TWI650897B - Fuel cell electrode material, method for manufacturing fuel cell electrode material, and fuel cell device - Google Patents

Abstract

A fuel cell electrode material is disclosed herein comprising a plurality of pores having a substantially uniform size of from about 500 nm to about 5 mm, a variation of less than about 20%, and a porosity of from about 40 to about 85%. rate. The fuel cell electrode material can be used in a catalyst layer, a gas fusion layer or a water treatment layer in a fuel cell device. A plurality of fuel cell devices comprising a plurality of fine array porous fuel cell electrode materials having different designs and methods of preparing fine array porous fuel cell electrode materials are also disclosed herein.

Description

Fuel cell electrode material, method for manufacturing fuel cell electrode material, and fuel cell device

The present invention relates to a fuel cell electrode material for a plurality of fuel cell devices, and more particularly to a fine array porous fuel cell electrode material and the use of the fuel cell electrode material in a plurality of fuel cell devices.

A plurality of fuel cells are one type of electrochemical device. The electrochemical device converts chemical energy in a fuel into electrical energy by performing a chemical reaction using an oxidant. The fuel includes hydrogen and hydrocarbons such as diesel and methanol. The oxidizing agent is, for example, oxygen or hydrogen peroxide. Due to the high energy efficiency of the fuel cell and the ability to continuously generate electricity as long as there is fuel supply, the fuel cell has a wide range of applications, including transportation, material handling, stationary backup power, mobile backup power and emergency backup power. application.

A fuel cell typically requires a plurality of catalyst layers on the cathode assembly and the anode assembly to reduce the activation energy of the chemical reaction used to generate electricity. The catalyst layer is generally designed to have a plurality of finely dispersed crystal grains which are noble metal catalysts on a conductive support, and which have a high surface area to increase the active surface area of the catalyst and electrocatalysis active. The noble metal catalyst is, for example, platinum, and the conductive carrier is, for example, carbon paper, carbon cloth, and carbon nanotubes. However, such a configuration generally has problems such as high cost and insufficient reliability, thus limiting the practical application of the plural fuel cells.

Accordingly, a first object of the present invention is to provide a fuel cell electrode material for a fuel cell device.

Thus, the fuel cell electrode material of the present invention typically comprises a fine array of porous materials comprising a plurality of pores, wherein the pores have a pore size of from about 500 nm to 5 mm, and preferably from about 1000 to 50,000 nm; The size is substantially uniform and varies by less than about 20%; and the fine array porous material has a porosity of about 40-85%. In some embodiments, the fine array porous material can be composed of a metal such as nickel, aluminum, copper, gold, silver, titanium, iron, platinum, palladium, rhodium, manganese, cobalt or chromium. In some embodiments, the fine array porous material may be composed of, for example, stainless steel, platinum-cobalt, platinum-iron, platinum-chromium, platinum-nickel, platinum-titanium, platinum-manganese, platinum-copper, platinum-vanadium, Alloys of platinum-chromium-cobalt, platinum-iron-chromium, platinum-iron-manganese, platinum-iron-cobalt, platinum-iron-nickel, platinum-iron-copper, platinum-chromium-copper or platinum-cobalt-gallium composition. In some embodiments, the fine array porous material may be selected from the group consisting of CoTMPP-TiO ₂ , MnO _x -CoTMPP, CoFe ₂ O ₄ , Pt-WO ₃ , Pt-TiO ₂ , Pt-Cu-MO _x , It is composed of metal oxides of MnO ₂ , CrO ₂ , Cu _x Mn _y O _z , LaMnO ₃ and La _1-x Sr _x FeO ₃ .

In some embodiments, a fuel cell electrode material can be used in the cathode catalyst layer or the anode catalyst layer, and typically comprises a fine array of porous material having a porosity of about 74%. In some embodiments, the fine array porous material consists essentially entirely of a catalytic material: for example, a metal (eg, ruthenium, palladium, nickel, aluminum, copper, silver, gold, titanium, iron, platinum, manganese, cobalt) And chromium), an alloy (such as a platinum alloy, such as platinum-cobalt, platinum-iron, platinum-chromium, platinum-nickel, platinum-titanium, platinum-manganese, platinum-copper, platinum-vanadium, platinum - chromium-cobalt, platinum-iron-chromium, platinum-iron-manganese, platinum-iron-cobalt, platinum-iron-nickel, platinum-iron-copper, platinum-chromium-copper, platinum-cobalt-gallium, or a metal Oxide (for example, CoTMPP-TiO ₂ , MnO _x -CoTMPP, CoFe ₂ O ₄ , Pt-WO ₃ , Pt-TiO ₂ , Pt-Cu-MO _x MnO ₂ , CrO ₂ , Cu _x Mn _y O _z , LaMnO ₃ And La _1-x Sr _x FeO ₃ ). In some other embodiments, the fine array porous material can comprise a catalyst carrier and a catalyst component. The catalyst carrier is composed of a cost-effective metal (such as nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt and zinc), a conductive ceramic material (such as zinc oxide, copper oxide, indium tin oxide). , AZO, IZO, IGZO) or a conductive polymer (such as polypyrrole, polyphenylene sulfide, phthalocyanine, polyaniline and polythiophene). The catalyst component contains at least one of platinum, rhodium, palladium, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP, and CoFe ₂ O ₄ . In some embodiments, the catalyst component can be applied to the surface of the catalyst carrier. In some other embodiments, a plurality of particles as the catalyst component can be disposed in the pores of the fine array porous catalyst support. In some other embodiments, the particles as a catalyst component may be attached to the surface of a plurality of particles as a second catalyst carrier such as a carbon nanotube or carbon nanotube, and they are disposed together The pores of the fine array of porous catalyst support.

In some embodiments, a fuel cell electrode material can be used for the water treatment layer facing the cathode or the anode, and the fuel cell electrode material is typically surface treated, such as in the fine array porous fuel cell electrode material. A designated region is oxidized by the metal or coated with a hydrophilic material to render the designated region hydrophilic. Hydrophilic surface treatment of the water treatment layer electrode material can be accomplished in some embodiments by coating the electrode material with a hydrophilic plasma, in some instances by utilizing a surfactant (eg, dodecane) Ammonium sulfonate, sodium dodecyl sulfonate, sodium dioctyl succinate, perfluorooctane sulfonate, perfluorobutyl sulfonate, sodium laurate sarcosinate, perfluorodecanoic acid The electrode material is treated with an ester or perfluorooctanoate, or in some embodiments by using a chemical having a plurality of hydrophilic functional groups [eg, hydroxyl (OH) or carboxylic acid (COOH)] The material is chemically modified to complete.

In some embodiments, a fuel cell electrode material can be used for the gas diffusion layer opposite the cathode or the anode, and the fuel cell electrode material is typically surface treated, such as by applying a hydrophobic material in a designated area. To make the designated area hydrophobic. Hydrophobic surface treatment of the gas diffusion layer electrode material may be accomplished in some embodiments by coating a hydrophobic material with the hydrophobic material, or in some instances by using fluorononanone, decane or The fluorocarbon is processed to treat the electrode material.

Also disclosed herein is a fuel cell device employing the above-mentioned fine array porous fuel cell electrode material. The fuel cell device includes a membrane electrolyte assembly. The membrane electrolyte assembly comprises a polymer electrolyte membrane, an anode catalyst layer and a cathode catalyst layer, wherein the polymer electrolyte membrane is sandwiched between the anode layer and the cathode layer; the anode catalyst layer and the cathode catalyst At least one of the layers comprises a fine array of porous fuel cell electrode material having a porosity of about 74% and a catalyst.

In some embodiments of the fuel cell device, the fuel cell electrode material is composed of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt, and zinc; It is at least one of platinum, rhodium, palladium, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP or CoFe ₂ O ₄ . In some embodiments, the catalyst is uniformly applied to the surface of the fine array of porous material; in some other embodiments, the plurality of particles as the catalyst are disposed within the pores of the fine array of porous material. In some other embodiments, at least one of the anode catalyst layer and the cathode catalyst layer further comprises a catalyst carrier, such as a carbon nanotube or a carbon nanosphere, wherein the plurality of particles as the catalyst carrier Provided in the pores of the fine array porous material of at least one of the anode catalyst layer and the cathode catalyst layer, and the particles as the catalyst carrier carry a plurality of particles and the particles are The catalyst particles on the outer surface of the particles as the catalyst carrier.

In some embodiments, the fuel cell device includes a design of a combined catalyst-gas diffusion layer. In these embodiments, at least one of the anode catalyst layer and the cathode catalyst layer is also constructed to diffuse the reactive gases therethrough. In some embodiments, a specified region of the anode catalyst layer, the cathode catalyst layer, or both is surface treated to become hydrophobic to facilitate diffusion of the reactant gases therethrough. In some embodiments, the fuel cell device can include a design of a separate catalyst-gas diffusion layer. In these embodiments, the fuel cell device further includes an anode gas diffusion layer and a cathode gas diffusion layer, wherein the anode gas diffusion layer and the cathode gas diffusion layer are respectively arranged on the anode catalyst layer and the cathode contact The dielectric layer is opposite to one side of the polymer electrolyte membrane; and at least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises a second fine array fuel cell electrode material as described above. In some embodiments, the hole size of the second fine array fuel cell electrode material of at least one of the anode gas diffusion layer and the cathode gas diffusion layer is smaller than in the anode catalyst layer and the cathode catalyst layer. The hole size of the at least one fuel cell electrode material; and at least one of the anode gas diffusion layer and the cathode gas diffusion layer further comprises a second catalyst selected from at least one of cerium and palladium.

In some embodiments, the fuel cell device further comprises a water treatment layer. The water treatment layer is arranged at the bottom of the anode gas diffusion layer, the anode catalyst layer, the cathode catalyst layer and the cathode gas diffusion layer, wherein the water treatment layer comprises a third fine array porous fuel cell as disclosed above An electrode material, wherein a pore size of the third fine array porous fuel cell electrode material in the water treatment layer is greater than the fine array porous fuel cell electrode material in at least one of the anode catalyst layer and the cathode catalyst layer a pore size, and a pore size larger than the second fine array porous fuel cell electrode material of at least one of the anode gas diffusion layer and the cathode gas diffusion layer; and the third fineness in the water treatment layer The array porous fuel cell electrode material is selectively surface treated to form hydrophilicity. In some embodiments, the fuel cell device further includes an anode water treatment layer and a cathode water treatment layer, wherein the anode water treatment layer and the cathode water treatment layer are respectively arranged on the anode catalyst layer and the polymer Between the electrolyte membranes, and between the cathode catalyst layer and the polymer electrolyte membrane; at least one of the anode water treatment layer and the cathode water treatment layer comprises a second fine array porous fuel cell electrode material, and the second fine The pore size of the array porous fuel cell electrode material is larger than the pore size of the fine array porous fuel cell electrode material of at least one of the anode catalyst layer and the cathode catalyst layer; and the anode catalyst layer and the cathode contact The media layer is constructed to allow the reaction gas to diffuse therein.

In some embodiments, the fuel cell device includes a membrane electrolyte assembly, wherein the membrane electrolyte assembly includes an anode gas diffusion layer, an anode catalyst layer, a polymer electrolyte membrane, and a cathode contact sequentially from the anode to the cathode. a dielectric layer, wherein at least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises a fine array of porous fuel cell electrode material. In some embodiments of the fuel cell device, at least one of the anode catalyst layer and the cathode catalyst layer comprises a catalyst carrier selected from the group consisting of carbon nanotubes or carbon nanotubes.

Also disclosed herein are several methods of making a fine array porous fuel cell electrode material as described above, comprising the step (i) of preparing the fine array porous material by 3D printing or by a template fabrication process. In some embodiments of the methods, the fine array porous material can be fabricated by 3D printing. In some embodiments of the methods, the fine array porous material may be prepared by a template manufacturing process comprising the following sub-steps: a) electrophoretically fabricating a colloidal particle template; b) infiltrating an electrode material into the colloid a particle template; and c) removing the colloidal particle template. In some embodiments, the sub-step b) is accomplished by at least one of electrodeposition, physical vapor deposition, chemical vapor deposition, or sol gel processes.

In some embodiments, the methods further comprise the step (ii) of fabricating a second fine array of porous material on top of the fine array of porous material by 3D printing or by a template fabrication process. In some embodiments, the second fine array porous material in the step (ii) is constructed to have a pore size, and the pore size is larger than the pore size of the fine array porous material, and the second fine array porous material is Constructed with a hydrophilic surface. The second microarray porous material may be composed of a hydrophilic conductive polymer in some embodiments, or may be surface treated to form hydrophilicity in some other embodiments. In one example, the second fine array porous material is composed of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt, and zinc, and the surface of the second fine array porous material It is treated via an oxidation reaction. In another example, the second microarray porous material can be coated with a hydrophilic material.

In some embodiments, the method may further comprise the step (ii) of dispersing a plurality of particles as a catalyst carrier into the surface of the fine array porous material or the voids of the fine array porous material, wherein the catalyst The carrier carries a plurality of particles as a catalyst. The catalyst carrier can be a carbon nanotube or a carbon nanosphere. In some embodiments, the method may further comprise the step (iii) performed immediately after the step (ii), the step (iii) being the particles to be used as a catalyst and in the electrode material of the fuel cell The fine array of porous materials are combined and, in some embodiments, can be accomplished by heating.

In some embodiments, the method may further comprise the step (ii) of applying an anti-corrosion treatment to the fine array of porous material. For example, when the fine array porous material is composed of a metal such as zinc, titanium, and nickel, the corrosion treatment in the step (ii) may be an oxidation treatment in some embodiments, and may be an oxidation treatment in some other embodiments. The surface is coated with a resist material.

The fine array porous fuel cell electrode material described herein can also be applied to other types of fuel cell devices such as solid oxide fuel cells, direct methanol fuel cells, phosphoric acid fuel cells, fuel cells, and melting. Carbonate fuel cell or PFC. There is also provided a fuel cell device comprising a fine array of porous fuel cell electrode materials, wherein the fuel cell device is a solid oxide fuel cell, a direct methanol fuel cell, a phosphoric acid fuel cell, a fuel cell, a molten carbonate fuel cell or a PFC At least one of them.

A fine array porous fuel cell electrode material disclosed herein has the following advantages over conventional fuel cell electrode materials such as carbon paper/carbon coating/carbon nanotube coated with a plurality of catalyst particles. First, it has a very high effective electrocatalytic area due to the significantly higher surface-area-volume ratio of the fine array porous structure. Second, the film structure eliminates the problem of gradual loss of reliability due to the detachment of the catalyst particles of the conventional fuel cell from the conductive carrier. Third, it eliminates the use of a binder used in conventional fuel cells to closely attach the catalyst particles to the conductive carrier, thereby substantially reducing the amount of catalyst used and the cost of manufacturing the plurality of fuel cells. And greatly enhance the reliability. Fourth, designing a compound that is less expensive or a metal oxide (such as copper, iron, aluminum, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP, CoFe ₂ O _{4 ,} etc.) to form an expensive precious metal The micro-array porous conductive carrier of the catalyst (for example, platinum) can further reduce the manufacturing cost of the plurality of fuel cells, and can be higher than the conventional carbon paper/carbon cloth/carbon nanotube/carbon nanosphere. Electrical conductivity. Fifth, the presence of a periodic structure of the fine microarray porous fuel cell electrode material eliminates the problem of thermal buildup at some locations due to localized defects or uneven distribution of complex catalyst particles on a plurality of carbon-based conductive supports. Sixth, the presence of a periodic structure of the fine microarray porous fuel cell electrode material further enables reaction gases or reactive solvents (eg, H ₂ , O ₂ , ethanol, methanol), waste product (eg, water) across/through the material ) and the efficient distribution and transmission of electrons. Finally, some ideas can be combined in the multiple catalyst layer and the multiple gas diffusion layers of the fuel cell to simplify design, reduce cost, and improve reliability.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a conventional proton exchange membrane fuel cell device having a plurality of catalyst layers composed of carbon nanotubes coated with finely dispersed catalyst particles. The proton exchange membrane fuel cell device 100 includes an anode end plate 101, an anode bipolar plate 102, an anode gasket 103, an anode gas diffusion layer 104, a membrane electrode assembly 105, and a cathode gas diffusion sequentially from an anode to a cathode. A layer 106, a cathode gasket 107, a cathode dual electrode plate 108 and a cathode end plate 109. A plurality of gas passages are typically disposed on both the anode bipolar plate 102 and the cathode bipolar plate 108 as a path for separately injecting hydrogen and oxygen into the anode and cathode of the fuel cell. Limited to the view, FIG. 1 illustrates only the oxygen gas channel 110 on the cathode bipolar plate 108. The membrane electrode assembly 105 typically includes a polymer electrolyte membrane 111 sandwiched between an anode catalyst layer 112 and a cathode catalyst layer 113. Typically, both the anode catalyst layer and the cathode catalyst layer comprise a catalyst carrier, each coated with a very fine powder as an anode catalyst and a very fine powder as a cathode catalyst. The catalyst carrier is typically composed of a carbon paper, carbon cloth or carbon nanotube film; the anode catalyst may be a metal such as platinum, an alloy such as Pt-Ru, a metal such as cerium oxide. An oxide, a metal sulfide such as Mo _x Ru _y S _z and Mo _x Rh _y S _z , or a chalcogenide such as (Ru _1-x Mo _x )SeO _z ; and the cathode catalyst may be platinum Or nickel. Figure 1 also shows a picture of a typical anode catalyst layer comprising a film having carbon nanotubes 114 coated with platinum nanoparticles 115.

The conventional fuel cell described in Fig. 1 has the following disadvantages. First, it is generally necessary to stably attach and effectively disperse the catalyst particles on the surface of the conductive support using a binder. Moreover, the presence of a binder reduces the effective electrocatalytic area of the catalyst in the fuel cell. Therefore, in order to compensate for the reduction of the effective electrocatalytic area, it is necessary to use a large amount of catalyst to achieve the level of power output. Second, the plurality of catalyst particles coated on the surface of the electrically conductive support are loose and readily accessible from the carrier during a shock/shock environment or during gas ingress or when water/other reaction products are treated from the fuel cell. Fall off. These will cause the reliability of these fuel cells.

2 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials in accordance with some embodiments herein. As shown in FIG. 2, the membrane electrode assembly 200 includes a polymer electrolyte membrane 201 sandwiched between an anode catalyst layer 202 and a cathode catalyst layer 203. Both the anode catalyst layer 202 and the cathode catalyst layer 203 can comprise a fuel cell electrode material having a fine array of porous structures 204. The fuel cell electrode material 204 typically comprises a fine array of porous materials having a plurality of pores, wherein the pores have a pore size of between about 500 nm and 5 mm; the pores are substantially uniform in size and have a variation of less than about 20%. And the fine array porous material has a porosity of about 40-85%. In some preferred embodiments, a fuel cell electrode material can comprise a highly compact microarray porous material having a porosity of about 74%. For a porous material, the fine array porous material theoretically has a High surface-area-to-volume ratio.

In some embodiments, as described in 205, a fine array of porous material may be composed entirely of platinum or some other fuel cell catalyst material and thus may be used directly as one of the membrane electrode assemblies of a fuel cell. Catalyst layer material. In some other embodiments, a fine array of porous supports composed of a metal/alloy such as copper, aluminum, iron, nickel, and stainless steel or a conductive metal oxide such as Zn _x O _1-x may be uniform on the surface thereof. The fuel cell catalyst material, such as platinum, shown in 205 is applied. In some other embodiments, a fine array of porous materials can serve as a high surface-area conductive support to carry a plurality of particles, and the particles are a plurality of catalysts in the catalyst layers of a fuel cell. In some other embodiments, as described in 206, a fine array of porous cells consisting of a metal/alloy such as copper, aluminum, iron, stainless steel, and nickel, or a conductive metal oxide such as Zn _x O _1-x The carrier may be uniformly coated with nanoparticles of a fuel cell catalyst such as platinum in its pores. In some other embodiments, as described in 207, a second conductive support such as a carbon nanotube, graphene, and carbon nanosphere carries the catalyst particles on the surface, the second conductive carrier together with The catalyst particles are disposed in the holes of a first fine array of porous conductive support, and the first fine array porous conductive support is composed of copper, aluminum, iron, stainless steel or nickel or by, for example, Zn _x O _1-x consists of a conductive metal oxide.

The fuel cell electrode material as described above can also be used as a gas diffusion layer material due to the presence of periodic plural pores in the fine array porous structure, and the gas diffusion layer material allows reaction of, for example, hydrogen and oxygen. The gas is uniformly and efficiently dispersed through the pores of the fine array porous structure, while at the same time, the contact on the surface of the fine array porous conductive support or within the pores of the fine array porous conductive support The presence of the medium results in an efficient catalytic reaction in the fuel cell. These features allow for the design of a single combined catalyst-gas diffusion layer in a fuel cell device, and the single combined catalyst-gas diffusion layer functions as a catalyst layer and a gas diffusion in the fuel cell. Floor. The combined catalyst-gas diffusion layer with a fine array of porous structures can greatly simplify the design and manufacture of fuel cell modules. Furthermore, a hydrophobic/hydrophilic design based on processing a plurality of specific regions of the fine array porous fuel cell electrode material facilitates the design of the fine array porous fuel cell electrode material of the fuel cell The treatment of the final reaction product, such as water, is also possible. 3 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials according to some embodiments herein. The fuel cell membrane electrode assembly 300 includes a polymer electrolyte membrane 301, a combined anode catalyst-gas diffusion layer 302, a combined cathode catalyst-gas diffusion layer 303, and a water treatment layer 304, wherein the polymerization The electrolyte membrane 301 is interposed between the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303, and the water treatment layer 304 is disposed on the polymer electrolyte membrane 301, the combination The anode catalyst-gas diffusion layer 302 and the bottom of the combined cathode catalyst-gas diffusion layer 303. The combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303 both comprise a fine array of porous fuel cell electrode material, and the fine array porous fuel cell electrode material is completely composed of an anode The catalyst or cathodic catalyst is composed of, or alternatively, comprises a fine array of porous metal supports coated or impregnated with a plurality of particles and the particles are anode catalysts with or without a second catalyst carrier or with or without a second catalyst. The cathode catalyst of the carrier is shown as 205, 206 and 207 in Figure 2. In addition to functioning as a plurality of catalyst layers, the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303 also function as a plurality of gas diffusion layers in the fuel cell membrane electrode assembly. Optionally, in order to further increase the gas diffusion efficiency of the layers in the fuel cell, the combined anode catalyst-gas diffusion layer 302 and the combined cathode catalyst-gas diffusion layer 303 may be surface treated to increase the position. The hydrophobicity of some of the two layers. The water treatment layer 304 also contains a fine array of porous material and is designed to treat this final reaction product, such as water, within the fuel cell, and is optionally surface treated to increase hydrophilicity in order to further increase the water treatment efficiency.

4 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials according to some embodiments herein. Referring to FIG. 4A, the fuel cell membrane electrode assembly 400 includes an anode gas diffusion layer 401, an anode catalyst layer 402, a polymer electrolyte membrane 403, a cathode catalyst layer 404, and a cathode sequentially arranged from the anode to the cathode. Gas diffusion layer 405. In some embodiments, both the anode catalyst layer 402 and the cathode catalyst layer 404 can comprise a plurality of fine array porous fuel cell electrode materials as disclosed in FIG. 2 (205, 206, and 207), and such subtle The array porous fuel cell electrode materials respectively comprise an anode catalyst and a cathode catalyst, and the anode gas diffusion layer 401 and the cathode gas diffusion layer 405 may comprise a gas diffusion material having no fine array porous structure. In some other embodiments, the anode gas diffusion layer 401 and the cathode gas diffusion layer 405 may comprise a plurality of fine array porous electrode materials, and the anode catalyst layer 402 and the cathode catalyst layer 404 may comprise one without A conventional catalyst layer material of a fine array of porous structures is coated with an anode catalyst and a cathode catalyst, respectively, and the conventional catalyst layer material is, for example, carbon paper, carbon cloth or carbon nanotubes. In some other embodiments, the anode catalyst layer 402, the cathode catalyst layer 404, the anode gas diffusion layer 401, and the cathode gas diffusion layer 405 may all comprise a plurality of fine array porous fuel cell electrode materials, but have different The size or composition of the hole. In some embodiments, the anode catalyst layer 402 and the anode gas diffusion layer 401, or the cathode catalyst layer 404 and the cathode gas diffusion layer 405 may be a fine array porous fuel cell electrode material having a uniform pore size. a block, and the fine array porous fuel cell electrode material is coated or infiltrated with a plurality of particles of an anode/cathode catalyst which is a second catalyst carrier, the block being adjacent to the portion of the polymer electrolyte membrane 403 The anode/cathode catalyst layer 402/404 is formed; and the portion having no complex catalyst component forms the anode/cathode gas diffusion layer 401/405. In some embodiments, the fuel cell membrane electrode assembly can further include an additional anode/cathode catalyst layer between the polymer electrolyte membrane 403 and the anode/cathode catalyst layer 402/404. In one example, as depicted in Figure 4C, a conventional carbon-derived catalyst layer 423 comprises a carbon paper/carbon cloth/carbon nanotube coated with an anode/cathode catalyst disposed in the fine array porous contact On one side of the dielectric layer 422, the fine array porous catalyst layer 422 comprises a plurality of particles in the holes and the particles are a plurality of carbon carriers carrying a plurality of anode/cathode catalyst particles, and the fine array porous gas A diffusion layer 421 is disposed on the other side of the fine array porous catalyst layer 422.

In an embodiment as shown in FIG. 4B, the fuel cell membrane electrode assembly 410 includes an anode gas diffusion layer 411, an anode catalyst layer 412, a polymer electrolyte membrane 413, and a cathode array arranged in an order from the anode to the cathode. a cathode catalyst layer 414 and a cathode gas diffusion layer 415, wherein the anode catalyst layer 412 and the cathode catalyst layer 414 both comprise a plurality of fine array porous fuel cell electrode materials having the platinum catalyst; The diffusion layer 411 and the cathode gas diffusion layer 415 both comprise a fine array of porous fuel cell electrode material, and the fine array porous fuel cell electrode material has a hole size, and the hole size is smaller than that used in the anode catalyst layer 412. And a pore size of the fine array porous fuel cell electrode material in the cathode catalyst layer 414, and coated with the rhodium/platinum catalyst. With such a configuration, the anode gas diffusion layer 411 and the cathode gas diffusion layer 415 not only provide a plurality of diffusion paths to allow a reaction gas such as hydrogen and oxygen to be present in the anode catalyst layer 412 and the cathode catalyst layer of the fuel cell. Reacting on the surface of 414, and as a filter layer for removing carbon monoxide from the reaction gas by the presence of the ruthenium/platinum, to prevent carbon monoxide present in the reaction gas from being poisoned at the anode catalyst layer 412 and the cathode The platinum catalyst in the catalyst layer 414.

Figure 5 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials according to some embodiments herein. Referring to FIG. 5A, the fuel cell membrane electrode assembly 500 includes an anode gas diffusion layer 501, an anode catalyst layer 502, a polymer electrolyte membrane 503, a cathode catalyst layer 504, and a cathode sequentially arranged from the anode to the cathode. The gas diffusion layer 505 also includes a water treatment layer 506 disposed at the bottom of the layers 501-505. The composition and structure of the above layers 501-505 are similar to the anode gas diffusion layer 401, the anode catalyst layer 402, the polymer electrolyte membrane 403, and the cathode catalyst layer 404 in the fuel cell membrane electrode assembly as described in FIG. 4A. And a cathode gas diffusion layer 405. The water treatment layer 506 comprises a fine array of porous material, and the pore size of the fine array porous material is about 0.5-100 times the pore size of the anode gas diffusion layer 501 and the cathode gas diffusion layer 505, and is designed The final liquid reaction product, such as water, is treated within the fuel cell and is optionally surface treated to increase hydrophilicity in order to further increase the processing efficiency.

In another embodiment, as shown in FIG. 5B, the fuel cell membrane electrode assembly 510 includes an anode combined catalyst-gas diffusion layer 511, an anode water treatment layer 512, and an aggregation sequentially arranged from the anode to the cathode. An electrolyte membrane 513, a cathode water treatment layer 514, and a cathode combined catalyst-gas diffusion layer 515. The anode combined catalyst-gas diffusion layer 511 and the cathode combined catalyst-gas diffusion layer 515 both comprise a plurality of fine array porous fuel cell electrode materials as described in FIG. 3 and having a smaller pore size. They are coated with an anode catalyst and a cathode catalyst, respectively. Both the anode combined catalyst-gas diffusion layer 511 and the cathode combined catalyst-gas diffusion layer 515 serve as a catalyst layer and a diffusion layer in the fuel cell. Both the anode water treatment layer 512 and the cathode water treatment layer 514 comprise a plurality of fine array porous materials and are designed to treat the final liquid reaction product, such as water, within the fuel cell. The anode array water treatment layer 512 and the fine array porous material in the cathode water treatment layer 514 have a pore size, which is selectively larger or smaller than the anode combined catalyst-gas diffusion layer 511 and the cathode combined catalyst-gas diffusion. The pore size of the fine array porous fuel cell electrode material in layer 515. The anode water treatment layer 512 and the cathode water treatment layer 514 are optionally surface treated to have more hydrophilicity on the surface, which in turn increases water treatment benefits; and more preferably they are surface treated on the surface It has more hydrophobicity to keep water away from the anode combined catalyst-gas diffusion layer 511 and the cathode combined catalyst-gas diffusion layer 515, while allowing a plurality of reactive gases to flow efficiently to be combined with the anode. The catalyst-gas diffusion layer 511 is in contact with the catalyst in the cathode combined catalyst-gas diffusion layer 515.

Figure 6 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials according to some embodiments herein. The fuel cell membrane electrode assembly 600 includes an anode gas diffusion layer 601, an anode catalyst layer 602, a polymer electrolyte membrane 603, a cathode catalyst layer 604, and a cathode gas diffusion layer 605, which are sequentially arranged from the anode to the cathode. . The anode catalyst layer 602 and the cathode catalyst layer 604 comprise a conductive carrier such as carbon paper, carbon cloth, carbon nanotube film or carbon nanosphere film, respectively coated with a plurality of anode catalysts and plural Cathode catalyst. The anode gas diffusion layer 601 and the cathode gas diffusion layer 605 each comprise a fine matrix porous material, and in order to further increase the gas diffusion efficiency of the layers in the fuel cell, the fine matrix porous material is selectively surface treated to Increase the hydrophobicity of the surface of the layers.

In some embodiments of a fuel cell device comprising a fine array of porous fuel cell electrode materials, whether it is a catalyst layer, a gas diffusion layer or a water treatment layer, the fine array porous fuel cell electrode material may be borrowed All or part of the electrode material is surface-treated by an oxidation reaction to avoid acid and alkali corrosion caused by the acid and alkali present in the fuel cell device or the electrochemical reaction carried out in the fuel cell.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the simple equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still Within the scope of the invention patent.

100‧‧‧Proton exchange membrane fuel cell device

101‧‧‧Anode end plate

102‧‧‧Anode bipolar plate

103‧‧‧Anode washer

104‧‧‧Anode gas diffusion layer

105‧‧‧ membrane electrode assembly

106‧‧‧ cathode gas diffusion layer

107‧‧‧Cathode Washer

108‧‧‧Cathode double electrode plate

109‧‧‧ Cathode end plate

110‧‧‧Oxygen gas channel

111‧‧‧ polymer electrolyte membrane

112‧‧‧Anode catalyst layer

113‧‧‧ Cathode catalyst layer

114‧‧‧Carbon nanotubes

115‧‧‧Platinum nanoparticles

200‧‧‧ membrane electrode assembly

201‧‧‧ polymer electrolyte membrane

202‧‧‧Anode catalyst layer

203‧‧‧ Cathode catalyst layer

204‧‧‧Microarray porous structure

205‧‧‧ fuel cell electrode material

206‧‧‧ fuel cell electrode material

207‧‧‧ Fuel cell electrode material

300‧‧‧ fuel cell membrane electrode assembly

301‧‧‧ polymer electrolyte membrane

302‧‧‧Combined anode catalyst-gas diffusion layer

303‧‧‧Combined Cathodic Catalyst-Gas Diffusion Layer

304‧‧‧ water treatment layer

400‧‧‧ fuel cell membrane electrode assembly

401‧‧‧Anode gas diffusion layer

402‧‧‧Anode catalyst layer

403‧‧‧ polymer electrolyte membrane

404‧‧‧Cathodic catalyst layer

405‧‧‧ cathode gas diffusion layer

410‧‧‧ fuel cell membrane electrode assembly

411‧‧‧Anode gas diffusion layer

412‧‧‧Anode catalyst layer

413‧‧‧ polymer electrolyte membrane

414‧‧‧ Cathode catalyst layer

415‧‧‧ cathode gas diffusion layer

421‧‧‧Microarray porous gas diffusion layer

422‧‧‧Microarray porous catalyst layer

423‧‧‧carbon-derived catalyst layer

500‧‧‧ fuel cell membrane electrode assembly

501‧‧‧Anode gas diffusion layer

502‧‧‧Anode catalyst layer

503‧‧‧ polymer electrolyte membrane

504‧‧‧ Cathode catalyst layer

505‧‧‧ cathode gas diffusion layer

506‧‧‧Water treatment layer

510‧‧‧ fuel cell membrane electrode assembly

511‧‧‧Anode combined catalyst-gas diffusion layer

512‧‧‧Anode water treatment layer

513‧‧‧ polymer electrolyte membrane

514‧‧‧cathode water treatment layer

515‧‧‧Cathode combined catalyst-gas diffusion layer

600‧‧‧ fuel cell membrane electrode assembly

601‧‧‧Anode gas diffusion layer

602‧‧‧Anode catalyst layer

603‧‧‧ polymer electrolyte membrane

604‧‧‧ Cathode catalyst layer

605‧‧‧ cathode gas diffusion layer

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: Figure 1 illustrates a conventional proton exchange membrane fuel cell device having a plurality of catalytic layers, wherein the catalytic layers are A plurality of carbon nanotubes coated with a plurality of finely dispersed catalyst particles; FIG. 2 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials, according to some embodiments herein; FIG. 3 illustrates some embodiments according to the present disclosure A fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials; Figure 4 illustrates a fuel cell membrane electrode assembly comprising a plurality of fine array porous electrode materials, according to some embodiments herein; Figure 5 illustrates a plurality of embodiments according to some embodiments herein The fuel cell membrane electrode assembly comprises a plurality of fine array porous electrode materials; and Figure 6 illustrates that another fuel cell membrane electrode assembly comprises a plurality of fine array porous electrode materials, according to some embodiments herein.

Claims (40)

A fuel cell electrode material for a fuel cell device, the fuel cell electrode material comprising: a fine array of porous materials, comprising a plurality of pores, wherein the pores have a pore size of about 1000 to 50000 nm; The size is substantially uniform and the amount of change is less than about 20%; and the fine array porous material has a porosity of about 40%-85%, wherein the fine array porous material is a metal, a conductive ceramic material or a conductive high a molecule selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, manganese, cobalt, and zinc. The ceramic material is selected from the group consisting of zinc oxide, copper oxide, indium tin oxide, AZO, IZO, and IGZO. The conductive polymer is selected from the group consisting of polypyrrole, polyphenylene sulfide, phthalocyanine, polyaniline and polythiophene; a plurality of catalyst carrier particles and a plurality of catalyst particles, wherein the catalyst particles are disposed on the catalyst carrier particles Surfaces, and the catalyst carrier particles carrying the catalyst particles are disposed within the pores of the fine array of porous material. The fuel cell electrode material of claim 1, wherein the fine array porous material has a porosity of about 74%. The fuel cell electrode material according to claim 2, wherein the fine array porous material is coated with at least one of platinum, rhodium, palladium, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP, and CoFe ₂ O ₄ . The fuel cell electrode material according to claim 2, wherein the catalyst particles are composed of at least one of platinum, rhodium, palladium, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP, and CoFe ₂ O ₄ , wherein The catalyst particles are disposed within the pores of the fine array of porous material. The fuel cell electrode material according to claim 1, wherein the catalyst carrier particles comprise at least one of a carbon nanotube, a graphene or a carbon nanosphere. The fuel cell electrode material according to claim 5, wherein the catalyst particles are composed of at least one of platinum, rhodium, palladium, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP or CoFe ₂ O ₄ . The fuel cell electrode material according to claim 1, wherein a specified region of the fine array porous material is surface-treated to form hydrophilicity. The fuel cell electrode material according to claim 7, wherein the fine array porous material is surface-treated, by performing oxidation reaction on the surface of the fuel cell electrode material, by using a hydrophilic plasma coating. The surface of the fuel cell electrode material is completed by treating the surface of the fuel cell electrode material with a surfactant, or by using a chemical reagent having at least one hydrophilic functional group. The surface of the electrode material is chemically modified to complete. The fuel cell electrode material of claim 1, wherein a specified region of the fine array porous material is surface treated to form hydrophobicity. A fuel cell device comprising a membrane electrolyte assembly, wherein the membrane electrolyte assembly comprises a polymer electrolyte membrane, an anode catalyst layer and a cathode catalyst layer, wherein the polymer electrolyte membrane is sandwiched between the anode layer and the cathode At least one of the anode catalyst layer and the cathode catalyst layer comprises the fuel cell electrode material and a catalyst according to claim 1. The fuel cell device according to claim 10, wherein the fine array porous material in the fuel cell electrode material is composed of a metal selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, Manganese, cobalt and zinc; the catalyst is at least one of platinum, rhodium, palladium, CoPc, CoTMPP-TiO ₂ , MnO _x -CoTMPP or CoFe ₂ O ₄ . The fuel cell device of claim 11, wherein the catalyst is uniformly applied to a surface of the fine array porous material. The fuel cell device of claim 11, wherein a plurality of particles of the catalyst are disposed in the pores of the fine array of porous material. The fuel cell device of claim 11, wherein at least one of the anode catalyst layer and the cathode catalyst layer further comprises a catalyst carrier selected from the group consisting of carbon nanotubes, graphene or At least one of the carbon nanospheres, wherein the plurality of particles as the catalyst carrier are disposed in the pores of the fine array porous material of at least one of the anode catalyst layer and the cathode catalyst layer, and The particles as the catalyst carrier carry a plurality of particles which are the catalyst particles on the outer surface of the particles as the catalyst carrier. The fuel cell device of claim 10, wherein at least one of the anode catalyst layer and the cathode catalyst layer is further configured to diffuse the reactive gases therethrough. The fuel cell device according to claim 15, wherein a designated region of the anode catalyst layer, the cathode catalyst layer or both is surface-treated to become hydrophobic to facilitate diffusion of the reaction gases therethrough. The fuel cell device according to claim 10, further comprising an anode gas diffusion layer and a cathode gas diffusion layer, wherein the anode gas diffusion layer and the cathode The gas diffusion layer is respectively disposed on a side opposite to the polymer electrolyte membrane of the anode catalyst layer and the cathode catalyst layer; and at least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises The second microarray fuel cell electrode material of claim 1. The fuel cell device of claim 17, wherein the hole size of the second fuel cell electrode material of at least one of the anode gas diffusion layer and the cathode gas diffusion layer is smaller than the anode catalyst layer and the a size of the hole of the fuel cell electrode material of at least one of the cathode catalyst layers; and at least one of the anode gas diffusion layer and the cathode gas diffusion layer further comprises a second selected from at least one of tantalum and palladium catalyst. The fuel cell device according to claim 17, further comprising a water treatment layer arranged at the bottom of the anode gas diffusion layer, the anode catalyst layer, the cathode catalyst layer and the cathode gas diffusion layer, wherein the water treatment The layer includes the third fuel cell electrode material according to claim 1, wherein a pore size of the third fuel cell electrode material in the water treatment layer is greater than at least the anode catalyst layer and the cathode catalyst layer a hole size of the fuel cell electrode material of one of the holes, and a hole size larger than the second fuel cell electrode material of at least one of the anode gas diffusion layer and the cathode gas diffusion layer; and in the water treatment layer The third fuel cell electrode material is selectively surface treated to form hydrophilicity. The fuel cell device according to claim 10, further comprising an anode water treatment layer and a cathode water treatment layer, wherein the anode water treatment layer and the cathode water treatment layer are respectively arranged on the anode catalyst layer and the polymerization Between the electrolyte membranes, and between the cathode catalyst layer and the polymer electrolyte membrane; the anode water At least one of the physical layer and the cathode water treatment layer comprises a second fuel cell electrode material as claimed in claim 1, and a pore size of the second fuel cell electrode material is greater than that in the anode catalyst layer and the cathode a pore size of the fuel cell electrode material of at least one of the catalyst layers; and the anode catalyst layer and the cathode catalyst layer are configured to allow diffusion of the reactive gas therein. The fuel cell device according to claim 10, comprising a membrane electrolyte assembly, wherein the membrane electrolyte assembly comprises an anode gas diffusion layer, an anode catalyst layer, a polymer electrolyte membrane and a cathode sequentially from the anode to the cathode. a catalyst layer, wherein at least one of the anode gas diffusion layer and the cathode gas diffusion layer comprises a fuel cell electrode material as recited in claim 1. The fuel cell device according to claim 21, wherein at least one of the anode catalyst layer and the cathode catalyst layer comprises a catalyst carrier selected from the group consisting of carbon nanotubes or carbon nanotubes. A method of manufacturing the fuel cell electrode material according to claim 1, comprising the steps of: (i) preparing the fine array porous material by 3D printing or by a template manufacturing method; wherein the template manufacturing method comprises The following sub-steps: a) electrophoretically fabricating a colloidal particle template; b) infiltrating an electrode material into the colloidal particle template; and c) removing the colloidal particle template; dispersing a plurality of catalytic carrier particles into the fine array porous The surface of the material or the voids of the fine array of porous material, wherein the catalyst carrier carries a plurality of particles as a catalyst. The method of manufacturing a fuel cell electrode material according to claim 23, wherein the sub-step b) of the template manufacturing method is by at least one of electrodeposition, physical vapor deposition, chemical vapor deposition, or sol-gel method. carry out. The method of producing a fuel cell electrode material according to claim 23, further comprising the step (ii) performed immediately after the step (i), by means of 3D printing or by a template manufacturing method on top of the fine array porous material A second fine array of porous material is fabricated thereon. The method of manufacturing a fuel cell electrode material according to claim 25, wherein the second fine array porous material in the step (ii) is constructed to have a pore size larger than a pore size of the fine array porous material, and The second microarray porous material is constructed with a hydrophilic surface. The method of producing a fuel cell electrode material according to claim 26, wherein the second fine array porous material in the step (ii) is composed of a hydrophilic conductive polymer. The method of producing a fuel cell electrode material according to claim 26, wherein the second fine array porous material in the step (ii) is surface-treated to form hydrophilicity. The method of manufacturing a fuel cell electrode material according to claim 28, wherein the second fine array porous material in the step (ii) is selected from the group consisting of nickel, aluminum, copper, iron, titanium, chromium, A metal of manganese, cobalt, and zinc is formed, and the surface of the second fine array porous material is treated via an oxidation reaction. The method of producing a fuel cell electrode material according to claim 28, wherein the second fine array porous material in the step (ii) is coated with a hydrophilic material. The method of producing a fuel cell electrode material according to claim 23, wherein the catalyst carrier is selected from at least one of a carbon nanotube or a carbon nanotube. The method of manufacturing a fuel cell electrode material according to claim 31, further comprising Immediately after the step (iii), which is carried out after the step (ii), the particles as a catalyst are combined with the fine array porous material in the electrode material of the fuel cell. The method of producing a fuel cell electrode material according to claim 32, wherein the step (iii) is performed by heating. The method of producing a fuel cell electrode material according to claim 23, which further comprises the step (ii) which is carried out immediately after the step (i), wherein the fine array porous material is subjected to an anti-corrosion treatment. The method for producing a fuel cell electrode material according to claim 23, wherein the fine array porous material in the step (i) is composed of a metal selected from the group consisting of zinc, titanium and nickel; and in the step (ii) This anti-corrosion treatment is a one-oxidation treatment. The method of producing a fuel cell electrode material according to claim 34, wherein the fine array porous material in the step (i) is composed of a metal selected from the group consisting of zinc, titanium, and nickel; and in the step (ii) The anti-corrosion treatment in the surface is coated with a resist material. A fuel cell device comprising the fuel cell electrode material according to claim 1, wherein the fuel cell device is at least a solid oxide fuel cell, a direct methanol fuel cell, a phosphoric acid fuel cell, a molten carbonate fuel cell or a PFC One. The fuel cell electrode material according to claim 8, wherein the fine array porous material is surface-treated, and the surface of the fuel cell electrode material is treated by using a surfactant, wherein the surfactant is Is ammonium dodecyl sulfate, sodium dodecyl sulfate, dioctyl succinate At least one of sodium, perfluorooctane sulfonate, perfluorobutane sulfonate, sodium laurate sarcosinate, perfluorodecanoate or perfluorooctanoate. The fuel cell electrode material according to claim 8, wherein the fine array porous material is surface-treated, and the surface of the fuel cell electrode material is chemically modified by using a chemical agent having a plurality of hydrophilic functional groups. This is accomplished wherein the hydrophilic functional group is a hydroxyl group or a carboxylic acid group. The fuel cell electrode material according to claim 9, wherein the fine array porous material is surface-treated, by using a hydrophobic plasma coated on the surface of the fuel cell electrode material, or by using fluorine At least one of an anthrone, a siloxane, or a fluorocarbon is processed to treat the surface of the fuel cell electrode material.