# Patent

## Title
Membrane electrode assembly and fuel cell using the same

## Abstract

A membrane electrode assembly includes a proton exchange membrane, a first electrode and a second electrode. The proton exchange membrane has two opposite surfaces, a first surface and a second surface. The first electrode is located adjacent to the first surface of the proton exchange membrane, and the first electrode includes a first diffusion layer and a first catalyst layer. The second electrode is located adjacent to the second surface of the proton exchange membrane, and the second electrode includes a second diffusion layer and a second catalyst layer. At least one of the first diffusion layer and the second diffusion layer includes a carbon nanotube structure. A fuel cell using the membrane electrode assembly is also provided.

## Background
RELATED APPLICATIONS
This application is related to applications entitled “MEMBRANE ELECTRODE ASSEMBLY AND FUEL CELL USING THE SAME”, U.S. patent application Ser. No.12/384,942, filed Apr. 9, 2009; “MEMBRANE ELECTRODE ASSEMBLY AND BIOFUEL CELL USING THE SAME”, U.S. patent Application Ser. No.12/384,964, filed Apr. 9, 2009; and “MEMBRANE ELECTRODE ASSEMBLY AND BIOFUEL CELL USING THE SAME”, U.S. patent application Ser. No.12/384,963, filed Apr. 9, 2009. The disclosures of the above-identified applications are incorporated herein by reference. “MEMBRANE ELECTRODE ASSEMBLY AND METHOD FOR MAKING THE SAME”, U.S. patent application Ser. No. 12/006,309, filed Dec. 29, 2007; “MEMBRANE ELECTRODE ASSEMBLY AND METHOD FOR MAKING THE SAME”, U.S. patent application Ser. No. 12/006,336, filed Dec. 29, 2007; “MEMBRANE ELECTRODE ASSEMBLY AND METHOD FOR MAKING THE SAME”, U.S. patent application Ser. No. 12/200,338, filed Aug. 28, 2008 are also related applications.
BACKGROUND
1. Technical Field
The disclosure generally relates to membrane electrode assemblies and fuel cell using the same, and particularly, to a membrane electrode assembly based on carbon nanotubes and a fuel cell using the same.
2. Description of Related Art
Fuel cells can generally be classified into alkaline, solid oxide, and proton exchange membrane fuel cells. The proton exchange membrane fuel cell has received increasingly more attention and has developed rapidly in recent years. Typically, the proton exchange membrane fuel cell includes a number of separated fuel cell work units. Each work unit includes a fuel cell membrane electrode assembly (MEA), flow field plates (FFP), current collector plates (CCP), as well as related support equipments, such as blowers, valves, and pipelines.
Referring to FIG. 11, the MEA 50 generally includes a proton exchange membrane 51 and two electrodes 54 located adjacent to two opposite surfaces of the proton exchange membrane 51 according to the prior art. Furthermore, each electrode 54 includes a catalyst layer 52 and a diffusion layer 53. The catalyst layer 52 is sandwiched between the diffusion layer 53 and the proton exchange membrane 51. The proton exchange membrane 51 is typically made of a material selected from the group consisting of erfluorosulfonic acid, polystyrene sulfonic acid, polystyrene trifluoroacetic acid, phenol formaldehyde resin acid, and hydrocarbons. The catalyst layer 52 includes catalyst materials and carriers. The catalyst materials can be metal particles, such as platinum particles, gold particles, ruthenium particles or combinations thereof. The carriers are generally carbon particles, such as graphite, carbon black, carbon fiber or carbon nanotubes. The diffusion layer 53 is constituted of carbon fiber paper.
However, the carbon fiber paper has the following disadvantages. Firstly, the carbon fibers in the carbon fiber paper are not uniformly dispersed, and therefore, the micropores therein defined by the carbon fibers are not uniform. Thus, such structure prevents the diffusion layer from uniformly diffusing the gases that are needed for the MEA. Secondly, the carbon fiber paper has high electrical resistance, thereby the travel of electrons between the diffusion layer and the external electrical circuit is restricted. As a result, the reaction activity of the MEA is reduced.
What is needed, therefore, are a membrane electrode assembly and a fuel cell using the same having improved reaction activity.



BRIEF DESCRIPTION OF THE DRAWINGS
Many aspects of the present membrane electrode assembly and fuel cell using the same can be better understood with references to the following drawings. The components in the drawings are not necessarily drawn to scale, the emphasis instead being placed upon clearly illustrating the principles of the present membrane electrode assembly and fuel cell using the same.
FIG. 1 is a schematic view of a membrane electrode assembly in accordance with an embodiment.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a drawn carbon nanotube film.
FIG. 3A is a schematic view of carbon nanotube of the drawn carbon nanotube film of FIG. 2 joined end to end.
FIG. 3B shows the drawn carbon nanotube films are situated side-by-side to increase the area of the carbon nanotube structure.
FIG. 3C Shows an SEM image of one embodiment of a carbon nanotube film structure including include at least two stacked drawn carbon nanotube
FIG. 3D is an exploded, isometric view of the carbon nanotube film structure of FIG. 3C.
FIG 3E is an exploded, isometric view of another embodiment a carbon nanotube film structure.
FIG. 4 is a Scanning Electron Microscope (SEM) image of an untwisted carbon nanotube wire.
FIG. 5 is a Scanning Electron Microscope (SEM) image of a twisted carbon nanotube wire.
FIG. 6 is a Scanning Electron Microscope (SEM) image of a pressed carbon nanotube film with the carbon nanotubes.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a pressed carbon nanotube film with the carbon nanotubes arranged along two or more directions.
FIG. 8 is a Scanning Electron Microscope (SEM) image of a flocculent carbon nanotube film.
FIG. 9 is a schematic view of a fuel cell in accordance with an embodiment.
FIG. 10 is a schematic view of a fuel cell in accordance with another embodiment.
FIG. 11 is a schematic view of a membrane electrode assembly of the prior art.



Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate at least one present embodiment of the membrane electrode assembly and fuel cell using the same, in at least one form, and such exemplifications are not to be construed as limiting the scope of the disclosure in any manner.
DETAILED DESCRIPTION
References will now be made to the drawings, in detail, to describe embodiments of the membrane electrode assembly and fuel cell using the same.
Referring to FIG. 1, a membrane electrode assembly 100 is provided according to an embodiment. The membrane electrode assembly 100 includes a proton exchange membrane 102, a first electrode 104 and a second electrode 106. The proton exchange membrane 102 has two opposite surfaces. The first electrode 104 is located adjacent to the first surface of the proton exchange membrane 102 and the second electrode 106 is located adjacent to the second surface of the proton exchange membrane 102. Furthermore, the first electrode 104 includes a first diffusion layer 104a and a first catalyst layer 104b, and the second electrode 106 includes a second diffusion layer 106a and a second catalyst layer 106b. The first catalyst layer 104b can be located adjacent to at least one surface of the first diffusion layer 104a. The second catalyst layer 106b can be located adjacent to at least one surface of the second diffusion layer 106a. In the embodiment of FIG. 1, the first catalyst layer 104b is located between the first diffusion layer 104a and the proton exchange membrane 102, and contacts with the first diffusion layer 104a and the proton exchange membrane 102. The second catalyst layer 106b is located between the second diffusion layer 106a and the proton exchange membrane 102, and contacts with the second diffusion layer 106a and the proton exchange membrane 102.
The first diffusion layer 104a includes a carbon nanotube structure. The carbon nanotube structure includes a plurality of carbon nanotubes distributed uniformly therein. A plurality of carbon nanotubes are arranged orderly or disorderly, entangled or arranged along a primary direction in the carbon nanotube structure. For example, the carbon nanotubes can be entangled with each other, forming a carbon nanotube structure with disordered arrangement of carbon nanotubes. Alternatively, if the carbon nanotube structure includes ordered arrangement of carbon nanotubes, the carbon nanotubes can be primarily oriented along the same direction, or along two or more directions. The carbon nanotubes in the carbon nanotube structure can be selected from a group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, and/or multi-walled carbon nanotubes. The length of the carbon nanotubes can range from about 200 to about 900 micrometers in one embodiment.
The carbon nanotube structure can include at least one carbon nanotube film, at least one carbon nanotube wire or combinations thereof. The carbon nanotubes of the first diffusion layer 104a can be in the structure of a carbon nanotube film or carbon nanotube wire. In one embodiment, the carbon nanotube structure has an overall planar structure. The carbon nanotube film can be a drawn carbon nanotube film, a pressed carbon nanotube film, or a flocculent carbon nanotube film. The area and the thickness of the carbon nanotube structure are unlimited and could be made according to user's specific needs. The carbon nanotube structure can be a free-standing structure, e.g. the carbon nanotube structure can keep its integrity without the use of a supporter.
In one embodiment, the carbon nanotube structure includes one drawn carbon nanotube film. Referring to FIGS. 2, and 3A, each drawn carbon nanotube film includes a plurality of successively oriented carbon nanotube segments 143 joined end-to-end by van der Waals attractive force therebetween. One example of carbon nanotube segments 143 joined end-to-end when drawing the carbon nanotube film is described in the article, “Spinning and processing continuous yarns from 4-inch wafer scale super aligned carbon nanotube arrays,” (Adv. Mater. 2006, 18, 1505-1510, 2006 Wiley-VCH Verlag GmbH & Co KGaA, Weinheim), incorporated herein by reference. Each carbon nanotube segment 143 includes a plurality of carbon nanotubes 145 parallel to each other, and combined by van der Waals attractive force therebetween. The carbon nanotube segments 143 can vary in width, thickness, uniformity and shape. The carbon nanotubes 145 in the drawn carbon nanotube film are also typically oriented along a preferred orientation.
The drawn carbon nanotube film 14 can be pulled out from a super-aligned carbon nanotube array 144 on a substrate. A width and a length of the drawn carbon nanotube film 14 are dependent on a size of the carbon nanotube array 144. In one embodiment, if the substrate is a 4-inch P-type silicon wafer, the width of the drawn carbon nanotube film 14 is in a range from about 0.5 nanometers to about 10 centimeters, and the thickness of the drawn carbon nanotube film 14 is in a range from about 0.5 nanometers to about 100 micrometers. The length of the carbon nanotube film drawn 14 from a 4-inch P-type silicon wafer can be greater than 10 meters.
Referring from FIG. 3B through FIG. 3E, the carbon nanotube structure includes two or more drawn carbon nanotube films 14. The two or more drawn carbon nanotube films 14 can be situated side-by-side and/or stacked with each other to form a planar carbon nanotube structure. Adjacent drawn carbon nanotube films 14 can be combined with each other by van der Waals attractive force therebetween. An angle α between the preferred orientations of the carbon nanotubes 145 in the two adjacent stacked drawn carbon nanotube films 14 is in a range of0≦α≦90°. Thus, the carbon nanotube structure includes a plurality of micropores defined by the stacked drawn carbon nanotube films 14. The micropores of one embodiment are distributed in the carbon nanotube structure uniformly. Diameters of the micropores can range from about 1 to about 10 micrometers. The micropores can be used to diffuse the gas. It is to be understood that there can be some variation in the carbon nanotube structure.
Further, the carbon nanotube structure can include at least one carbon nanotube wire. A single carbon nanotube wire can be folded, convoluted or otherwise shaped to form the planar carbon nanotube structure. Alternatively the carbon nanotube structure can include a plurality of carbon nanotube wires, the carbon nanotube wires can be located side by side, crossed, or weaved together to form the planar carbon nanotube structure. The carbon nanotube wire can be twisted or untwisted. The untwisted carbon nanotube wire is formed by treating the drawn carbon nanotube film with an organic solvent. Specifically, the drawn carbon nanotube film is treated by applying the organic solvent to the drawn carbon nanotube film so as to soak the entire surface of the drawn carbon nanotube film in the organic solvent. After being soaked by the organic solvent, the adjacent paralleled carbon nanotubes in the drawn carbon nanotube film will be bundled together, due to the surface tension of the organic solvent when the organic solvent volatilizing, and thus, the drawn carbon nanotube film is shrunk into untwisted carbon nanotube wire. The organic solvent is volatile. Referring to FIG. 4, the untwisted carbon nanotube wire includes a plurality of carbon nanotubes substantially oriented along the same direction (e.g., a direction along the length of the untwisted carbon nanotube wire). The carbon nanotubes are parallel to the axis of the untwisted carbon nanotube wire. A length of the untwisted carbon nanotube wire can be set as desired. A diameter of the untwisted carbon nanotube wire can be in a range from about 0.5 nanometers to about 100 micrometers.
The twisted carbon nanotube wire can be formed by twisting a drawn carbon nanotube film by using a mechanical force to turn two ends of the carbon nanotube film in opposite directions. Referring to FIG. 5, the twisted carbon nanotube wire includes a plurality of carbon nanotubes oriented around an axial direction of the twisted carbon nanotube wire. The carbon nanotubes are aligned around the axis of the carbon nanotube twisted wire like a helix.
Referring to FIG. 6 and FIG. 7, the carbon nanotube structure can include at least one pressed carbon nanotube film. The pressed carbon nanotube film can be isotropic. The carbon nanotubes in the pressed carbon nanotube film can be substantially arranged along the same direction or arranged along two or more directions as shown in FIG. 7. The carbon nanotubes in the pressed carbon nanotube film can rest upon each other. The adjacent carbon nanotubes are combined and attracted by van der Waals attractive force, thereby forming a free-standing structure after being pressed. An angle between a primary alignment direction of the carbon nanotubes and a base of the pressed carbon nanotube film can be in a range from about 0 degrees to about 15 degrees. The pressed carbon nanotube film can be formed by pressing a carbon nanotube array. The angle is closely related to pressure applied to the carbon nanotube array. The greater the pressure, the smaller the angle. The carbon nanotubes in the pressed carbon nanotube film can be parallel to the surface of the pressed carbon nanotube film when the angle is 0 degrees. A length and a width of the pressed carbon nanotube film can be set as desired. Also, multiple pressed carbon nanotube films can be stated upon one another.
Referring to FIG. 8, the carbon nanotube structure may include at least one flocculent carbon nanotube film. The flocculent carbon nanotube film is formed of a plurality of carbon nanotubes entangled with each other. The length of the carbon nanotubes in the flocculent carbon nanotube film can be larger than 10 micrometers. The adjacent carbon nanotubes are combined and entangled by van der Waals attractive force therebetween, thereby forming a microporous structure. Further, the flocculent carbon nanotube film is isotropic. The sizes of the micropores can be less than 10 micrometers. The micropores can be used to diffuse the gas and/or fuel. The length and a width of the flocculent carbon nanotube film is not limited. In one embodiment, the flocculent carbon nanotube film includes a plurality of long, curved, disordered carbon nanotubes entangled with each other.
In other embodiments, the carbon nanotube structure can include other materials thus becoming carbon nanotube composite. The carbon nanotube composite includes a carbon nanotube structure and a plurality of fillers dispersed therein. The filler can be comprised of a material selected from a group consisting of metal, ceramic, glass, carbon fiber and combinations thereof. In embodiments where carbon nanotube structure includes metal, the conductivity of the carbon nanotube structure will be increased.
Alternatively, the carbon nanotube composite includes a carbon fiber paper and a plurality of carbon nanotubes dispersed therein. The carbon nanotubes filled in the carbon fiber paper will increase the conductivity of the carbon fiber paper. Furthermore, the carbon fiber paper filled with carbon nanotubes has smaller micropores which allow the carbon fiber paper to diffuse gas uniformly. In one embodiment, mass ratio of the carbon nanotubes to the carbon fiber paper ranges from about 1% to about 15%.
The catalyst layers 104b, 106b include a plurality of catalyst materials and a plurality of carriers. The catalyst materials can include metal particles. The metal particles can be selected from a group consisting of platinum particles, gold particles, ruthenium particles and combinations thereof. The carriers can include carbon particles. The carbon particles can be comprised of a material selected from a group consisting of graphite, carbon black, carbon fiber, carbon nanotubes and combinations thereof. The distribution of the metal particles can be less than 0.5 milligram per square centimeter. In one embodiment, the metal particles are platinum and the carbon particles are carbon nanotubes.
The first electrode 104 can be fabricated by the following steps of: (a) providing metal particles and carbon particles, and putting them into a dispersion solution; (b) adding water and an active surface agent to the dispersion solution to obtain a catalyst slurry; and (c) coating the catalyst slurry on the carbon nanotube structure and drying the catalyst slurry, thereby forming the catalyst layer on the carbon nanotube structure to obtain the first electrode 104.
The material of the proton exchange membrane 102 can be selected from a group consisting of perfluorosulfonic acid, polystyrene sulfonic acid, polystyrene trifluoroacetic acid, phenol-formaldehyde resin acid, and hydrocarbons.
When the first diffusion layer 104a includes a carbon nanotube structure, the second diffusion layer 106a can be a carbon fiber paper. In one embodiment, both of the first diffusion layer 104a and the second diffusion layer 106a include a carbon nanotube structure.
Referring to FIG. 9, a fuel cell 10 is further provided according to one embodiment. The fuel cell 10 includes a membrane electrode assembly (MEA) 100, a first flow field plates (FFP) 108a, a second flow field plates (FFP) 108b, a first current collector plate (CCP) 110a, a second current collector plate (CCP) 110b, as well as first support equipment 112a and second support equipment 112b. The membrane electrode assembly 100 can be the membrane electrode assembly (MEA) 100 provided in one embodiment.
The FFP 108a, 108b is made of metals or conductive carbon materials. The first FFP 108a is located adjacent to a surface of the first diffusion layer 104a facing away from the proton exchange membrane 102. The second FFP 108b is located adjacent to a surface of the second diffusion layer 106a facing away from the proton exchange membrane 102. Each FFP 108a, 108b has at least one flow field groove 114. The flow field groove 114 is contacted with the diffusion layer 104a, 106a. Thus, the flow field groove 114 is used to transport the fuel gases, the oxidant gases, and the reaction product (e.g., water).
The CCP 110a , 110b is made of conductive materials such as metal. The first CCP 110a is located adjacent to a surface of the first FFP 108a facing away from the proton exchange membrane 102. The second CCP 110b is located adjacent to a surface of the second FFP 108b facing away from the proton exchange membrane 102. Thus, the CCP 110a , 110b is used to collect and conduct the electrons generated by the work process of MEA 100.
Referring to FIG. 10, a fuel cell 10 is further provided according another embodiment. The fuel cell 10 has similar structure to the fuel cell 10 provided in the previous embodiments except that it has no CCP because the carbon nanotube structure has excellent conductivity and can collect and conduct the electrons. The carbon nanotube structure can perform all of the functions of the CCP, thus eliminating the need for the CCP. This will reduce the materials needed to make the fuel cell 10. In other embodiments (not shown) one CCP will be employed on one side of the proton exchange membrane 102, while the carbon nanotube structure will collect and conduct electrons on the other side.
The related support equipments 112a, 112b include blowers, valves, and pipelines. The blower is connected with the FFP 108a, 108b via pipelines. The blowers blow the fuel gases and the oxidant gases.
In the working process of the fuel cell 10, oxygen is applied to the first electrode 104 and hydrogen is applied to the second electrode 106. In the second electrode 106, after the hydrogen has been applied to the second catalyst layer 106b, a reaction of each hydrogen molecule is as follows: H2→2H++2e . The hydrogen ions generated by the above-described reaction reach the cathode through the proton exchange membrane 102. At the same time, the electrons generated by the reaction also arrive at the first electrode 104 by an external electrical circuit. In the first electrode 104, oxygen is also applied to the first catalyst layer 104b. Thus, the oxygen reacts with the hydrogen ions and electrons as shown in the following equation: 1⁄2O2+2H++2e→H2O. In the electrochemical reaction process, the electrons generate an electrical current, and as a result, are able to output electrical energy to the load 120.
In one embodiment, the diffusion layer includes the carbon nanotube structure. The carbon nanotube structure includes a plurality of micropores uniformly distributed therein. As such, on one side of MEA 100, the hydrogen can be effectively and uniformly diffused in the carbon nanotube structure. The hydrogen is better able to make contact with metal particles in the catalyst layer. Thus, the catalytic reaction activity of the metal particles with the hydrogen is enhanced. On the other side of the MEA 100, the oxidant gases are also uniformly diffused to the catalyst layer through the carbon nanotube structure, thereby making better contact with the metal particles of the catalyst layer. Thus, the catalytic reaction activity of the metal particles with the hydrogen ions and electrons is enhanced. Due to the carbon nanotube structure having good conductivity, the electrons needed or generated in the reactions are quickly conducted by the carbon nanotube structure. This presents a more efficient membrane electrode assembly.
Finally, it is to be understood that the above-described embodiments are intended to illustrate rather than limit the disclosure. Variations may be made to the embodiments without departing from the spirit of the disclosure as claimed. The above-described embodiments illustrate the scope of the disclosure but do not restrict the scope of the disclosure.
It is also to be understood that the above description and the claims drawn to a method may include some indication in reference to certain steps. However, the indication used is only to be viewed for identification purposes and not as a suggestion as to an order for the steps.

## Claims

1. A membrane electrode assembly comprising:
a proton exchange membrane comprising a first surface and a second surface;
a first electrode, located on the first surface, comprising a first catalyst layer and a first diffusion layer in contact with each other, wherein the first catalyst layer is located between the first surface and the first diffusion layer; and
a second electrode, located on the second surface, comprising a second catalyst layer and a second diffusion layer in contact with each other, wherein the second catalyst layer is located between the second surface and the second diffusion layer;
wherein at least one of the first diffusion layer and the second diffusion layer comprises a carbon nanotube structure comprising at least one drawn carbon nanotube film, the at least one drawn carbon nanotube film comprises a plurality of carbon nanotube segments successively oriented along a fixed direction, and joined end-to-end by van der Waals attractive force therebetween along the fixed direction, wherein each carbon nanotube segment comprises a plurality of carbon nanotubes parallel to each other and combined by van der Waals attractive force therebetween, and the carbon nanotubes of the at least one drawn carbon nanotube film are oriented along the fixed direction.

2. The membrane electrode assembly as claimed in claim 1, wherein the carbon nanotube structure comprises a plurality of carbon nanotubes.

3. The membrane electrode assembly as claimed in claim 1, wherein the carbon nanotube structure comprises at least one carbon nanotube wire or combinations thereof.

4. The membrane electrode assembly as claimed in claim 1, wherein the at least one carbon nanotube film comprises a plurality of carbon nanotubes, wherein a majority of the plurality of carbon nanotubes are arranged along a same direction.

5. The membrane electrode assembly as claimed in claim 3, wherein the at least one carbon nanotube wire is an untwisted carbon nanotube wire comprising a plurality of carbon nanotubes joined end-to-end by van der Waals attractive force, the plurality of carbon nanotubes are parallel to an axis of the untwisted carbon nanotube wire.

6. The membrane electrode assembly as claimed in claim 3, wherein the at least one carbon nanotube wire is a carbon nanotube twisted wire comprising a plurality of carbon nanotubes aligned around an axis of the carbon nanotube twisted wire.

7. The membrane electrode assembly as claimed in claim 1, wherein the carbon nanotube structure comprises a plurality of micropores, and the diameters of the micropores range from about 1 to about 10 micrometers.

8. The membrane electrode assembly as claimed in claim 1, wherein the carbon nanotube structure comprises a carbon nanotube composite.

9. The membrane electrode assembly as claimed in claim 8, wherein the carbon nanotube composite comprises a plurality of carbon nanotubes and at least one other material.

10. The membrane electrode assembly as claimed in claim 8, wherein the carbon nanotube composite comprises a carbon fiber paper and a plurality of carbon nanotubes dispersed therein.

11. The membrane electrode assembly as claimed in claim 1, wherein each of the first and second catalyst layers comprises a plurality of metal particles and a plurality of carbon particles.

12. The membrane electrode assembly as claimed in claim 11, wherein the metal particles are selected from a group consisting of platinum particles, gold particles, ruthenium particles and combinations thereof, and the carbon particles are comprised of a material selected from a group consisting of graphite, carbon black, carbon fiber, carbon nanotubes and combinations thereof.

13. The membrane electrode assembly as claimed in claim 1, wherein the carbon nanotube structure comprises two or more stacked drawn carbon nanotube films, each of the two or more stacked drawn carbon nanotube films comprises a plurality of carbon nanotubes, majority of the plurality of carbon nanotubes oriented along a same oriented direction, an angle between the oriented directions of the carbon nanotubes of the two adjacent stacked drawn carbon nanotube films is in a range from about 0 degrees to about 90 degrees.