Patent Application
20240258547
The present disclosure relates to radical scavengers for fuel cells, for example, radical scavengers for proton exchange membrane (PEM) fuel cells.
Fuel cells have shown promise as an alternative power source for vehicles and other transportation applications. Fuel cells operate with a renewable energy carrier, such as hydrogen. Fuel cells also operate without emitting toxic or greenhouse gases. One of the current limitations of widespread adoption and use of this clean and sustainable technology is the relatively expensive cost of the fuel cell.
According to one embodiment, a fuel cell proton exchange membrane (PEM) is disclosed. The fuel cell PEM may include a peroxide decomposition radical scavenger material. The peroxide decomposition radical scavenger material may be M/MOx (1≤x≤3), where M is Ta, W, Dy, Mo, La, Nd, V, Gd, Er, or Sm. The peroxide decomposition radical scavenger material may be mixed with at least one of Ce/CeOx (0.5≤x≤4) and Mn/MnOx (0.5≤x≤4).
According to another embodiment, a fuel cell proton exchange membrane (PEM) is disclosed. The fuel cell PEM may include a peroxide decomposition radical scavenger material. The peroxide decomposition radical scavenger material may be a Ce—M—O compound, where M is a metal element other than Ce. For example, M may be Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, or Mo. The Ce—M—O compound may be Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, Ce2WO6, Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4.
According to yet another embodiment, a fuel cell is disclosed. The fuel cell may include a membrane electrode assembly (MEA). The MEA may further include catalyst layers, a polymer electrolyte membrane (PEM) situated between the catalyst layers, and gas diffusion layers (GDLs) separated from the PEM by the catalyst layers. The fuel cell may also include bipolar plates connected to the GDLs. The PEM may have a peroxide decomposition radical scavenger material. The peroxide decomposition radical scavenger material may be M/MOx (1≤x≤3), where M is Ta, W, Dy, Mo, La, Nd, V, Gd, Er, or Sm. The peroxide decomposition radical scavenger material may be mixed with at least one of Ce/CeOx (0.5≤x≤4) and Mn/MnOx (0.5≤x≤4).
Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments can take various and alternative forms. The figures are not necessarily to scale; some features could be exaggerated or minimized to show details of components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the embodiments. As those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures can be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for applications or implementations.
This present disclosure is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing embodiments of the present disclosure and is not intended to be limiting in any way.
As used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
The description of a group or class of materials as suitable for a given purpose in connection with one or more embodiments implies that mixtures of any two or more of the members of the group or class are suitable. Description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description and does not necessarily preclude chemical interactions among constituents of the mixture once mixed.
Except where expressly indicated, all numerical quantities in this description indicating dimensions or material properties are to be understood as modified by the word “about” in describing the broadest scope of the present disclosure.
The first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation. Unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
The term “substantially” may be used herein to describe disclosed or claimed embodiments. The term “substantially” may modify any value or relative characteristic disclosed or claimed in the present disclosure. “Substantially” may signify that the value or relative characteristic it modifies is within +0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic.
Reference is being made in detail to compositions, embodiments, and methods of embodiments known to the inventors. However, disclosed embodiments are merely exemplary of the present disclosure which may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, rather merely as representative bases for teaching one skilled in the art to variously employ the present disclosure.
PEM fuel cells show great potential as an alternative solution for energy production and consumption. Particularly, PEM fuel cells are being developed as electrical power sources for automobile applications. However, widespread adoption requires further research into lifetime and cost reduction for components used in the PEM fuel cells. These components may include a PEM, catalyst layers, and gas diffusion layers (GDLs).
A typical single PEM fuel cell is composed of a PEM, an anode layer, a cathode layer, and GDLs. These components form a membrane electrode assembly (MEA), which is surrounded by two flow field plates. A catalyst material, such as platinum (Pt) catalysts, is included in the catalyst layer of both the anode and cathode layers of the PEM fuel cell. At the anode layer, Pt catalysts catalyze a hydrogen oxidation reaction (HOR, H2→2H++2e−), where H2 is oxidized to generate electrons and protons (H+). At the cathode layer, Pt catalysts catalyze an oxygen reduction reaction (ORR, 1/2O2+2H++2e−→H2O), where O2 reacts with H+ and is reduced to form water.
During the operation of the PEM fuel cell, hydrogen peroxide (H2O2) may be generated in a fuel cell acidic environment. Decomposition of H2O2 may lead to the generation of radical species in the fuel cell acidic environment. The radical species may be hydroxyl radicals (•OH), hydrogen radicals (•H), and/or hydroperoxyl radicals (•OOH). The radical species may diffuse into the PEM and other fuel cell components. The formation of H2O2 may depend on the operating conditions of the PEM fuel cell. For example, under hot and dry conditions, more H2O2 can be generated, and therefore, more radical species can be generated in the fuel cell acidic environment. The radical species can attack the PEM and other fuel cell components, which consequently reduces the durability of the PEM fuel cell.
To prevent fuel cell components from attack by radical species, peroxide decomposition radical scavenger materials such as cerium (Ce)/cerium oxide (CeOx) or manganese (Mn)/manganese oxide (MnOx) have been utilized to remove the radical species in the fuel cell acidic environment. Although radical scavengers, for example, Ce/CeOx, can suppress the degradation of some fuel cell components, recent studies have indicated that because Ce can be ionized to Ce3+ ions in the fuel cell acidic environment, the ionized Ce can migrate from one location to another in the PEM fuel cell. Depending on a water flux and an electrical potential in the PEM fuel cell, Ce3+ ions may be transported and/or aggregated in certain fuel cell components, such as the PEM and/or the catalyst layers. As such, Ce/CeOx may not be an ideal to act as a radical scavenger to protect the fuel cell components from attack by radical species in the PEM fuel cell.
Aspects of the present disclosure relates to peroxide decomposition radical scavenger materials for fuel cells. As disclosed herein, first-principles density functional theory (DFT) algorithms, calculations and/or methodologies are used to model the chemical reactivities of metals (M), metal oxides (MOx or Ce—M—O), and Ce—Mn mixtures against H2O2 to identify radical scavengers that are comparably more effective than Ce/CeOx and/or Mn/MnOx and less soluble than Ce/CeOx and/or Mn/MnOx in a fuel cell acidic environment. Particularly, a data-driven materials screening method is employed for such identifications. The comparably superior radical scavengers may be incorporated in fuel cell components, such as the PEM, catalyst layers, and GDLs, to protect the fuel cell components from attack by radical species, thereby enhancing the durability of the PEM fuel cell. Depending on where the radical scavengers are incorporated into the fuel cell, a loading level of the radical scavengers may be in a range of 0.1 to 200 μg cm−2. The loading level of the radical scavengers may be measured based on the weight of the metal element(s) in the radical scavengers, not metal oxide derivatives.
The processor 12 may be configured to read into memory and execute computer-executable instructions residing in a DFT software module 18 of the non-volatile storage 16 and embodying DFT slab model algorithms, calculations and/or methodologies of one or more embodiments. The DFT software module 18 may include operating systems and applications. The DFT software module 18 may be compiled or interpreted from computer programs created using a variety of programming languages and/or technologies, including, without limitation, and either alone or in combination, Java, C, C++, C #, Objective C, Fortran, Pascal, Java Script, Python, Perl, and PL/SQL.
Upon execution by the processor 12, the computer-executable instructions of the DFT software module 18 may cause the computing platform 10 to implement one or more of the DFT algorithms and/or methodologies disclosed herein. The non-volatile storage 16 may also include DFT data 20 supporting the functions, features, calculations, and processes of the one or more embodiments described herein.
The program code embodying the algorithms and/or methodologies described herein is capable of being individually or collectively distributed as a program product in a variety of different forms. The program code may be distributed using a computer readable storage medium having computer readable program instructions thereon for causing a processor to carry out aspects of one or more embodiments. The computer readable storage medium, which is inherently non-transitory, may include volatile and non-volatile, and removable and non-removable tangible media implemented in any method or technology for storage of information, such as computer-readable instructions, data structures, program modules, or other data. The computer readable storage media may further include RAM, ROM, erasable programmable read-only memory (EPROM), electrically erasable programmable read-only memory (EEPROM), flash memory or other solid state memory technology, portable compact disc read-only memory (CD-ROM), or other optical storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium that can be used to store the desired information and which can be read by a computer. Computer readable program instructions may be downloaded to a computer, another type of programmable data processing apparatus, or another device from a computer readable storage medium or to an external computer or external storage device via a network.
Computer readable program instructions stored in the computer readable medium may be used to direct a computer, other types of programmable data processing apparatus, or other devices to function in a particular manner, such that the instructions stored in the computer readable medium produce an article of manufacture including instructions that implement the functions, acts, and/or operations specified in the flowcharts or diagrams. In certain alternative embodiments, the functions, acts, and/or operations specified in the flowcharts and diagrams may be re-ordered, processed serially, and/or processed concurrently consistent with one or more embodiments. Moreover, any of the flowcharts and/or diagrams may include more or fewer nodes or blocks than those illustrated consistent with one or more embodiments.
Referring to
To better understand the chemical reactivity of a radical scavenger candidate against H2O2, the data-driven materials screening method is first used to examine the chemical reactivities of Ce/CeOx and Mn/MnOx against H2O2 under similar conditions. The chemical reactivities of Ce/CeOx and Mn/MnOx against H2O2 may then be used as references for the identification of radical scavenger candidates that are comparably more effective than Ce/CeOx and/or Mn/MnOx and less soluble than Ce/CeOx and/or Mn/MnOx in a fuel cell acidic environment.
According to reaction (1), after reacting with H2O2, MnO is turned into Mn2O3. Point A also represents the situation where radical species (e.g. •OH) and the radical scavenger, herein MnO, are abundantly present in the reaction environment.
Next, using the data-driven materials screening method, chemical reactivities of Ce/CeOx against H2O2 may be evaluated. First, Ce may react with H2O2 to generate CeH3 and Ce7O12, (i.e., can also be written as CeO1.71). Reaction (2) is included hereby to illustrate this reaction:
According to reaction (2), the most stable decomposition reaction between Ce and H2O2 may occur when the molar fraction of Ce is about 0.647. The reaction enthalpy of reaction (2) is about −1.742 eV/atom. The reaction products CeH3 and Ce7O12 may further react with H2O2 to fully oxidize Ce to CeO2. CeO2 may not react with H2O2. Reaction (3) is included hereby to illustrate the reaction between CeH3 and H2O2:
According to reaction (3), the most stable decomposition reaction between CeH3 and H2O2 may occur when the molar fraction of CeH3 is about 0.222. The reaction enthalpy of reaction (3) is about −0.938 eV/atom. Reaction (4) is also included hereby to illustrate the reaction between Ce7O12 and H2O2:
According to reaction (4), the most stable decomposition reaction between CeO1.71 and H2O2 may occur when the molar fraction of CeO1.71 is about 0.775. The reaction enthalpy of reaction (3) is about −0.328 eV/atom.
Table 1 provides information of the most stable decomposition reactions between Ce/CeOx and H2O2. Particularly, Table 1 provides a reaction equation of the most stable decomposition reaction of each chain reaction. Table 1 further provides a molar fraction between H2O2 and each Ce-containing compound. Table 1 also provides a first penalty point (e.g. PP1) regarding the molar fraction, where PP1 of 1.00 is assigned to the reaction between Ce and H2O2. In addition, Table 1 provides a reaction enthalpy of each chain reaction and assigns a second penalty point (e.g. PP2) regarding the reaction enthalpy of each chain reaction, where PP2 of 1.00 is assigned to the reaction between Ce and H2O2.
Furthermore, Table 1 provides a sum of the first and second penalty points, i.e., ΣPP. As shown in Table 1, ΣPP(Ce) equals PP1+ PP2, which is 2.00. To adjust the ratio of CeH3 between reactions (2) and (3) and the ratio of Ce7O12 (i.e., CeO1.71) between reactions (2) and (4), Table 1 provides a ratio R, where, for CeH3, R(CeH3) equals 0.235/0.222, which is about 105.9%; for Ce7O12 (i.e., CeO1.71), R(Ce7O12) equals 0.059/(0.775*7), which is about 1.1%. Table 1 also provides an adjusted sum of the first and second penalty points, i.e., ΣPP′, where, for CeH3, ΣPP′(CeH3) equals 2.01*105.9%, which is about 2.13; for Ce7O12 (i.e., CeO1.71), ΣPP′(Ce7O12) equals 7.19*1.1%, which is about 0.08. Table 1 further provides a total of the adjusted sum of penalty points for all the Ce/CeOx chain reactions, i.e., reaction (2), (3) and (4), which is about 4.21.
Next, using the data-driven materials screening method, chemical reactivities of Mn/MnOx against H2O2 may also be evaluated. First, Mn may react with H2O2 to generate MnO. Reaction (5) is included hereby to illustrate this reaction:
According to reaction (5), the most stable decomposition reaction between Mn and H2O2 may occur when the molar fraction of Mn is about 0.5. The reaction enthalpy of reaction (5) is about −0.863 eV/atom. The reaction product MnO may further react with H2O2 to give Mn2O3. Reaction (6) is included hereby to illustrate the reaction between MnO and H2O2:
According to reaction (6), the most stable decomposition reaction between MnO and H2O2 may occur when the molar fraction of MnO is about 0.667. The reaction enthalpy of reaction (6) is about −0.312 eV/atom. The reaction product Mn2O3 (i.e., MnO1.5) may further react with H2O2 to fully oxidize Mn to MnO2. MnO2 may not react with H2O2. Reaction (7) is included hereby to illustrate the reaction between Mn2O3 (i.e., MnO1.5) and H2O2:
According to reaction (7), the most stable decomposition reaction between MnO1.5 and H2O2 may occur when the molar fraction of MnO1.5 is about 0.667. The reaction enthalpy of reaction (7) is about −0.123 eV/atom.
Table 2 provides information of the most stable decomposition reactions between Mn/MnOx and H2O2. Particularly, Table 2 provides a reaction equation of the most stable decomposition reaction of each chain reaction. The reaction between Ce and H2O2 in Table 1 is used herein as a reference. Table 2 provides a molar fraction between H2O2 and each Mn-containing compound. Table 1 also provides a third penalty point (e.g. PP3) regarding the molar fraction, where PP3 equals 0.55 (i.e., the molar fraction between H2O2 and Ce as shown in Table 1) divided by the molar fraction between H2O2 and Mn or Mn-containing compound. For example, the molar fraction between H2O2 and Mn is 1.00, and therefore, PP3(Mn) equals 0.55/1.00, which is 0.55.
Table 2 further provides a reaction enthalpy of each chain reaction and assigns a fourth penalty point (e.g. PP4) regarding the reaction enthalpy of each chain reaction, where PP4 equals −1.742 eV/atom (i.e., the reaction enthalpy between H2O2 and Ce as shown in Table 1) divided by the reaction enthalpy between H2O2 and Mn or Mn-containing compound. For example, the reaction enthalpy of the reaction between H2O2 and Mn is about −0.863 eV/atom, and therefore, PP4(Mn) equals−1.742/−0.863, which is about 2.02.
Furthermore, Table 2 provides a sum of the third and fourth penalty points, i.e., ΣPP. As shown in Table 2, ΣPP(Mn) equals PP3+ PP4, which is about 2.56. To adjust the ratio of MnO between reactions (5) and (6) and the ratio of Mn2O3 (i.e., MnO1.5) between reactions (6) and (7), Table 2 provides a ratio R, where, for MnO, R(MnO) equals 0.5/0.667, which is about 75%; for Mn2O3 (i.e., MnO1.5), R(Mn2O3) equals 0.333/(0.667*2), which is about 25%. Table 2 also provides an adjusted sum of the third and fourth penalty points, i.e., ΣPP′, where, for MnO, ΣPP′(MnO) equals 6.68*75%, which is about 5.00; for Mn2O3 (i.e., MnO1.5), ΣPP′(Mn2O3) equals 15.26*25%, which is about 3.81. Table 2 further provides a total of the adjusted sum of penalty points for all the Mn/MnOx chain reactions, i.e., reaction (5), (6) and (7), which is about 11.38.
In view of Tables 1 and 2, the total of the adjusted sum of penalty points for reactions between Mn/MnOx and H2O2 is about 11.38, which is larger than that (i.e. 4.21) for reactions between Ce/CeOx and H2O2. This indicates that Ce/CeOx may react with H2O2 more favorably than Mn/MnOx in similar reaction environments, making Ce/CeOx a relatively better radical scavenger than Mn/MnOx.
Apart from those CeOx and MnOx compounds in Tables 1 and 2, other CeOx and MnOx compounds with different oxidation states may also react with H2O2 in similar reaction environments. Using the data-driven materials screening method as described above, chemical reactivities of other CeOx and/or MnOx compounds against H2O2 may further be evaluated. Some of these CeOx and MnOx compounds include CeO, CeO1.5, CeO1.8, CeO1.81, CeO1.88, and MnO1.33.
Table 3 provides information of the most stable decomposition reaction between each of the CeOx and MnOx compounds and H2O2. Particularly, Table 3 provides a reaction equation of the most stable decomposition reaction of each reaction. The reaction between Ce and H2O2 in Table 1 is used herein as a reference. Table 3 provides a molar fraction between H2O2 and each of the CeOx and MnOx compounds. Table 3 further provides a fifth penalty point (e.g. PP5) regarding the molar fraction, where PP5 equals 0.55 (i.e., the molar fraction between H2O2 and Ce as shown in Table 1) divided by the molar fraction between H2O2 and each of the CeOx and MnOx compounds. For example, the molar fraction between H2O2 and CeO is 1.00, and therefore, PP5(CeO) equals 0.55/1.00, which is 0.55.
In addition, Table 3 provides a reaction enthalpy of each reaction and assigns a sixth penalty point (e.g. PP6) regarding the reaction enthalpy of each reaction, where PP6 equals−1.742 eV/atom (i.e., the reaction enthalpy between H2O2 and Ce as shown in Table 1) divided by the reaction enthalpy between H2O2 and each of the CeOx and MnOx compounds. For example, the reaction enthalpy of the reaction between H2O2 and CeO is about −0.943 eV/atom, and therefore, PP6(CeO) equals−1.742/−0.943, which is about 1.85. Furthermore, Table 3 provides a sum of the fifth and sixth penalty points, i.e., ΣPP=PP5+ PP6.
According to the sum of the fifth and sixth penalty points in Table 3, CeO, CeO1.5, and CeO1.5 appear to react with H2O2 more favorably than MnO1.33, and the reactivity of CeO1.51 against H2O2 appears to be comparable to that of MnO1.33. Table 3 also shows that CeO1.88 reacts with H2O2 less favorably than MnO1.33. Furthermore, Table 3 appears to suggest that metal oxides with lower oxidation states may react with H2O2 more favorably than those with higher oxidation states. For example, CeO1.5 appears to react with H2O2 more favorably than CeO1.88 in similar reaction environments.
Next, the data-driven materials screening method is used to evaluate other metal elements except Ce and Mn to identify comparable radical scavengers for fuel cells. Some of these metal elements may include, aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), antimony (Sb), tellurium (Te), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), tantalum (Ta), tungsten (W), and bismuth (Bi).
Table 4 provides information of the most stable decomposition reaction between each metal element and H2O2. The decomposition product in each reaction is obtained using “interface reactions” module kit, available on materialsproject.org. Particularly, Table 4 provides a reaction equation of the most stable decomposition reaction of each reaction. The reaction between Ce and H2O2 in Table 1 is used herein as a reference. Table 4 provides a molar fraction between H2O2 and each metal element. Table 4 further provides a seventh penalty point (e.g. PP7) regarding the molar fraction, where PP7 equals 0.55 (i.e., the molar fraction between H2O2 and Ce as shown in Table 1) divided by the molar fraction between H2O2 and each metal element. For example, the molar fraction between H2O2 and Al is 0.75, and therefore, PP7(Al) equals 0.55/0.75, which is 0.73.
In addition, Table 4 provides a reaction enthalpy of each reaction and assigns an eighth penalty point (e.g. PP8) regarding the reaction enthalpy of each reaction, where PP8 equals −1.742 eV/atom (i.e., the reaction enthalpy between H2O2 and Ce as shown in Table 1) divided by the reaction enthalpy between H2O2 and each metal element. For example, the reaction enthalpy of the reaction between H2O2 and Al is about −1.428 eV/atom, and therefore, PP8(Al) equals−1.742/−1.428, which is about 1.22. Furthermore, Table 4 provides a sum of the seventh and eighth penalty points, i.e., ΣPP(M)=PP7+ PP8.
As discussed in Tables 1 and 2, the sum of the penalty points for the reaction between Ce and H2O2 is 2, and that for the reaction between Mn and H2O2 is 2.56. Referring to Table 4, metal elements whose sum of penalty points above 2.56 are excluded for further consideration as radical scavenger candidates for fuel cells. These metal elements appear to be Fe, Co, Ni, Cu, Zn, Sb, Te, Eu, and Bi. The remaining metal elements, including Al, Si, Ti, V, Cr, Ga, Y, Zr, Nb, Mo, In, Sn, La, Pr, Nd, Sm, Gd, Dy, Er, Ta, and W, are to be considered as radical scavenger candidates for fuel cells.
Using the data-driven materials screening method, chemical reactivities of each M/MOx and H2O2 may be evaluated, where M may be Al, Si, Ti, V, Cr, Ga, Y, Zr, Nb, Mo, In, Sn, La, Pr, Nd, Sm, Gd, Dy, Er, Ta, and W. Table 5 provides information of the most stable decomposition reactions between each M/MOx and H2O2. Particularly, Table 5 provides a reaction equation of the most stable decomposition reaction of each chain reaction. The reaction between Ce/CeOx and H2O2 in Table 1 is used herein as a reference. Table 5 provides a molar fraction between H2O2 and each M-containing compound. Table 5 further provides a ninth penalty point (e.g. PP9) regarding the molar fraction, where PP9 equals 0.55 (i.e., the molar fraction between H2O2 and Ce as shown in Table 1) divided by the molar fraction between H2O2 and M or M-containing compound. For example, the molar fraction between H2O2 and Al is 0.75, and therefore, PP9(Al) equals 0.55/0.75, which is 0.73.
In addition, Table 5 provides a reaction enthalpy of each reaction and assigns a tenth penalty point (e.g. PP10) regarding the reaction enthalpy of each reaction, where PP10 equals−1.742 eV/atom (i.e., the reaction enthalpy between H2O2 and Ce as shown in Table 1) divided by the reaction enthalpy between H2O2 and M or M-containing compound. For example, the reaction enthalpy of the reaction between H2O2 and Al is about −1.428 eV/atom, and therefore, PP10(Al) equals−1.742/−1.428, which is about 1.22.
Furthermore, Table 5 provides a sum of the tenth and eleventh penalty points, i.e., ΣPP=PP10+ PP11. As shown in Table 5, some M/MOx react with H2O2 through multiple steps. To adjust the ratio of MOx between the chain reactions, Table 5 provides a ratio R. For example, for Al/AlOx, after 0.571 Al reacting with 0.429 H2O2, the product Al2O3may continue reacting with H2O2 until Al is fully oxidized to Al11O18. Therefore, to adjust the ratio of Al2O3(i.e., AlO1.5) between the two chain reactions, a ratio R(Al2O3) is calculated as 0.286/(0.88*2), which is about 162.5%.
Table 5 further provides an adjusted sum of the ninth and tenth penalty points, i.e., ΣPP′. For example, for Al2O3(i.e., AlO1.5), the adjusted sum of PP9(Al2O3) and PP10(Al2O3) is calculated as 20.56*162.5%, which is about 33.46. Table 5 further provides a total of the adjusted sum of penalty points for all the M/MOx chain reactions, i.e. ΣPP″. For example, for Al/AlOx, the total of the adjust sum of penalty points is about 35.41.
According to Table 5, some M/MOx react with H2O2 through one step, such as Si/SiO2 or Sn/SnO2, in which cases when M is oxidized to MOx, MOx may not further react with H2O2. A general reaction between such a M/MOx and H2O2 can be described as: aM+bH2O2→cMOx+ other products (e.g. H2O or H2), where 0<a<1, 0<b<1, and 0<c<1. Still referring to Table 5, some other M/MOx react with H2O2 through multiple steps, such as Al/AlOx or Ti/TiOx, in which cases when M first reacts with H2O2, the intermediate product(s) may further react with H2O2 until M is fully oxidized to an oxidation state where MOx no longer reacts with H2O2.
Table 6 provides a summary of the information of M/MOx in Table 5 in an order from the lowest total of the adjusted sum of penalty points to the highest total of the adjusted sum of penalty points. Table 6 also provides information of whether the reaction between M/MOx and H2O2 is a one-step or multiple-step reaction.
According to Table 6, when M=Nb, Ta, Si, Ga, Sn, W, In, or Dy, M/MOx may react with H2O2 more favorably than Ce/CeOx. Further, when M=Zr, Ti, La, Nd, Mo, V, Pr, Gd, Y, Er, and Sm, M/MOx reacts with H2O2 less favorably than Ce/CeOx but more favorably than Mn/MnOx.
For a M/MOx to be comparably more effective than Ce/CeOx and/or Mn/MnOx as radical scavengers for fuel cells, M/MOx needs not only reacting with H2O2 more favorably than Ce/CeOx and/or Mn/MnOx, but needs to be more stable (e.g. less soluble) than Ce/CeOx and/or Mn/MnOx in a fuel cell acidic environment.
In order to evaluate possible thermodynamically stable phases of the M/MOx in Table 6, a Pourbaix diagram of each metal element can be generated from materialsproject.org using pourbaixdiagram app. For example,
Table 7 provides a summary of possible thermodynamically stable phases of the M/MOx in Table 6 when present in a fuel cell acidic environment. Such information may be obtained from a Pourbaix diagram of each metal element which can be generated from materialsproject.org using pourbaixdiagram app. The fuel cell acidic environment may correspond to an area where a voltage potential E(V) is between 0 V to 1 V and where a pH value is between 1 and 4 in the Pourbaix diagram of each metal element. Table 7 also provides the M/MOx in an order from the lowest total of the adjusted sum of penalty points to the highest total of the adjust sum of penalty points as described in Table 6.
Table 7 suggests that some M/MOx may be stable as ions in the fuel cell acidic environment, for example, when M=In, Dy, La, Nd, Pr, Gd, Y, Er and Sm. Among these metal elements, however, In/InOx and Dy/DyOx appear to react with H2O2 more favorably than Ce/CeOx. Table 7 further suggests that some other M/MOx may be passivated to metal oxides in the fuel cell acidic environment, for example, when M=Nb, Ta, Si, Ga, Sn, W, Zr, Ti, and Mo. These metal oxides do not react with H2O2, and thus stable in the fuel cell acidic environment, making these M/MOx suitable to be used as radical scavengers for fuel cells. Furthermore, among these M/MOx, Nb/NbOx, Ta/TaOx, Si/SiOx, Ga/GaOx, Sn/SnOx, and W/WOx appear to react with H2O2 more favorably than Ce/CeOx; Zr/ZrOx and Ti/TiOx appear to react with H2O2 less favorably than Ce/CeOx but more favorably than Mn/MnOx.
In view of Tables 6 and 7, M/MOx may be categorized into several groups in terms of the following factors: (1) the reactivity of M/MOx against H2O2; (2) reaction step(s) when M/MOx reacts with H2O2 (i.e. a one-step or multiple-step reaction); (3) possible thermodynamically stable phases of M in a fuel cell acidic environment.
Table 8 shows a summary of M/MOx in Tables 6 and 7 categorized in six groups. Particularly, Group I may include Nb/NbOx, which appears to react with H2O2 more favorably than Ce/CeOx (i.e., also more favorably than Mn/MnOx) and appears to be stable as metal oxides in a fuel cell acidic environment. Group II may include M/MOx with M=Ta, Si, Ga, Sn, W, which appear to react with H2O2 more favorably than Ce/CeOx (i.e., also more favorably than Mn/MnOx) and appear to be stable as metal oxides in a fuel cell acidic environment. The M/MOx in Group II, however, may react with H2O2 less favorably than Nb/NbOx in Group I. Group III may include Dy/DyOx, which appears to react with H2O2 more favorably than Ce/CeOx (i.e., also more favorably than Mn/MnOx) but appears to be present as metal ions (i.e. Dy3+) in a fuel cell acidic environment. Group IV may include In/InOx, which appears to react with H2O2 more favorably than Ce/CeOx (i.e., also more favorably than Mn/MnOx) but appears to be present as metal ions (i.e. In3+) in a fuel cell acidic environment. Group V may include M/MOx with M=Zr, Ti, Mo, which appear to react with H2O2 more favorably than Mn/MnOx but less favorably than Ce/CeOx and appear to be stable as metal oxides in a fuel cell acidic environment. Lastly, Group VI may include M/MOx with M=La, Nd, V, Pr, Gd, Y, Er, Sm, which appear to react with H2O2 more favorably than Mn/MnOx but less favorably than Ce/CeOx and appear to be present as metal ions in a fuel cell acidic environment. As such, each of the M/MOx in Table 8 may be used as radical scavengers for fuel cells due to their comparability to Ce/CeOx and/or Mn/MnOx in terms of their reactivities against H2O2 and their stability in a fuel cell acidic environment.
Next, the data-driven materials screening method is used to evaluate Ce—Mn mixtures as radical scavengers for fuel cells. The Ce—Mn mixtures may have different ratios of Ce and Mn. Some of these Ce—Mn mixtures may include Ce0.25Mn0.75, Ce0.5Mn0.5, and Ce0.75Mn0.25. Table 9 provides information of a total of the adjusted sum of penalty points for all Ce—Mn chain reactions, i.e. ΣPP″(Ce—Mn). The total of the adjusted sum of penalty points can be calculated as discussed above, for example, in Table 5. Although Table 9 shows radical scavengers having three different ratios of Ce and Mn, that is, 25% Ce and 75% Mn, 50% Ce and 50% Mn, and 75% Ce and 25% Mn, Ce—Mn mixtures having other ratios of Ce and Mn may also be analyzed using the data-driven materials screening method.
As shown in Table 9, as the ratio of Ce increases, the reactivity of Ce—Mn mixtures may also increase. This is consistent with the results in Tables 1 and 2, where Ce/CeOx is shown to react with H2O2 more favorably than Mn/MnOx. Particularly, when the Ce—Mn mixture includes 25% Ce and 75% Mn, i.e., Ce0.25Mn0.75, the Ce—Mn mixture appears to be comparably more effective than Mn/MnOx as a radical scavenger.
Next, the data-driven materials screening method is used to evaluate Ce—M—O compounds which may be suitable to be used as radical scavengers for fuel cells, where M may be Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, or Mo. Some of the Ce—M—O compounds may include CeNbO4, CeTaO4, CeTa7O19, Ce2Si2O7, Ce2Zr2O7, Ce2TiO5, CeNb3O9, CeTa3O9, Ce3TaO7, Ce2WO6, Ce9DyO20, CeZr11O24, Ce7ZrO16, CeZr7O16, Ce2Ti2O7, and Ce2Mo4O15. Among these Ce—M—O compounds, CeNbO4, CeTaO4, CeTa7O19, Ce2Si2O7, Ce2Zr2O7, and Ce2TiO5 may be stable at temperature equals 0 K and above; the other Ce—M—O compounds, CeNb3O9, CeTa3O9, Ce3TaO7, Ce2WO6, Ce9DyO20, CeZr11O24, Ce7ZrO16, CeZr7O16, Ce2Ti2O7, Ce2Mo4O15, may become stable at room temperature. Furthermore, among the Ce—M—O compounds, CeTa7O19, Ce9DyO20, CeZr11O24, Ce7ZrO16, and CeZr7O16 may not react with H2O2. As such, the data-driven materials screening method is used to evaluate the remaining Ce—M—O compounds that may react with H2O2.
Table 11 provides information of the reaction between each Ce—M—O compound and H2O2. Particularly, Table 11 provides a reaction equation of the most stable decomposition reaction between each Ce—M—O compound and H2O2. For each Ce—M—O compound, a first penalty point based on a molar fraction between H2O2 and each Ce—M—O compound and a second penalty point based on a reaction enthalpy of each reaction are calculated. The calculation method is analogous to those described in Tables 2 to 5. Table 11 further provides a sum of the penalty points, i.e., ΣPP(Ce—M—O). The reaction between Ce and H2O2 in Table 1 is used herein as a reference. Also, as shown in Table 1, Σ′PP(Ce/CeOx) is about 4.21; as shown in Table 2, ΣPP(Mn/MnOx) is about 11.38.
Table 11 also provides a molecular weight (MW) of each Ce—M—O compound. Table 11 further provides a sum of the penalty points of each Ce—M—O compound per MW, i.e., ΣPP(Ce—M—O) per MW. To easily compare the reactivity of each Ce—M—O compound against H2O2 with Ce and/or Mn, Table 11 provides a sum of the penalty points of Ce per its MW (about 140.12 g/mol), i.e., ΣPP(Ce) per MW=2.00/140.12, which is about 14.3 mg; and a sum of the penalty points of Mn per its MW (about 54.94), i.e., ΣPP(Mn) per MW=2.56/54.94, which is about 46.7 mg.
Table 12 provides a summary of the information illustrated in Table 11 in an order from the lowest ΣPP(Ce—M—O) per MW to the highest ΣPP(Ce—M—O) per MW.
According to Table 12, Ce—M—O compounds such as Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, and Ce2WO6 may be superior radical scavengers to Ce. Further, although the reactivity of each Ce—M—O compound such as Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4 against H2O2 appears to be lower than that of Ce against H2O2, each of these Ce—M—O compounds appears to react with H2O2 more favorably than Mn. Taken together, all the Ce—M—O compounds, i.e., Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, Ce2WO6, Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4, appear to be comparably effective to Ce and/or Mn as radical scavengers for fuel cells.
To synthesize a M/MOx radical scavenger material, various metal containing precursors may be annealed with a stoichiometric amount in slightly reducing heat treatment condition using N2, Ar, or H2 mixture gas, etc., where a heat treatment temperature may be in a range of 150 to 1,000° C. to yield a desired chemistry. A heat treatment time may be in a range of 30 seconds to 24 hours. Depending on the oxidation state, it may be possible to carry out heat treatment in air.
During the operation of the fuel cell 30, H2O2 may be generated in a fuel cell acidic environment. Decomposition of H2O2 may lead to the generation of radical species in the fuel cell acidic environment. The radical species may include •OH, •H, and •OOH. The radical species may diffuse into the PEM 32 and other fuel cell components. To prevent fuel cell components from attack by the radical species, peroxide decomposition radical scavenger materials may be incorporated into the fuel cell components.
In one embodiment, the radical scavenger is M/MOx (1≤x≤3), where M may be Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, Mo, La, Nd, V, Pr, Gd, Y, Er, or Sm. In another embodiment, the radical scavenger is M/MOx (1≤x≤3) mixed with at least one of Ce/CeOx (0.5≤x≤4) and Mn/MnOx (0.5≤x≤4). In yet another embodiment, the radical scavenger may be a Ce—Mn mixture. Some examples of the Ce—Mn mixture may include Ce0.25Mn0.75, Ce0.5Mn0.5, or Ce0.75Mn0.25. In still yet another embodiment, the radical scavenger may be a Ce—M—O compound, where M is a metal element other than Ce. For example, M may be Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, or Mo. Some examples of the Ce—M—O compound may include Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, Ce2WO6, Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4. In some other embodiments, the radical scavenger may be any of the combination of M/MOx (1≤x≤3, M=Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, Mo, La, Nd, V, Pr, Gd, Y, Er, or Sm), Ce/CeOx (0.5≤x≤4), Mn/MnOx (0.5≤x≤4), a Ce—Mn mixture, or a Ce—M—O compound (M=Ta, Zr, Ti, W, Si, Mo, or Nb).
Referring to
Apart from the PEM 32, radical scavengers may also be incorporated into other fuel cell components which are susceptible to radical attacks. These fuel cell components may be the first and second catalyst layers 34 and 36, or the first and second GDLs 38 and 40. In some embodiments, a loading level of radical scavengers onto a fuel cell component may be in a range of 0.1 to 200 μg cm2.
The radical scavengers M/MOx (1≤x≤3, M=Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, Mo, La, Nd, V, Pr, Gd, Y, Er, or Sm) discussed in the present disclosure may each act as a radical scavenger system that reacts with H2O2 in a reaction environment (e.g. a fuel cell acidic environment), thereby scavenging radicals (e.g. •OH, •H, and •OOH) in the reaction environment. In some embodiments, MOx, a reactive intermediate oxide, may react with H2O2 until M is fully oxidized to an oxidation state where MOx no longer reacts with H2O2 in the reaction environment.
Now, a method of incorporating peroxide decomposition radical scavenger materials into a fuel cell component will be described. The fuel cell component may be a PEM, a catalyst layer, and/or a GDL. A loading level of radical scavengers onto the fuel cell component may be in a range of, for example, 0.1 to 200 μg cm−2. The loading level of radical scavengers may be based on the weight of the metal element(s) in the radical scavengers, not the metal oxide derivatives.
In one embodiment, a metal element material (M) may be added into the fuel cell component. The metal element material may not be oxidized before adding into the fuel cell component. The metal element material may be Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, Mo, La, Nd, V, Pr, Gd, Y, Er, or Sm. A reactive intermediate oxide of the metal element material (MOx, 1≤x≤3) may then be added into the fuel cell component. In some embodiments, M/MOx may be mixed with at least one of Ce/CeOx (0.5≤x≤4) and Mn/MnOx (0.5≤x≤4). In some other embodiments, M/MOx may be mixed with a Ce—Mn mixture. The Ce—Mn mixture may be Ce0.25Mn0.75, Ce0.5Mn0.5, or Ce0.75Mn0.25. In yet some other embodiments, M/MOx may be mixed with a Ce—M—O compound. The Ce—M—O compound may be Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, Ce2WO6, Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4.
In another embodiment, to incorporate peroxide decomposition radical scavenger materials into a fuel cell component, a Ce—Mn mixture may be added into the fuel cell component. The Ce—Mn mixture may be Ce0.25Mn0.75, Ce0.5Mn0.5, or Ce0.75Mn0.25. In some embodiments, the Ce—Mn mixture may be mixed with M/MOx (1≤x≤3, M=Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, Mo, La, Nd, V, Pr, Gd, Y, Er, or Sm). In some other embodiments, the Ce—Mn mixture may be mixed with at least one of Ce/CeOx (0.5≤x≤4) and Mn/MnOx (0.5≤x≤4). In yet some other embodiments, the Ce—Mn mixture may be mixed with a Ce—M—O compound. The Ce—M—O compound may be Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, Ce2WO6, Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4.
In yet another embodiment, to incorporate peroxide decomposition radical scavenger materials into a fuel cell component, a Ce—M—O compound may be added into the fuel cell component. M is a metal element other than Ce. M may be Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, or Mo. The Ce—M—O compound may be Ce3TaO7, Ce2Zr2O7, Ce2Ti2O7, Ce2TiO5, Ce2WO6, Ce2Si2O7, CeTa3O9, Ce2Mo4O15, CeTaO4, CeNb3O9, and CeNbO4. In some embodiments, the Ce—M—O compound may be mixed with at least one of M/MOx (1≤x≤3, M=Nb, Ta, Si, Ga, Sn, W, Dy, In, Zr, Ti, Mo, La, Nd, V, Pr, Gd, Y, Er, or Sm). In some other embodiments, the Ce—M—O compound may be mixed with at least one of Ce/CeOx (0.5≤x≤4) and Mn/MnOx (0.5≤x≤4). In yet some other embodiments, the Ce—M—O compound may be mixed with a Ce—Mn mixture. The Ce—Mn mixture may be Ce0.25Mn0.75, Ce0.5Mn0.5, or Ce0.75Mn0.25.
While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. The words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments can be combined to form further embodiments of the present disclosure that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. These attributes can include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. As such, to the extent any embodiments are described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics, these embodiments are not outside the scope of the disclosure and can be desirable for particular applications.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2021/030564 | 5/4/2021 | WO |
