This disclosure relates to humidification of fuel cells, and, in particular, to the use of a segmented exchange membrane to produce water for humidification of fuel cell feed gases.
An acid based polymer electrolyte membrane (PEM) conducts protons from the anode to the cathode in PEM fuel cells more efficiently when the PEM is fully humidified. The PEM loses its ability to conduct protons as it dries under low relative humidity operations in PEM fuel cells. Attempts to develop acid based membranes with high acid loading have been made by reducing the membrane thickness and improving the water transport from the cathode to the anode. The designs attempt to make the PEM less dependent on humidification for efficient proton conduction. However, developing a membrane with high acid loading to improve the proton conductivity has been extremely challenging and expensive. And reduction in membrane thickness to improve the water transport from the cathode to the anode leads to compromise on membrane mechanical strength. In addition, reduction in membrane thickness proportionally increases the crossover rate of hydrogen from the anode to the cathode and oxygen from the cathode to the anode, adversely affecting the durability of the membrane and the electrocatalyst.
To overcome membrane dehydration and maintain the ionic conductivity, PEM fuel cell stacks can employ external humidifiers on both the anode and the cathode to humidify the anode feed gas and cathode oxidant. However, these external humidifiers add cost, complexity, and operational challenges to the PEMFC system and reduce system reliability.
Disclosed herein are implementations of membrane electrode assemblies for a fuel cell. One implementation comprises a segmented membrane including a porous support having a surface area, the surface area divided into a first portion and a second portion. An alkaline segment is formed from the first portion of the porous support imbibed with an alkaline ionomer. An acid segment is formed from the second portion of the porous support imbibed with an acid ionomer. The alkaline segment is sized to provide a humidification amount to a feed gas passing through the acid segment.
Another implementation of a membrane electrode assembly has a segmented membrane comprising a porous support having a surface area, the surface area divided into a first portion and a second portion. A first fuel cell segment is formed from the first portion of the porous support imbibed with a first ionomer. A second fuel cell segment is formed from the second portion of the porous support imbibed with a second ionomer different from the first ionomer.
Also disclosed is a method of making a membrane electrode assembly. One method comprises masking a first portion of a porous support on each side of the porous support, leaving a second portion exposed. The second portion is imbibed with an acid ionomer to form an acid segment and then cured. The masking is removed from the first portion. The first portion is then imbibed with an alkaline ionomer to form an alkaline segment and cured.
These and other aspects of the present disclosure are disclosed in the following detailed description of the embodiments, the appended claims and the accompanying figures.
The disclosure is best understood from the following detailed description when read in conjunction with the accompanying drawings. It is emphasized that, according to common practice, the various features of the drawings are not to-scale. On the contrary, the dimensions of the various features are arbitrarily expanded or reduced for clarity.
The segmented membrane 100 comprises a porous support 110, shown in
The first fuel cell segment comprising the membrane electrode assembly 100 can be one of an alkaline fuel cell, an acid fuel cell, an intermediate temperature proton conducting fuel cell, a low temperature solid oxide fuel cell, a phosphoric acid fuel cell and a ceramic fuel cell, and the second fuel cell segment 108 is another of an alkaline fuel cell, an acid fuel cell, an intermediate temperature proton conducting fuel cell, a low temperature solid oxide fuel cell, a phosphoric acid fuel cell and a ceramic fuel cell. The first fuel cell segment 106 and the second fuel cell segment 108 can be selected to enhance the overall performance of the fuel cell 70.
One non-limiting example of the use of a segmented membrane 100 to improve the performance of a fuel cell 70 is the use of an alkaline segment and an acid segment to provide humidification to one or both fuel cell feeds.
In conventional acid membrane based PEM fuel cells, water is generated at the cathode. In conventional alkaline membrane based alkaline fuel cells, water is generated at the anode. As disclosed herein, a segmented membrane is developed, the segments utilizing different ionomers to generate water for humidification within the fuel cell. To humidify the anode feed gas without using an external humidifier, the segmented membrane has a portion of the membrane having an alkaline ionomer to allow water generation at the anode, with a second portion having an acid ionomer. With the segmented membrane, the incoming anode feed gas is humidified with this water generated at the anode. Use of the segmented membrane eliminates the need to use an external humidifier at the anode. In another implementation of the segmented membrane disclosed herein, to humidify the cathode oxidant without using an external humidifier, the segmented membrane is further divided into two alkaline ionomer sections, one section having the anode and the cathode on opposite sides from the other section. The anode of the one section generates water to humidify the oxidant fed to the other section and/or the acid ionomer segment.
For the example illustrated in
The first portion 112 has a first surface area and the second portion 114 has a second surface area. The first surface area of the first portion 112 is sized based on the flow rate of the hydrogen, or feed gas 30, to provide sufficient alkaline ionomer volume to humidify the hydrogen, or other feed gas, to at least 80% RH. The surface area of the alkaline segment 106 will typically be smaller than the surface area of the acid segment 108.
The anode catalyst layer 104 and the cathode catalyst layer 104′ can be the same catalyst material or can be different from the other. As a non-limiting example, the anode and cathode catalyst layers 104, 104′ can both be a carbon platinum (Pt/C) catalyst. Other alternative catalyst materials for oxygen reduction in an alkaline segment include, but are not limited to, Ag—Au, Ag—Cu, Ag—Pd, Ag—Co, Mo2C/C, Ag/LaMnO, Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT, and Mn2O3. Other alternative catalyst materials for oxygen reduction in an acid segment include, but are not limited to, Pt—Co/C, Pt—Ni/C, and Pt—Fe/C.
To further optimize the fuel cell performance, the cathode catalyst layer 104′ can be a catalyst specific to alkaline fuel cells on the alkaline segment 106 of the segmented membrane 100 and a catalyst specific to acid fuel cells on the acid segment 108 of the segmented membrane 100. The anode catalyst layer 104 can be common to both the acid and alkaline segments 108, 106.
The gas diffusion layers 102, 102′ are one or more types of carbon material, including, but not limited to, non-woven carbon fiber paper or woven carbon cloth. The gas diffusion layers 102, 102′ provide conductivity and assist the feed gas and oxidant to come in contact with the catalyst layers 104, 104′.
The acid ionomer used in the acid segment 108 can be any liquid acidic ionomer used in fuel cells. As a non-limiting example, a perfluorosulfonic acid (PFSA) ionomer such as Nafion™ PFSA lonomer Dispersion from The Chemours Company (Formerly DuPont Chemical Company), Aquivion™ PFSA lonomer from Solvay, and Flemion™ PFSA lonomer from Asahi Glass Company Ltd.
The alkaline ionomer used in the alkaline segment 106 can be any liquid alkaline ionomer used in alkaline fuel cells. As non-limiting examples, an alkaline ionomer from ACTA, a liquid ionomer based on 4-vinyl benzyl trimethyl hydroxide with a compatible monomer/polymer, and an alkaline ionomer from Tokuyama Corp. can be used. Although
In another implementation of the segmented membrane disclosed herein, the first portion 112 and the second portion 114 can be two separate portions of a porous substrate 110 that are separately made into the alkaline segment 106 and the acid segment 108. As illustrated in
In yet another implementation of the segmented membrane 200 disclosed herein, the alkaline segment 106 is divided into a first alkaline segment 202 adjacent the acid segment 108 and a second alkaline segment 204, as shown in
As illustrated in
Also disclosed are methods of making the membrane electrode assemblies herein. One method of making the segmented membrane 100 for the membrane electrode assembly is shown in the schematic of
To prepare the membrane electrode assembly 20, an anode catalyst 104 is layered on both the alkaline segment 106 and the acid segment 108 on one side of the segmented membrane 100 in step S5. In step S6, an anode gas diffusion layer 102 is layered on the anode catalyst 104. A cathode catalyst 104′ is layered on both the alkaline segment 106 and the acid segment 108 of the other side of the segmented membrane 100 in step S7. A cathode gas diffusion layer 102′ is layered on the cathode catalyst 104′ in step S8. An anode gas inlet 30 is formed on an anode catalyst side at a portion of the gas diffusion layer 102 on the alkaline segment 106 in step S9, and an oxidant inlet 40 is formed on a cathode catalyst side at the gas diffusion layer 102′ in step S10. Note that the order of steps can be changed so long as the layers are in the appropriate positions.
A feed gas inlet 214 is provided at the anode catalyst 208 of the second alkaline segment 204 and another feed gas inlet 216 is provided at the anode catalyst 206 of the first alkaline segment 202 in step S10. An oxidant inlet 218 is provided at the cathode catalyst 212 of the second alkaline segment 204 and another oxidant inlet 220 is provided at the cathode catalyst 210 of the first alkaline segment 202 in step S11. In step S12, a barrier layer 222 is positioned between the oxidant inlet 218 of the second alkaline segment 204 and the feed gas inlet 216 of the first alkaline segment 202. In step S13, a water separation membrane 224 is formed between the oxidant inlet 220 of the first alkaline segment 202 and the feed gas inlet 214 of the second alkaline segment 204.
For simplicity of explanation, although the figures and descriptions herein may include sequences or series of steps or stages, elements of the methods disclosed herein may occur in various orders or concurrently. Additionally, elements of the methods disclosed herein may occur with other elements not explicitly presented and described herein. Furthermore, not all elements of the methods described herein may be required to implement a method in accordance with this disclosure. Although aspects, features, and elements are described herein in particular combinations, each aspect, feature, or element may be used independently or in various combinations with or without other aspects, features, and elements.
As used herein, the terminology “example,” “embodiment,” “implementation,” “aspect,” “feature,” or “element” indicate serving as an example, instance, or illustration. Unless expressly indicated, any example, embodiment, implementation, aspect, feature, or element is independent of each other example, embodiment, implementation, aspect, feature, or element and may be used in combination with any other example, embodiment, implementation, aspect, feature, or element.
As used herein, the terminology “determine” and “identify,” or any variations thereof, includes selecting, ascertaining, computing, looking up, receiving, determining, establishing, obtaining, or otherwise identifying or determining in any manner whatsoever using one or more of the devices shown and described herein.
As used herein, the terminology “or” is intended to mean an inclusive “or” rather than an exclusive “or.” That is, unless specified otherwise, or clear from context, “X includes A or B” is intended to indicate any of the natural inclusive permutations. If X includes A; X includes B; or X includes both A and B, then “X includes A or B” is satisfied under any of the foregoing instances. In addition, the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form.
While the disclosure has been described in connection with certain embodiments, it is to be understood that the disclosure is not to be limited to the disclosed embodiments but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as is permitted under the law.
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