at a very small thickness t3 of 0 to 1 nm.
According to the method for manufacturing a fuel cell separator of the second embodiment, the step of manufacturing the separator 13 can be simplified by performing plasma nitriding at the same time that sputtering is performed. The manufacturing time of the separator 13 can thereby be reduced and productivity can be increased.
According to the method for manufacturing a separator of the second embodiment, it is possible to minimize the treatment temperature, i.e., the heating temperature relating to the separator blank 51 (see
In the first and the second embodiments, a description was provided with reference to a case wherein hydrogen gas was used as a reducing gas during sputtering, the hydrogen gas was ionized and caused to collide with the oxide film 66, and the hydrogen was reacted with oxygen so that the oxide film was chemically removed. However, the reducing gas is not limited thereto. A halogen gas (HCI, CI2, HF, or the like), ammonia (NH3) gas, argon (Ar) gas, or the like can be used instead of hydrogen gas.
If argon (Ar) gas is used, the argon gas is ionized and caused to collide with the oxide film 66 during sputtering, as a result of which the oxide film will be physically removed. The same effect as the one obtained in the foregoing examples can thereby be exhibited.
The reducing gas can be selected from among hydrogen gas, halide gases, ammonia gas, and a variety of other gases, allowing for increased design flexibility.
In the foregoing examples, a description was provided with reference to a case wherein nitrogen gas was used as a nitriding gas, and the nitrogen gas was ionized and caused to collide with the surface 21 of the separator 13 during plasma nitriding, so that the titanium nitriding film 71 was formed on the surface 21. However, the nitriding gas is not limited thereto. Ammonia (NH3) gas can be used, for example, instead of nitrogen gas. The nitriding gas can be selected from among nitrogen gas, ammonia gas, and the like, allowing for increased design flexibility.
Additionally, if ammonia gas is used as a nitriding gas, the ammonia gas can be also used as a reducing gas, allowing the equipment to be simplified.
In the foregoing examples, furthermore, a description was provided with reference to a case wherein the proportion of nitrogen gas 55 to hydrogen gas 56 in the container 31 was set to be in a nitrogen gas/hydrogen gas ratio of 7:3. However, the ratio of the nitrogen gas and the hydrogen gas is not limited thereto, and any desired ratio can be selected.
In the foregoing examples, a description was also provided for examples wherein the treatment time was set at five hours. However, the treatment time is not limited thereto; any desired treatment time can be selected.
In the second embodiment, a description was also provided for an example wherein a single apparatus 30 for manufacturing a fuel cell separator was used for the sputtering and plasma nitriding treatments. However, the method is not limited thereto; an apparatus for sputtering and an apparatus for plasma nitriding can each be used separately.
The method for manufacturing a fuel cell separator according to the present invention is particularly useful for the manufacture of a titanium separator.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-183817 | Jun 2004 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP05/08841 | 5/10/2005 | WO | 00 | 12/18/2006 |
