Method for preparing an alumina template, membrane electrode and fuel cell

Abstract

The application discloses a preparation method of an aluminum oxide template, a membrane electrode and a preparation method thereof and a fuel cell. The preparation method of the aluminum oxide template is characterized by the following steps: an anodic oxidation method is performed on an aluminum substrate, and etching treatment is performed, so that a plurality of first holes and a plurality of second holes are formed on the obtained aluminum oxide template, and the aluminum oxide template containing at least two different holes is obtained. In the premise of maintaining the structural stability and the hole structure stability of the aluminum oxide template, the area proportion of the holes on the aluminum substrate is improved, the gap between the holes is reduced, the nanometer material array with smaller interval gaps can be formed by using the aluminum oxide template, the waste of nanometer materials caused by falling into the nanometer materials in the gaps is avoided, the deposition efficiency of the nanometer materials is improved, and the utilization rate of noble metals is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of batteries, in particular to a preparation method of an aluminum oxide template, a membrane electrode and a preparation method thereof, and a fuel cell. BACKGROUND

[0002] An anodic aluminum oxide (AAO) template electrode and a membrane electrode are core components of a proton exchange membrane fuel cell (PEMFC), are the final place of multiphase material transport and electrochemical reaction causing energy conversion, and determine the performance, service life and cost of the PEMFC.

[0003] At present, researches on ordered membrane electrodes mainly focus on constructing ordered catalyst layer components and structures, such as ordered carriers, ordered catalysts and ordered proton conductors. In the preparation process of the membrane electrode, a porous aluminum oxide template can be used to deposit noble metals such as platinum or platinum alloy in the pore channels of the aluminum oxide template, to generate an ordered catalyst nanometer array, so as to obtain a one-dimensional ordered nanometer array catalyst electrode, and then a membrane electrode is obtained by pressing. In the process of preparing the catalyst nanometer array, noble metals such as platinum or platinum alloy are deposited on the aluminum oxide template, and the aluminum oxide template needs to be removed subsequently, thereby losing a part of the noble metals, and the production cost is greatly increased due to the high price of the noble metals.

[0004] Therefore, how to improve the utilization rate of noble metals in the preparation of ordered membrane electrodes and reduce the production cost is a problem to be solved in the prior art. SUMMARY

[0005] Therefore, the present application provides a preparation method of an aluminum oxide template, a membrane electrode and a preparation method thereof, and a fuel cell, to improve the utilization rate of noble metals.

[0006] The present application is implemented in the following manner. A preparation method of an aluminum oxide template is provided, which comprises: providing an aluminum substrate, treating the aluminum substrate to obtain an aluminum oxide template intermediate, the aluminum oxide template intermediate having a plurality of first holes arranged at intervals; forming a plurality of second holes arranged at intervals in a region of the aluminum oxide template intermediate which does not form the first holes, to obtain an aluminum oxide template.

[0007] Optionally, in some embodiments of the present application, the aluminum substrate is treated by an anodic oxidation method, which comprises: pretreating the aluminum substrate to remove an oxide layer on the surface of the aluminum substrate; using the aluminum substrate from which the oxide layer is removed as an anode, using an aluminum foil from which the oxide film is not removed as a cathode, using an acid solution as an electrolyte, and performing anodic oxidation on the aluminum substrate under constant current passing; and / or forming the plurality of second holes arranged at intervals by etching.

[0008] Optionally, in some embodiments of the present application, the acid solution is selected from one or more of an oxalic acid aqueous solution, a phosphoric acid aqueous solution, a sulfuric acid aqueous solution, a chromic acid aqueous solution, or a citric acid aqueous solution; and / or the etching method is plasma etching, the power of the plasma etching is 30-80 W, the gas flow rate is 0.4-0.8 L / min, and the etching time is 40-180 s.

[0009] Optionally, in some embodiments of the present application, the second hole has a smaller diameter than the first hole; and / or the diameter of the first hole is 60-120 nm; and / or two adjacent first holes have a first spacing, and the first spacing is 180-300 nm; and / or the diameter of the second hole is 30-40 nm; and / or on the alumina template, the density of the second hole is greater than the density of the first hole.

[0010] Optionally, in some embodiments of the present application, the first holes form a first array, the first array includes a plurality of first hole columns arranged at intervals, the second holes form a second array, the second array includes a plurality of second hole columns arranged at intervals, and the first hole columns and the second hole columns are arranged alternately; and / or each first hole is surrounded by a plurality of second holes; and / or on the alumina template, the density of the second hole is 1-2 times the density of the first hole.

[0011] Correspondingly, the present application also provides a preparation method of a membrane electrode, which comprises: providing a substrate and an alumina template, wherein the alumina template is prepared by the above-mentioned preparation method of an alumina template, and the alumina template includes a plurality of first holes arranged at intervals and a plurality of second holes arranged at intervals; arranging the alumina template on the substrate; using the alumina template as a mask to form a vertically oriented carbon nanotube array on the substrate, and then removing the alumina template; depositing a noble metal on the carbon nanotube array to obtain an ordered nanometer array catalytic electrode; using the ordered nanometer array catalytic electrode as a cathode and / or an anode, arranging a proton exchange membrane between the cathode and the anode, and pressing to form a membrane electrode.

[0012] Optionally, in some embodiments of the present application, the step of forming the carbon nanotube array comprises: placing the substrate with the alumina template attached thereon in an atmosphere of acetylene, so that the acetylene is vapor-deposited to form the carbon nanotube array; and / or the step of removing the alumina template comprises: dissolving and removing the alumina template using an alkali solution; and / or the carbon nanotube array comprises first carbon nanotubes corresponding to the first holes in the alumina template, and second carbon nanotubes corresponding to the second holes in the alumina template; and / or the step of depositing a noble metal on the carbon nanotube array comprises: using the substrate with the carbon nanotube array formed thereon as a working electrode, contacting the side of the working electrode on which the carbon nanotube array is formed with an electroplating solution containing a noble metal compound, using a platinum sheet as a counter electrode, and using a saturated calomel electrode as a reference electrode to perform electrodeposition, so as to deposit the noble metal on the carbon nanotube array.

[0013] Optionally, in some embodiments of the present application, the vapor-deposition temperature is 450-500°C, and the vapor-deposition time is 1-2 min; and / or the alkali solution is selected from one or more of an aqueous NaOH solution and an aqueous KOH solution; and / or the first carbon nanotubes have a diameter of 60-120 nm; and / or the distance between adjacent two first carbon nanotubes is 180-300 nm; and / or the second carbon nanotubes have a diameter of 30-40 nm; and / or in the carbon nanotube array, the density of the second carbon nanotubes is greater than the density of the first carbon nanotubes; and / or the noble metal compound comprises a first noble metal compound, and the first noble metal compound comprises one or more of chloroplatinic acid and sodium chloroplatinate; and / or the electroplating solution further comprises a sodium salt and ascorbic acid; and / or the electrodeposition has a charge of 8.3 mC-48.4 mC, and / or the electrodeposition has a deposition potential of 0.1 V-0.3 V.

[0014] Optionally, in some embodiments of the present application, the concentration of the first noble metal compound in the electroplating solution is 3-8 mM; and / or the sodium salt is selected from one or more of sodium sulfate, sodium nitrate, sodium chloride, and sodium acetate; and / or the concentration of the sodium salt is 0.02-0.30 mM.

[0015] Optionally, in some embodiments of the present application, the substrate comprises one or more of carbon paper, carbon cloth, gas diffusion layer; and / or when the substrate comprises a gas diffusion layer, the alumina template is attached to the gas diffusion layer, and the carbon nanotube array is formed on the gas diffusion layer; and / or the substrate comprises carbon paper and the gas diffusion layer formed on the carbon paper, and the step of forming the gas diffusion layer comprises: providing a mixed slurry comprising a polytetrafluoroethylene solution and carbon powder; coating the mixed slurry on the carbon paper, and then drying and sintering at 250-400°C to obtain the gas diffusion layer; and / or the material of the proton exchange membrane comprises one or more of perfluorosulfonic acid resin, sulfonated polystyrene-polyethylene or butylene-polystyrene.

[0016] Correspondingly, the present application also provides a membrane electrode prepared by the above-mentioned method for preparing a membrane electrode.

[0017] Correspondingly, the present application also provides a fuel cell comprising the above-mentioned membrane electrode.

[0018] The method for preparing an alumina template provided by the present application forms a plurality of first holes and a plurality of second holes on the obtained alumina template by an anodization method and etching treatment on the aluminum substrate, thereby obtaining the alumina template containing at least two different holes, improving the area proportion of the holes on the aluminum substrate under the premise of maintaining the structural stability and the hole structure stability of the alumina template, reducing the gap between the holes, and forming a nanomaterial array with smaller spacing gaps using the alumina template, which on one hand avoids the waste of nanomaterials caused by falling into the nanomaterials in the gaps, improves the deposition efficiency of the nanomaterials, and on the other hand, when the nanomaterial array is used as a carrier and a noble metal catalyst containing platinum is formed in situ thereon, the deposition efficiency of the noble metal catalyst is improved, the waste of the noble metal catalyst caused by falling into the gaps of the nanomaterial array is reduced, and the utilization rate of the noble metal is improved. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0020] Figure 1 A flowchart of an embodiment of the method for preparing an alumina template provided by the present application;

[0021] Figure 2 A structural diagram of an embodiment of the alumina template provided by the present application;

[0022] Figure 3 Figure 1 is a flow chart of an embodiment of a method for preparing a membrane electrode according to the present application. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments of the present application. Based on the embodiments in the present application, any other embodiments obtained by those skilled in the art without creative work fall within the scope of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application. In the present application, the orientation words such as "upper" and "lower" are the directions of the drawing surface in the drawings. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the present application can exist in the form of a range; it should be understood that the description in the form of a range is only for the convenience and brevity, and should not be understood as a hard limitation on the scope of the present application; therefore, it should be considered that the described range has been specifically disclosed all possible sub-ranges and single values within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, regardless of the range. In addition, whenever a numerical range is indicated in the present application, it means that any cited number (fraction or integer) within the indicated range is included.

[0024] In the present application, the association relationship of the associated objects described by "and / or" indicates that there can be three kinds of relationships, for example, A and / or B can represent the following three cases: A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural.

[0025] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one", "at least one of the following" or the like means any combination of these items, including any combination of single item (s) or multiple items (s). For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0026] The present application provides a preparation method of an anodic aluminum oxide (AAO) template, as shown in Figure 1 ,Figure 1 A flowchart of an embodiment of a preparation method of an aluminum oxide template provided in the present application is shown in the figure, and the method comprises the following steps:

[0027] Step S11: providing an aluminum substrate, and processing the aluminum substrate to obtain an aluminum oxide template intermediate, wherein the aluminum oxide template intermediate has a plurality of first holes arranged at intervals;

[0028] Step S12: forming a plurality of second holes arranged at intervals in the region of the aluminum oxide template intermediate where no first hole is formed, to obtain an aluminum oxide template.

[0029] In the embodiment, the first holes and the second holes are formed on the obtained aluminum oxide template by processing the aluminum substrate, so that the aluminum oxide template contains at least two different holes. On the premise of maintaining the structural stability and the hole structure stability of the aluminum oxide template, the area ratio of the holes (including the first holes and the second holes) on the aluminum substrate is improved, and the gap between the holes is reduced. The use of the aluminum oxide template can form a nanomaterial array with smaller interval gaps. On the one hand, this avoids the waste of nanomaterials caused by falling into the gaps, improves the deposition efficiency of nanomaterials, and on the other hand, when the nanomaterial array is used as a carrier and a platinum-containing noble metal catalyst is formed in situ thereon, the deposition efficiency of the noble metal catalyst is improved, the waste of the noble metal catalyst caused by falling into the gaps of the nanomaterial array is reduced, and the utilization rate of the noble metal is improved.

[0030] Further, in an embodiment, the second hole has a smaller hole diameter than the first hole. The second hole with a smaller hole diameter can be arranged between the first holes with a larger hole diameter, so that the area ratio of the holes on the aluminum oxide template is improved, and the hole density of the first holes with a larger hole diameter is reduced to avoid reducing the structural stability and the hole structure stability of the aluminum oxide template.

[0031] In the step S11:

[0032] The aluminum substrate can be an aluminum foil layer. It can be understood that the thickness and the area size (or the size) of the aluminum substrate can be set according to requirements, which are not limited here. The depth of the holes formed on the aluminum substrate can be set according to the thickness of the aluminum substrate, which is not limited here.

[0033] In an embodiment, the first hole is a through hole, the second hole is a through hole, and the aluminum oxide template is a through hole template. The aluminum oxide template can be used as a mask template to form a nanomaterial array on another substrate.

[0034] In an embodiment, the surface of the aluminum substrate can be oxidized, so that the surface can have an oxide layer, and the main component of the oxide layer can be aluminum oxide. Before the forming of the plurality of first holes on the aluminum substrate, the method can further include: pretreating the aluminum substrate to remove the oxide layer on the surface of the aluminum substrate.

[0035] In an embodiment, the pretreatment can be an immersion treatment of the surface of the aluminum substrate using an alkali solution. The alkali solution can be selected from one or more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium bicarbonate solution, etc. The concentration of the alkali solution can be 2wt% to 5wt%, and can be specifically 2wt% to 3wt%, 3wt% to 4wt%, 4wt% to 5wt%, etc. The temperature of the alkali solution can be 60 to 70°C, and can be specifically 60 to 65°C, 65 to 70°C, etc. The time of the immersion treatment can be 3 to 8 minutes, and can be specifically 3 to 5 minutes, 5 to 6 minutes, 6 to 8 minutes, etc.

[0036] Specifically, the immersion treatment of the surface of the aluminum substrate using the alkali solution can be specifically: soaking the aluminum substrate into the alkali solution, or coating and immersing the surface of the aluminum substrate with the alkali solution.

[0037] In an embodiment, the anodization method includes:

[0038] Step S111: pretreating the aluminum substrate to remove the oxide layer on the surface of the aluminum substrate;

[0039] Step S112: using the aluminum substrate with the oxide layer removed as an anode, using an aluminum foil without the oxide film removed as a cathode, using an acidic solution as an electrolyte, and anodizing the aluminum substrate under constant current.

[0040] The acidic solution can be selected from one or more of an oxalic acid aqueous solution, a phosphoric acid aqueous solution, a sulfuric acid aqueous solution, a chromic acid aqueous solution, or a citric acid aqueous solution.

[0041] In a specific embodiment, the acidic solution can be selected from a sulfuric acid aqueous solution, the concentration of the sulfuric acid aqueous solution can be 10 to 20wt%, the voltage of the constant current can be 10 to 30V, and the time can be 10 to 20 minutes.

[0042] In a specific embodiment, the acidic solution can be selected from an oxalic acid aqueous solution, the concentration of the oxalic acid aqueous solution can be 3 to 10wt%, the voltage of the constant current can be 40 to 60V, and the time can be 90 to 100 minutes.

[0043] In a specific embodiment, the acidic solution is selected from a mixed solution of chromic acid and phosphoric acid, wherein the mass fraction of the chromic acid is 1.5-2 wt%, the mass fraction of the phosphoric acid is 5-7 wt%, the voltage of the constant current passing through the electric field can be 18-22 V, and the time can be 10-20 min.

[0044] Specifically, the first hole diameter can be 60-120 nm, specifically 60-80 nm, 80-100 nm, 100-120 nm, etc.

[0045] In an embodiment, two adjacent first holes have a first spacing, which can be 180-300 nm, specifically 180-200 nm, 200-220 nm, 220-250 nm, 250-300 nm, etc. It can be understood that the first spacing is the distance between the centers of two adjacent first holes.

[0046] It can be understood that the second hole arranged between two adjacent first holes has a second hole diameter smaller than the first spacing, i.e., the first holes and the second holes are arranged at intervals and do not contact each other.

[0047] In the step S12:

[0048] In an embodiment, the method for forming the plurality of second holes arranged at intervals is etching.

[0049] In this embodiment, the etching can form a plurality of second holes with controllable hole diameters and controllable hole positions. Specifically, the etching method can include one or more of plasma etching, electron beam etching, and photolithography.

[0050] In an embodiment, the etching method is plasma etching, which is the most common form of dry etching. The principle is that the gas exposed to the electron region forms a plasma, and the ionized gas and high-energy electrons released by the gas form a gas, thereby forming a plasma or ion. When the ionized gas atoms are accelerated by the electric field, they will release enough power and surface driving force to tightly adhere to the material or etch the surface.

[0051] In a specific embodiment, a plurality of second holes arranged at intervals are formed on the alumina template intermediate body having a plurality of first holes by plasma etching, the second holes are formed in the region where the first holes are not formed, and the alumina template is obtained. The power of the plasma etching can be 30-80 W, the gas flow rate can be 0.4-0.8 L / min, and the etching time can be 40-180 s. Specifically, the plasma etching can be performed by a plasma device, such as an oxygen plasma machine.

[0052] Specifically, the second hole can have a pore size of 30-40 nm, specifically 30-33 nm, 33-35 nm, 35-38 nm, 38-40 nm, etc. The second hole has a relatively small pore size, which can support the arrangement of at least one second hole between two adjacent first holes.

[0053] In an embodiment, the plurality of first holes form a first array, and the plurality of second holes form a second array. The first array includes a plurality of first hole columns arranged at intervals, and the second array includes a plurality of second hole columns arranged at intervals. The first hole columns and the second hole columns are arranged alternately.

[0054] In this embodiment, the hole columns formed by the plurality of second holes with small pore sizes are arranged alternately with the hole columns formed by the first holes. On the premise of maintaining the stability of the alumina template structure and the stability of the hole structure, the area ratio of the holes on the aluminum substrate is improved, and a nano array with smaller gaps can be formed using the alumina template, thereby avoiding the waste of nano materials falling into the gaps.

[0055] In another embodiment, the plurality of second holes are arranged around the first holes on the alumina template. That is, a plurality of second holes are arranged around and at intervals of each first hole. Specifically, the plurality of second holes around each first hole are uniformly distributed, and the number of second holes around each first hole can be three, four, five, etc. The pore size of the first hole is larger than that of the second hole. In this embodiment, the plurality of second holes with small pore sizes are arranged around the periphery of the first hole, thereby improving the area ratio of the total area of the holes including the second holes and the first holes on the aluminum substrate. Therefore, when a nano array is formed using the alumina template, a nano array with smaller gaps can be formed, thereby avoiding the waste of nano materials falling into the gaps.

[0056] Referring to Figure 2 , Figure 2 An embodiment of an alumina template provided in the present application is shown in the structural schematic diagram. The alumina template 100 includes a plurality of first holes A and a plurality of second holes B. The plurality of first holes A form a plurality of first hole columns 10 arranged at intervals, and the plurality of first hole columns 10 form a first array. The plurality of second holes B form a plurality of second hole columns 20 arranged at intervals, and the plurality of second hole columns 20 form a second array. The first hole columns 10 and the second hole columns 20 are arranged alternately.

[0057] In an embodiment, among the plurality of the second holes formed in the alumina template, part of the second holes form a second array, the second array comprises a plurality of second hole columns arranged at intervals, and the first array also comprises a plurality of first hole columns arranged at intervals, wherein the first hole columns and the second hole columns are arranged alternately; and the other part of the second holes are arranged at intervals along the periphery of each of the first holes, and the plurality of second holes arranged at the periphery of each of the first holes are uniformly distributed.

[0058] In an embodiment, on the alumina template, the hole density of the second holes is greater than the hole density of the first holes, that is, the number of the second holes per unit area on the alumina template is greater than the number of the first holes. In this embodiment, the second holes with smaller hole diameters are more densely arranged on the alumina template, arranged between two adjacent first holes, which can increase the area ratio of holes on the aluminum substrate, and a nano array with smaller gaps can be formed using the alumina template, thereby avoiding the waste of nano materials falling into the gaps. Specifically, the hole density of the second holes can be 1-2 times the hole density of the first holes, such as 1 times, 1.2 times, 1.5 times, 1.8 times, 2 times, etc.

[0059] Further, in combination with Figure 2 , the hole density of the second hole column 20 is greater than the hole density of the first hole column 10, that is, the number of the second holes B in the second hole column 20 is greater than the number of the first holes A in the first hole column 10. In this embodiment, the second holes B with smaller hole diameters form a more dense second hole column 20 arranged between two first hole columns 10, which can increase the area ratio of holes on the aluminum substrate, and a nano array with smaller gaps can be formed using the alumina template, thereby avoiding the waste of nano materials falling into the gaps. Specifically, the hole density of the second hole column 20 can be 1-2 times the hole density of the first hole column 10, such as 1 times, 1.2 times, 1.5 times, 1.8 times, 2 times, etc.

[0060] In a specific embodiment, the hole density of the second hole column 20 can be 2 times the hole density of the first hole column 10. That is, the number of the second holes B contained in one second hole column 20 is twice the number of the first holes A contained in one first hole column 10.

[0061] The application also provides an alumina template prepared by the preparation method of the alumina template.

[0062] The alumina template prepared by the application can be used as a mask to deposit nanomaterials in the first holes and the second holes to form a nanometer array. Specifically, nanomaterials can be deposited on the alumina template at the positions of the holes, while the positions without holes (i.e. the gaps between the holes) are shielded from the nanomaterials and the nanomaterials cannot be deposited there, so that the nanomaterial array is formed through the alumina template. Specifically, the nanometer array includes the nanomaterial array corresponding to the first holes and the nanomaterial array corresponding to the second holes, so that a nanometer material array with smaller spacing gaps is formed, thereby avoiding the waste of nanometer materials caused by falling into the nanometer materials in the gaps.

[0063] The application further provides a preparation method of a membrane electrode. Figure 3 , Figure 3 The application provides a flowchart of an embodiment of the preparation method of the membrane electrode, and specifically includes the following steps:

[0064] Step S31: providing a substrate and an alumina template, wherein the alumina template is prepared by the preparation method of the alumina template provided by the application, and the alumina template includes a plurality of first holes and a plurality of second holes arranged at intervals.

[0065] Step S32: attaching the alumina template to the substrate;

[0066] Step S33: using the alumina template as a mask to form a carbon nanotube array on the substrate, and then removing the alumina template;

[0067] Step S34: depositing noble metals on the carbon nanotube array to obtain an ordered nanometer array catalytic electrode;

[0068] Step S35: using the ordered nanometer array catalytic electrode as a cathode and / or anode, arranging a proton exchange membrane between the cathode and the anode, and pressing to form a membrane electrode.

[0069] In the preparation method of the membrane electrode of the embodiment, the alumina template prepared by the preparation method of the alumina template provided in the application is used when the carbon nanotube array is formed. Since the alumina template contains a plurality of first holes and a plurality of second holes, the carbon nanotube array formed contains first carbon nanotubes corresponding to the first holes and second carbon nanotubes corresponding to the second holes, and the carbon nanotube array contains at least two carbon nanotubes with different diameters. The second carbon nanotubes with smaller diameters are arranged between the first carbon nanotubes with larger diameters, reducing the gap of the carbon nanotube array. When the noble metal is deposited on the carbon nanotube array, the deposition efficiency of the noble metal can be improved, the waste of the noble metal can be reduced, and the preparation cost of the membrane electrode can be reduced. Specifically, the deposition efficiency of the noble metal on the carbon nanotube array can reach 84% to 90%.

[0070] In the step S31,

[0071] In an embodiment, the substrate comprises one or more of carbon paper, carbon cloth, and gas diffusion layer.

[0072] In an embodiment, the substrate comprises carbon paper and a gas diffusion layer formed on the carbon paper.

[0073] In a specific embodiment, the specific steps of forming the gas diffusion layer on the carbon paper comprise: providing a mixed slurry, wherein the mixed slurry comprises polytetrafluoroethylene, carbon powder, and a first solvent, coating the mixed slurry on the carbon paper, and then drying and sintering to obtain the gas diffusion layer.

[0074] In the mixed slurry, the mass fraction of the polytetrafluoroethylene can be 5-30 wt%, and specifically can be 5-10 wt%, 10-15 wt%, 15-20 wt%, 20-25 wt%, 25-30 wt%, etc.

[0075] In the mixed slurry, the mass fraction of the carbon powder can be 3-15 wt%, and specifically can be 3-5 wt%, 5-10 wt%, 10-15 wt%, etc.

[0076] The first solvent can be selected from one or more of ethanol, ethylene glycol, isopropyl alcohol, n-propanol, water, etc. In a specific embodiment, the first solvent is selected from ethanol and water.

[0077] The sintering temperature can be 250-400℃, and specifically can be 250-300℃, 300-350℃, 350-400℃, etc.

[0078] In another specific embodiment, the specific steps for forming the gas diffusion layer on the carbon paper include: mixing a polytetrafluoroethylene (PTFE) solution, carbon powder, and a first solvent to obtain a mixed slurry; coating the mixed slurry onto the carbon paper; and then drying and sintering to obtain the gas diffusion layer. The PTFE solution comprises PTFE and water, and the mass fraction of PTFE can be 30–40 wt%. Further, in addition to PTFE and water, the PTFE solution may also include polystyrene, and the mass fraction of polystyrene can be 10–20 wt%. The mixing can be performed using one or more of ultrasonic mixing or mechanical stirring. The mixing time can be 20–60 min, specifically 20–30 min, 30–40 min, 40–50 min, 50–60 min, etc.

[0079] In one embodiment, the mass fraction of polytetrafluoroethylene in the gas diffusion layer is 5-30 wt%, specifically 5-10 wt%, 10-15 wt%, 15-20 wt%, 20-25 wt%, 25-30 wt%, etc.

[0080] In step S32:

[0081] In one embodiment, the alumina template is adhered to the substrate, specifically by bonding the alumina template to the substrate using an adhesive. When the substrate includes a gas diffusion layer, the alumina template is bonded to the gas diffusion layer using an adhesive.

[0082] Furthermore, the step of preparing the adhesive can be specifically as follows: mixing acrylic acid with an aqueous solution of polyvinyl alcohol to obtain a first mixture; then adding an initiator to the first mixture to catalyze polymerization to obtain the adhesive.

[0083] In the adhesive, the polyvinyl alcohol accounts for 70-80% by mass, and the acrylic acid accounts for 20-30% by mass. Specifically, the adhesive can be prepared at room temperature.

[0084] The initiator may include one or more of sulfuric acid, sulfate, and persulfate. The sulfate may be selected from one or more of sodium sulfate and ammonium sulfate, and the persulfate may be selected from potassium persulfate.

[0085] In one embodiment, the initiator can be added in solution form, such as a sulfuric acid solution. The concentration of the sulfuric acid solution can be 6–10 mol·L⁻¹. -1 Specifically, it can be 6–7 mol·L⁻¹ -1 7-8 mol·L -1 8–9 mol·L-1 9-10 mol·L-1 -1 and the like.

[0086] In the step S33, the step S32 is followed by:

[0087] It can be understood that, when the first holes and the second holes in the alumina template are through holes, and the alumina template is attached to the substrate in the step S32, the bottom of the first holes and the second holes, which are originally through holes, is sealed by the substrate, so that in the step S33, the carbon nanotubes are deposited in the channels of the alumina template by using the alumina template as a mask, and the first carbon nanotubes grown from the substrate along the channels of the first holes and the second carbon nanotubes grown from the substrate along the channels of the second holes form the carbon nanotube array.

[0088] Specifically, each carbon nanotube in the carbon nanotube array can be vertically oriented, that is, the carbon nanotube grows in a direction perpendicular to the substrate.

[0089] It can be understood that, when the substrate includes a gas diffusion layer, the carbon nanotube array is formed on the gas diffusion layer.

[0090] In an embodiment, the diameter of the first carbon nanotube can be 60-120 nm, and specifically can be 60-80 nm, 80-100 nm, 100-120 nm, or the like.

[0091] In an embodiment, the distance between two adjacent first carbon nanotubes can be 180-300 nm, and specifically can be 180-200 nm, 200-220 nm, 220-250 nm, 250-300 nm, or the like.

[0092] Further, when the pore size of the first holes is larger than that of the second holes, the diameter of the first carbon nanotubes formed correspondingly is larger than that of the second carbon nanotubes.

[0093] Specifically, the diameter of the second carbon nanotube can be 30-40 nm, and specifically can be 30-33 nm, 33-35 nm, 35-38 nm, 38-40 nm, or the like. The diameter of the second carbon nanotube is relatively small, much smaller than the distance between two adjacent first carbon nanotubes, so that one or more second carbon nanotubes with a relatively small diameter can be formed between two first carbon nanotubes with a relatively large diameter, thereby increasing the density of the carbon nanotubes in the carbon nanotube array and reducing the gap between different carbon nanotubes.

[0094] Specifically, in the carbon nanotube array, the density of the second carbon nanotube is greater than the density of the first carbon nanotube. Specifically, the density of the second carbon nanotube is 1-2 times, such as 1 times, 1.2 times, 1.5 times, 1.8 times, 2 times, etc. of the density of the first carbon nanotube.

[0095] Specifically, the carbon nanotube array with carbon nanotubes of different diameter sizes can be generated on the substrate by a vapor deposition method.

[0096] In an embodiment, the step of forming the carbon nanotube array is: placing the substrate with the alumina template attached thereon in an atmosphere of acetylene, so that the acetylene is vapor deposited to form the carbon nanotube array. Specifically, the temperature of vapor deposition can be 450-500°C, the pressure can be 4000-5000 Pa, and the time can be 1-2 min.

[0097] In an embodiment, the substrate is placed in a vapor deposition chamber, and 20-30 sccm of acetylene is introduced into the vapor deposition chamber, so that the pressure in the vapor deposition chamber is maintained at 4000-5000 Pa, and the reaction is carried out for 1-2 h.

[0098] Specifically, when 20 sccm of acetylene is introduced and the pressure is maintained at 4000 Pa, the reaction is carried out for 2 h; when 20 sccm of acetylene is introduced and the pressure is maintained at 5000 Pa, the reaction is carried out for 1 h; when 30 sccm of acetylene is introduced and the pressure is maintained at 4000 Pa, the reaction is carried out for 2 h; and when 30 sccm of acetylene is introduced and the pressure is maintained at 5000 Pa, the reaction is carried out for 1.5 h.

[0099] In a specific embodiment, the step of forming the carbon nanotube array is: placing the bonded alumina (AAO) template and the gas diffusion layer into a tube furnace, introducing acetylene at 500°C for 70 min, so that it is vapor deposited in the channels of the AAO template.

[0100] In a specific embodiment, the removing the alumina template specifically includes: removing the alumina template by dissolving with an alkali solution. The alkali solution can be selected from one or more of NaOH aqueous solution, KOH aqueous solution, etc. The concentration of the alkali solution can be 1-3 mol / L, such as 1-1.5 mol / L, 1.5-2 mol / L, 2-2.5 mol / L, 2.5-3 mol / L, etc.

[0101] When the alumina template is bonded to the substrate by a bonding agent, after the alumina template is removed, it further includes: removing the bonding agent. Specifically, the bonding agent can be removed using an organic solvent such as NMP (N-methyl pyrrolidone) or DMF (N,N-dimethylformamide).

[0102] The step S34 includes:

[0103] The step of depositing noble metal on the carbon nanotube array can be performed by electro-deposition.

[0104] The noble metal can be selected from one or more of platinum, gold, silver, palladium, copper, iron, cobalt, nickel, chromium, ruthenium. Further, in one embodiment, the noble metal is platinum or a platinum alloy, wherein the platinum alloy contains one or more of gold, silver, palladium, copper, nickel, cobalt, iron, ruthenium in addition to platinum.

[0105] In one embodiment, the substrate on which the carbon nanotube array is formed is used as a working electrode, the side of the working electrode on which the carbon nanotube array is formed is contacted with an electroplating solution containing a noble metal precursor, a platinum plate is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to perform electro-deposition, thereby depositing the noble metal on the carbon nanotube array to form an ordered nanometer array catalytic electrode.

[0106] Specifically, the electroplating solution contains a noble metal compound, a sodium salt, and an acid.

[0107] In one embodiment, the concentration of the acid in the electroplating solution is 0.01-0.20 M, and can be 0.01-0.05 M, 0.05-0.10 M, 0.10-0.15 M, 0.15-0.20 M, etc.

[0108] In one embodiment, the acid is selected from ascorbic acid. The ascorbic acid contained in the electroplating solution can make the noble metal nanoparticles deposited in a spherical shape, thereby making the noble metal deposited more uniformly on the carbon nanotube array.

[0109] In one embodiment, the sodium salt can be selected from one or more of sodium sulfate, sodium nitrate, sodium chloride, sodium acetate, etc. The concentration of the sodium salt can be 0.02-0.30 mM, and can be 0.02-0.10 mM, 0.10-0.15 mM, 0.15-0.20 mM, 0.20-0.25 mM, 0.25-0.30 mM, etc.

[0110] The concentration of the noble metal compound is 3-10 mM (range of mass concentration or molar concentration).

[0111] The noble metal compound contained in the electroplating solution can be set according to the type of the deposited noble metal. Specifically, the noble metal compound can include one or more of chloroplatinic acid, sodium chloroplatinate, chloroauric acid, silver nitrate, copper sulfate, iron sulfate, ferrous sulfate, cobalt sulfate, nickel chloride, nickel nitrate, palladium chloride, palladium nitrate, chromium chloride, chromium nitrate, or ruthenium trichloride. It can be understood that the noble metal compound also includes the hydrates of the above-mentioned metal salts.

[0112] In an embodiment, when the noble metal is platinum, the noble metal compound includes a first noble metal compound, which is a platinum precursor, and specifically can be one or more of chloroplatinic acid or sodium chloroplatinate. Specifically, the concentration of the platinum precursor is 3-8 mM, and specifically can be 3-4 mM, 4-5 mM, 5-6 mM, 6-8 mM, etc.

[0113] In an embodiment, the amount of electricity for electrodepositing can be 8.3 mC-48.4 mC (milli-Coulomb), and specifically can be 8.3 mC-10.0 mC, 10.0 mC-20.0 mC, 20.0 mC-30.0 mC, 30.0 mC-40.0 mC, 40.0 mC-48.4 mC, etc. The deposition potential for electrodepositing can be 0.1 V-0.3 V, and specifically can be 0.1 V-0.2 V, 0.3 V-0.3 V, etc. The time for electrodepositing can be 50-120 min, and specifically can be 50-80 min, 80-100 min, 100-120 min, etc.

[0114] In the step S35:

[0115] In an embodiment, the material of the proton exchange membrane includes one or more of perfluorosulfonic acid resin (Nafion resin), sulfonated polystyrene-polyethylene, or butylene-polyphenylethylene.

[0116] In a specific embodiment, a Nafion resin layer is formed on the surface of the ordered nanometer array catalytic electrode as a proton exchange membrane.

[0117] Specifically, a proton exchange solution is arranged on the surface of the ordered nanometer array catalytic electrode and is left to uniformly distribute the proton exchange solution in the ordered nanometer array catalytic electrode, and then dried to remove the solvent to form the proton exchange membrane. The concentration of the proton exchange solution is 5-8% wt, and specifically can be 5-6% wt, 6-7% wt, 7-8% wt, etc. The solvent in the proton exchange solution can be selected from one or more of ethanol and isopropyl alcohol. The time for leaving can be 20-30 min.

[0118] The ordered nanometer array catalytic electrode can be used as a cathode and / or anode, that is, the anode in the membrane electrode can be the ordered nanometer array catalytic electrode, or the cathode can be the ordered nanometer array catalytic electrode, or both the anode and the cathode are the ordered nanometer array catalytic electrode.

[0119] Specifically, the platinum loading of the ordered nanometer array catalytic electrode as the anode (i.e., the anode platinum loading) can be in the range of 0.1-0.2 mg / cm 2 The platinum loading of the ordered nanometer array catalytic electrode as the cathode (i.e., the cathode platinum loading) can be in the range of 0.2-0.3 mg / cm 2 .

[0120] In a specific embodiment, a 0.5wt% Nafion ethanol solution is added dropwise on the surface of the ordered nanometer array catalytic electrode, and left for a period of time to make it uniformly distributed in the ordered nanometer array, and then placed in a vacuum dryer for drying. After drying, the ordered nanometer array catalytic electrode is pressed with a proton exchange membrane to form a membrane electrode.

[0121] In this embodiment, the obtained membrane electrode comprises a cathode, an anode and a proton exchange membrane, and the proton exchange membrane is arranged between the cathode and the anode. At least one of the cathode and the anode is the ordered nanometer array catalytic electrode provided by the present application.

[0122] The present application also provides a membrane electrode prepared by the preparation method of the membrane electrode provided by the present application.

[0123] The present application also provides a fuel cell comprising the membrane electrode provided by the present application.

[0124] The present application will be described in detail below through specific embodiments. The following embodiments are only part of the embodiments of the present application, and are not a limitation of the present application.

[0125] Embodiment 1

[0126] This embodiment provides an AAO template and a preparation method, and a method for preparing an ordered platinum nanotube membrane electrode using the AAO template.

[0127] The preparation method of the AAO template comprises the following steps: placing an aluminum foil into a 2wt% sodium hydroxide solution with a temperature of 70°C for 3 minutes to remove the oxide film on the surface of the aluminum foil, and then placing the treated aluminum foil as an anode into an electrolytic cell, using an aluminum foil without removing the oxide film as a cathode, and using an oxalic acid aqueous solution as an electrolyte, at a current density of 110 mA·cm -2The first holes A are arrayed and have a diameter of 120 nm and a spacing of 300 nm. Then, the second holes B are arrayed in the spacing between the first holes A by plasma etching, and the second holes B have a diameter of 40 nm. Figure 2 .

[0128] The preparation method of the ordered platinum nanotube film electrode comprises the following steps:

[0129] Step 1, forming a gas diffusion layer

[0130] A polytetrafluoroethylene solution (1% by mass fraction), carbon nanotubes and an ethanol solution are ultrasonically stirred for 40 minutes to obtain a mixed slurry, the mixed slurry is coated on carbon paper, and then dried and sintered at 250-400 DEG C to obtain a gas diffusion layer.

[0131] Step 2, preparing a carbon nanotube array on the gas diffusion layer

[0132] An acrylic acid and polyvinyl alcohol aqueous solution are mixed to obtain a PVA / AA mixture (70% by mass percentage of polyvinyl alcohol and 30% by mass percentage of acrylic acid); then, an H2SO4 solution (10 mol·L -1 ) is added to the PVA / AA mixture, and stirred for 3 hours to obtain a binder.

[0133] The gas diffusion layer and the AAO template are bonded by the binder, and then placed in a tube furnace, and acetylene is introduced at 500 DEG C for 70 minutes, so that the carbon nanotubes are vapor deposited in the pore channels of the AAO template. Finally, the AAO template is removed using a 1 mol / L NaOH solution, and the binder is removed using NMP, to obtain a carbon nanotube array vertically grown on the gas diffusion layer.

[0134] Step 3, depositing PT particles on the carbon nanotube array

[0135] 0.28 g / L H2PtCl6·6H2O, 0.10 g / L ascorbic acid and 7.30 g / L Na2SO4 are mixed and left to stand for 3 hours to obtain a plating solution. Then, the gas diffusion layer with the carbon nanotube array is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. The side of the gas diffusion layer with the carbon nanotube array is in contact with the plating solution, the amount of electricity for electrodeposition is controlled to be 38 mC, and the deposition potential is 0.2 V. Platinum nanoparticles are deposited on the carbon nanotube array to obtain an ordered nanometer array catalytic electrode.

[0136] The deposition efficiency of platinum nanoparticles reached 85%. The deposition efficiency = the surface area of carbon nanotubes deposited with platinum nanoparticles / (the surface area of the template deposited with platinum nanoparticles + the surface area of carbon nanotubes).

[0137] Step 4, forming a membrane electrode

[0138] A Nafion / ethanol dilute solution with a concentration of 0.5wt% was added dropwise on the surface of the ordered nanometer array catalytic electrode, and was left for a period of time to make it uniformly distributed in the catalytic layer of the electrode, and then was placed in a vacuum dryer for drying. Then the dried ordered nanometer array catalytic electrode was pressed with a proton exchange membrane to form a membrane electrode, the platinum loading of the anode was 0.2mg / cm 2 , and the platinum loading of the cathode was 0.3mg / cm 2 .

[0139] Example 2

[0140] This example is basically the same as Example 1, and the only difference is that 0.28g / L H2PtCl6·6H2O, 0.24g / L RuCl3·H2O and 0.12g / L ascorbic acid were mixed with 7.50g / L Na2SO4 to obtain an electroplating solution, and platinum-ruthenium nanoparticles were deposited on the carbon nanotube array. The deposition efficiency of platinum-ruthenium nanoparticles was 80%.

[0141] Comparative Example 1

[0142] This comparative example is basically the same as Example 1, and the only difference is that in the preparation of the AAO template, only a plurality of first holes A arranged in an array were obtained, the hole diameter was 120nm, the hole spacing was 300nm, and the subsequent operation of forming second holes was not performed. In step 3, the deposition efficiency of platinum nanoparticles on the carbon nanotube array was 70%.

[0143] Comparative Example 2

[0144] This comparative example is basically the same as Example 1, and the only difference is that in the preparation of the AAO template, only a plurality of second holes A arranged in an array were obtained, the hole diameter was 40nm. In step 3, the deposition efficiency of platinum nanoparticles on the carbon nanotube array was 60%.

[0145] Comparative Example 3

[0146] This comparative example is basically the same as Example 1, and the only difference is that in step 3, dilute sulfuric acid (concentration of 0.10M) was used in the electroplating solution instead of ascorbic acid. The deposition efficiency of platinum nanoparticles was 65%.

[0147] As can be seen from Examples 1-2 and Comparative Examples 1-2, compared with the alumina template forming one kind of pore in Comparative Example 1-2, the alumina template including two kinds of pores prepared by using the preparation method of the alumina template provided in the present application can improve the deposition efficiency when used for preparing a membrane electrode, thereby reducing the waste of noble metal; and as can be seen from Comparative Example 3, the use of ascorbic acid in the plating solution in the present application can improve the deposition efficiency of noble metal, which may be due to the fact that ascorbic acid can make the noble metal nanoparticles formed by deposition spherical, thereby making the deposited noble metal more uniformly distributed on the carbon nanotube array, thereby improving the deposition uniformity and deposition efficiency of the noble metal.

[0148] The preparation method of the alumina template, the membrane electrode and the preparation method and the fuel cell thereof provided in the embodiments of the present application are described in detail above, and the principles and implementation manners of the present application are described by applying specific examples in the present text; the above description of the embodiments is only used to help understand the method of the present application and its core idea; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manners and application ranges will have changes; in view of the above, the content of the present description should not be understood as a limitation of the present application.

Claims

1. A method for preparing an alumina template, characterized by, The method comprises: providing an aluminum substrate, treating the aluminum substrate to obtain an alumina template intermediate, the alumina template intermediate having a plurality of first holes arranged at intervals; forming a plurality of second holes arranged at intervals in a region of the alumina template intermediate which does not form the first holes to obtain an alumina template; treating the aluminum substrate by an anodization method, the anodization method comprising: pretreating the aluminum substrate to remove an oxide layer on the surface of the aluminum substrate; using the aluminum substrate from which the oxide layer is removed as an anode, using an aluminum foil from which an oxide film is not removed as a cathode, using an acidic solution as an electrolyte, and anodizing the aluminum substrate under constant current; forming the plurality of second holes arranged at intervals by an etching method; the etching method is plasma etching.

2. The method according to claim 1, wherein: the acidic solution is selected from one or more of an aqueous oxalic acid solution, an aqueous phosphoric acid solution, an aqueous sulfuric acid solution, an aqueous chromic acid solution, or an aqueous citric acid solution; and / or the power of the plasma etching is 30-80 W, the gas flow rate is 0.4-0.8 L / min, and the etching time is 40-180 s.

3. The method according to any one of claims 1-2, wherein: the second holes have a smaller diameter than the first holes; and / or the diameter of the first holes is 60-120 nm; and / or adjacent two first holes have a first spacing of 180-300 nm; and / or the diameter of the second holes is 30-40 nm; and / or the density of the second holes is greater than the density of the first holes on the alumina template.

4. The method according to claim 3, wherein: the first holes form a first array comprising a plurality of first hole columns arranged at intervals, and the second holes form a second array comprising a plurality of second hole columns arranged at intervals, wherein the first hole columns and the second hole columns are arranged alternately; and / or each first hole is surrounded by a plurality of second holes; and / or the density of the second holes is 1-2 times the density of the first holes on the alumina template.

5. A method for producing a membrane electrode, characterized by, The method comprises: providing a substrate and an alumina template, wherein the alumina template is prepared by the method for preparing an alumina template according to any one of claims 1-4, and the alumina template comprises a plurality of first holes arranged at intervals and a plurality of second holes arranged at intervals; attaching the alumina template to the substrate; forming a vertically oriented carbon nanotube array on the substrate using the alumina template as a mask, and then removing the alumina template; depositing a noble metal on the carbon nanotube array to obtain an ordered nanometer array catalytic electrode; using the ordered nanometer array catalytic electrode as a cathode and / or anode, and attaching a proton exchange membrane between the cathode and the anode and pressing to form a membrane electrode.

6. The method according to claim 5, wherein: The step of forming the carbon nanotube array comprises: placing the substrate with the alumina template attached thereon in an atmosphere of acetylene, so that the acetylene is vapor deposited to form the carbon nanotube array; and / or The step of removing the alumina template comprises: removing the alumina template by dissolving with an alkali solution; and / or The carbon nanotube array comprises first carbon nanotubes corresponding to the first holes in the alumina template and second carbon nanotubes corresponding to the second holes in the alumina template; and / or The step of depositing a noble metal on the carbon nanotube array comprises: taking the substrate with the carbon nanotube array formed thereon as a working electrode, contacting the side of the working electrode with the carbon nanotube array formed thereon with an electroplating solution containing a noble metal compound, taking a platinum sheet as a counter electrode, and taking a saturated calomel electrode as a reference electrode to perform electrodeposition, so as to deposit the noble metal on the carbon nanotube array.

7. The preparation method according to claim 6, wherein The temperature of the vapor deposition is 450-500°C, and the time is 1-2 min; and / or The alkali solution is selected from one or more of NaOH aqueous solution and KOH aqueous solution; and / or The diameter of the first carbon nanotube is 60-120 nm; and / or The distance between two adjacent first carbon nanotubes is 180-300 nm; and / or The diameter of the second carbon nanotube is 30-40 nm; and / or In the carbon nanotube array, the density of the second carbon nanotube is greater than the density of the first carbon nanotube; and / or The noble metal compound comprises a first noble metal compound, and the first noble metal compound comprises one or more of chloroplatinic acid and sodium chloroplatinate; and / or The electroplating solution further comprises a sodium salt and ascorbic acid; and / or The amount of electricity for the electrodeposition is 8.3 mC-48.4 mC, and / or the deposition potential for the electrodeposition is 0.1 V-0.3 V.

8. The preparation method according to claim 7, wherein The concentration of the first noble metal compound in the electroplating solution is 3-8 mM; and / or The sodium salt is selected from one or more of sodium sulfate, sodium nitrate, sodium chloride, and sodium acetate; and / or The concentration of the sodium salt is 0.02-0.30 mM.

9. The preparation method according to claim 5, wherein The substrate comprises one or more of carbon paper, carbon cloth, and a gas diffusion layer; and / or When the substrate comprises a gas diffusion layer, the alumina template is attached to the gas diffusion layer, and the carbon nanotube array is formed on the gas diffusion layer; and / or The substrate comprises carbon paper and the gas diffusion layer formed on the carbon paper, and the step of forming the gas diffusion layer comprises: providing a mixed slurry, wherein the mixed slurry comprises a polytetrafluoroethylene solution and carbon powder; coating the mixed slurry on the carbon paper, and then drying and sintering at 250-400°C to obtain the gas diffusion layer; and / or The material of the proton exchange membrane comprises one or more of perfluorosulfonic acid resin, sulfonated polystyrene-polyethylene, or sulfonated polystyrene-polybutylene. ​ 10. A membrane electrode characterized by, The membrane electrode is produced by the production method according to any one of claims 5 to 9.

11. A fuel cell characterized by comprising: The membrane electrode according to claim 10.

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