Patent Application
20130029252
This application claims priority of Taiwan Patent Application No. 100126739, filed on Jul. 28, 2011, the entirety of which is incorporated by reference herein.
1. Field of the Invention
The present invention relates to an electrocatalyst, and in particular relates to an electrocatalyst used in a fuel cell.
2. Description of the Related Art
Fuel cells have received more and more attention because of their high energy density and eco-friendly character. A fuel cell is a novel energy supply system having high versatility. Through an electrochemical reaction, chemical energy of fuel can promptly be transformed into electricity by a fuel cell when required. Electricity can be generated continuously as long as fuel is supplied. Hydrogen and methanol are the most commonly used fuels for a fuel cell. Since hydrogen and methanol are both renewable energy sources having no environmental pollution, if a fuel cell can be used as a replacement of a petrochemical energy source, the lifetime of remaining petrified energy can be extended. Now, fuel cells are mainly used in automobiles, stationary electrical supply equipment, and portable electronic products. Micro-fuel cells such as a direct-methanol fuel cell (DMFC) used in portable electronic products are the most commercialized and popular products.
A direct-methanol fuel cell is a kind of proton exchange membrane fuel cell (PEMFC.) In the cell, methanol and water are mixed and transferred to an anode, wherein a methanol oxidation reaction (MOR) occurs, thus producing carbon dioxide (CO2), electrons, and protons. The protons and electrons are transferred to a cathode by a proton exchange membrane and external circuit respectively to perform an oxygen reduction reaction with oxygen, thus producing water and a direct current. Since the reactions at the anode and cathode are very slow at low temperature (operation temperature ≦80° C.), catalysts are needed to increase the reaction rate, to achieve the desirable electricity. That is, activity of the catalysts plays a key role that directly affects the efficiency of the cell and viability of commercialization.
Presently, the most efficient anode catalyst (such as PtRu) and cathode catalyst (such as Pt) both use Pt as the main component. However, the PtRu anode catalyst and the Pt cathode catalyst still have some disadvantages. For example, the catalytic performance of the PtRu anode catalyst with methanol is yet unsatisfactory. When the PtRu is used as a bimetal catalyst in a fuel cell, Pt is used to perform a dehyodrogenation reaction with methanol to release carbon monoxide (COads), while Ru is used to catalyze water to release OHad, which is an intermediate for oxidizing carbon monoxide. The COads absorbed on a Pt surface then reacts with adjacent OHads absorbed on an Ru surface to release CO2, thus completing an anode methanol oxidation half reaction. However, since the catalytic activity of Ru with water is yet unsatisfactory, the Pt surface is poisoned by excessive CO, resulting in a decrease of the catalytic activity of the Pt catalyst with methanol.
On the other hand, although Pt is the most efficient catalyst for catalyzing a cathode oxygen reduction reaction, the un-reacted methanol (as described above) may be transferred to the cathode by a proton exchange membrane and may react with the Pt. The Pt and the methanol undergo an oxidation reaction, resulting in an electric potential that reduces the catalytic activity of the catalyst and poisons the Pt surface by CO.
Although some Pd-based catalysts, with lower reactivity to methanol and therefore better resistance to CO poisoning, have been proposed, their oxygen reduction ability is insufficient.
Therefore, a novel anode catalyst with high methanol catalytic activity and good resistance against CO poisoning and a new cathode catalyst with high oxygen reduction reaction activity and good resistance against CO poisoning are required to improve the power generation efficiency of fuel cells.
An embodiment of the invention provides an electrocatalyst, including a four-element catalyst having a formula of XYZP, wherein X is Pt or Pd, Y and Z are different elements selected from Group 6, Group 8, Group 9, or Group 11 elements, and P is phosphorous, wherein Group 6 elements include Cr, Mo, or W, Group 8 elements include Fe, Ru, or Os, Group 9 elements include Co, Rh, or Ir, and Group 11 elements include Cu, Ag, or Au.
Another embodiment of the invention provides a fuel cell, including: a cathode electrode; an anode electrode; an electrolyte disposed between the cathode electrode and the anode electrode; a cathode electrode catalyst layer disposed between the cathode electrode and the electrolyte; and an anode electrode catalyst layer disposed between the anode electrode and the electrolyte, wherein at least one of the cathode electrode catalyst layer and the anode electrode catalyst layer includes the above described electrocatalyst.
A detailed description is given in the following embodiments with reference to the accompanying drawings.
The present invention can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
The following description is of the best-contemplated mode of carrying out the invention. This description is made for the purpose of illustrating the general principles of the invention and should not be taken in a limiting sense. The scope of the invention is best determined by reference to the appended claims.
In the disclosure, a four-element electrocatalyst with improved catalytic activity and stability is provided. The four-element electrocatalyst has a general formula of XYZP, wherein X is Pt or Pd, Y and Z are different elements selected from Group 6, Group 8, Group 9, or Group 11 elements, and P is phosphorous. The Group 6 elements include Cr, Mo, or W. The Group 8 elements include Fe, Ru, or Os. The Group 9 elements include Co, Rh, or Ir. The Group 11 elements include Cu, Ag, or Au.
A cathode electrode catalyst layer is formed by loading (such as adsorbing) a cathode electrode catalyst on a carrier. The cathode electrode catalyst is a four-element catalyst having a formula of XYZP, wherein X is Pd, Y and Z are different elements selected from Group 6 or Group 9 elements, and P is phosphorous. Examples of the cathode electrode catalyst include, but are not limited to, PdCoWP, PdCoCrP, PdCoMoP, PdRhWP, PdRhCrP, PdRhMoP, PdIrWP, PdIrCrP, PdIrMoP, PdCrWP, PdCrMoP, PdMoWP, PdCoRhP, PdCoIrP, or PdRhIrP. An atomic ratio of X:Y:Z:P may be, but are not limited to, between 30-97:1-60:1-50:0.01-30, or between 35-90:5-55:5-40:1-20.
An anode electrode catalyst layer is formed by loading (such as adsorbing) an anode electrode catalyst on a carrier. The anode electrode catalyst is a four-element catalyst having a formula of XYZP, wherein X is Pt, Y and Z are different elements selected from Group 6, Group 8, or Group 11 elements, and P is phosphorous. Examples of the anode electrode catalyst include, but are not limited to, PtRuWP, PtRuMoP, PtRuCrP, PtRuAuP, PtRuAgP, PtRuCuP, PtRuFeP, PtRuOsP, PtFeWP, PtFeMoP, PtFeCrP, PtFeAuP, PtFeAgP, PtFeCuP, PtFeOsP, PtOsWP, PtOsMoP, PtOsCrP, PtOsAuP, PtOsAgP, or PtOsCuP. An atomic ratio of X:Y:Z:P may be, but are not limited to, between 30-70:30-70:0.01-30:0.01-30, or between 35-60:35-60:0.05-20:0.05-20.
In addition, the cathode and anode electrode catalyst are loaded on the carrier, wherein examples of the carrier include, but are not limited to, activated carbon, carbon black, carbon nanoparticles, carbon nanotube, carbon nano-fiber, furnace black, graphitized carbon black, graphite, or combinations thereof. In one embodiment, the carrier may have a surface area between, but not limited to, 10 and 2000 m2/g, and a loading amount of the electrocatalyst loaded on the carrier may be between, but not limited to, 10 and 90%. Any catalyst precursor having the catalyst elements can be used to prepare the catalyst, and it is not limited to the catalyst precursor described in the examples.
Conventionally, the cathode electrode catalyst, such as Pt, may have good catalytic activity at the beginning, but its catalytic activity may decrease, or even completely be lost, because of the CO and/or methanol poisoning. Moreover, Pt is costly which limits its applications. Although Pd is cheaper and may be a substitute for Pt to reduce the cost, the catalytic activity of Pd is too low such that Pd can not be used as a good cathode electrode catalyst. Surprisingly, the oxygen reduction reaction catalytic activity of the four-element catalyst of the invention is higher than that of a commercial Pt catalyst. In addition, the four-element catalysts of the invention have much better CO and/or methanol poisoning resistance. In particular, the four-element catalysts containing Pd, such as PdCoWP, have higher catalytic activity when compared to the two-element or three element catalysts containing Pd, and have very high resistance toward CO and/or methanol poisoning. Moreover, the cost of the four-element catalysts containing Pd described above is only one-third to one-fourth the cost of the commercial Pt catalyst. In conclusion, the catalytic activity, resistance toward CO and/or methanol poisoning, and catalyst stability of the four-element catalysts containing Pd are all superior to that of the commercial Pt catalysts.
Commercial anode electrode catalysts, such as PtRu, do not have sufficient catalytic activity, and also suffer from the problem of CO poisoning. In addition, the catalytic stability of the PtRu is poor, and may lose its catalytic stability after a period of operation time. In comparison, the four-element catalysts of the current invention possess both high catalytic activity and stability and can maintain a desirable catalytic activity after a period of operation time.
Furthermore, the catalyst layer containing the four-element catalysts may only be disposed on one of the anode electrode and the cathode electrode, while on the other electrode, any known electrocatalyst can be disposed thereon.
Ketjen Black ECP300 was used as the catalyst carrier and was dispersed into ethylene glycol. Precursors including PdCl2, Co(NO3)2.6H2O, (NH4)6W12O39.xH2O (Ammonium tungsten oxide hydrate), and NaH2PO2.H2O were weighted (according to Table 1) and dissolved in an NaCl aqueous solution to form an aqueous metal salt solution. The aqueous metal salt solution was added into the ethylene glycol containing the carrier and uniformly dispersed. Then, the solution was stirred by a stirrer and refluxed for 2 hours at 150° C., such that the metal salts were reduced to metal nanoparticles and adsorbed onto the carrier. The temperature of the solution was then lowered to room temperature. The solution was then filtered, and the filter cake was washed with water, resulting in the cathode electrode catalyst of example 1, wherein the atomic ratio of Pd:Co:W:P was 68:15:10:7.
The cathode electrode catalysts of examples 2-4 were also formed by the method described above except that different amounts of metal salt precursors were used (referring to table 1.) In examples 1 and 2, the loading amount of the catalysts on carbon was 65 wt %. In examples 3 and 4, the loading amount of the catalysts on carbon was 40 wt %. Table 1 illustrates the catalytic activity of oxygen reduction reaction (ORR) measured by dispersing the resulting cathode electrode catalysts of examples 1-4 on a rotating glassy carbon electrode, followed by immersing it into a 0.5M of H2SO4(aq) at 40° C. Moreover, commercial Pt catalysts (Johnson Matthey Corp.) with different loading were used as comparative examples 1 and 2. Referring to Table 1, the oxygen reduction reaction catalytic activity of the four-element catalyst PdCoWP, with different atomic ratio and loading amounts, are all higher than those of the commercial Pt catalysts (comparative examples 1 and 2) at a voltage of 0.75V.
In addition, catalysts of examples 1-4 and comparative examples 1-2 were placed into a 1M methanol solution, and were tested for their catalytic activity of oxygen reduction reaction under a methanol environment using rotating glassy carbon electrodes. Table 2 illustrates the results, wherein the four-element catalyst PdCoWP still maintained good catalytic activity under a methanol environment. However, the commercial Pt catalysts were poisoned by CO and had no activity.
The sample of example 1 was calcined for 2 hours at 500° C. in a reducing atmosphere to obtain the catalyst of example 5. In addition, comparative examples 3-5 were also prepared.
The same procedure as in example 1 was repeated in the comparative examples except that the atomic ratio listed in table 3 was used. Precursors including PdCl2, Co(NO3)2.6H2O, and (NH4)6W12O39.xH2O (Ammonium tungsten oxide hydrate) were weighted to obtain a three-element catalyst PdCoW. The PdCoW catalyst was further calcined for 2 hours at 500° C. in a reducing atmosphere, thus obtaining the catalyst of comparative example 3. Likewise, precursors including PdCl2, Co(NO3)2.6H2O, and NaH2PO2.H2O were weighted to form a three-element catalyst PdCoP. The PdCoP catalyst was further calcined for 2 hours at 500° C. in a reducing atmosphere, thus obtaining the catalyst of comparative example 4. Also, precursors including PdCl2 and Co(NO3)2.6H2O were weighted to form a two-element catalyst PdCo. The PdCo was further calcined for 2 hours at 500° C. in a reducing atmosphere, thus obtaining the catalyst of comparative example 5.
Table 3 illustrates the oxygen reduction reaction catalytic activity of the four-element, three-element, and two-element catalysts under 0.5M H2SO4. The result of example 1, wherein the catalyst was not calcined, is also shown in table 3 for comparison. As shown in table 3, catalysts of examples 1 and 5 showed no activity lost after being calcined, thereby still had good catalytic activity. Compared to comparative examples 3-5, the four-element catalysts containing Pd, before and after calcination, had better catalytic activity when compared to the three-element catalysts containing Pd (PdCoW and PdCoP) and two-element catalyst containing Pd (PdCo.)
Furthermore, table 4 illustrates the oxygen reduction reaction catalytic activity of the catalysts of example 1, example 5, and comparative examples 3-5 under the 1M methanol solution. As shown in table 4, compared to the catalysts containing Pt, the catalysts containing Pd had better resistance toward CO and/or methanol poisoning under a methanol environment, wherein the four-element catalysts of examples 1 and 5 still had the highest catalytic activities.
Table 5 illustrates the catalytic activity of the four-element catalyst, the two-element catalyst, and the three-element catalysts at 0.7V. As shown in table 5, after discharging for three hours, the three-element catalyst of the comparative example 4 (PdCoP) barely discharged. The activity of the three-element catalyst of the comparative example 3 (PdCoW) was only slightly better than the comparative example 1 (commercial Pt catalyst.) However, the activity of the four-element catalyst of example 5 (PdCoWP) was 34.3 A/g, which was about twice of the activity of the comparative example 1 (commercial Pt catalyst.)
Table 6 illustrates the activity of example 5 and comparative examples 1, 3-5 in methanol solution at 0.7V. The commercial Pt catalyst (comparative example 1) and the three-element catalyst of comparative example 4 (PdCoP) were poisoned by CO and/or methanol and stopped discharging after reaction for three hours. However, the activity of the four-element catalyst of example 5 still achieved 32.6 A/g after reaction for three hours. It is clear that the four-element catalyst of example 5 possesses high catalytic activity, high stability, and high resistance toward CO and/or methanol poisoning. Moreover, the price of Pd is only one-third to one-fourth the price of Pt, and therefore the catalyst cost can be reduced.
The same procedure as in example 1 was repeated in example 6 PtRuWP except that the atomic ratio listed in table 7 was used, wherein Ketjen Black ECP300 was used as the carrier and H2PtCl6.6H20, RuCl3, (NH4)6W12O39.xH2O, and NaH9PO2.H2O were weighted as precursors according to the ratio in table 7. In addition, catalysts of example 7 (PtRuAuP) and example 8 (PtRuCuP) were also synthesized by using HAuCl4.3H2O and CuCl2.2H2O to replace (NH4)6W12O39.xH2O of example 6. Table 7 illustrates the activity of the four-element cathode electrode catalysts, wherein all of the four-element anode electrode catalysts achieved good catalytic activity toward methanol oxidation reaction.
Three-element catalysts PtRuW (comparative example 6) and PtRuP (comparative example 7) were synthesized by the method described previously. Commercial two-element catalysts PtRu were also provided as comparative examples 8 (Johnson Matthey Corp.) and comparative examples 9 (TANAKA Corp.), wherein the atomic ratio of Pt:Ru of comparative examples 8 and 9 were 1:1 and 1:1.5, respectively. Referring to table 8, the activity of the four-element cathode electrode catalyst was better than the three-element and the two-element catalysts.
In addition, table 9 illustrates the stability of the four-element, three-element, and two-element catalysts at 40° C. at 0.4V in 5M CH3OH solution. Compared to the two-element and three-element catalysts, the four-element cathode electrode catalyst of example 6 had the best stability.
While the invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.
| Number | Date | Country | Kind |
|---|---|---|---|
| 100126739 | Jul 2011 | TW | national |
