CN107658485B - Proton exchange membrane fuel cell membrane electrode and preparation method thereof - Google Patents
Proton exchange membrane fuel cell membrane electrode and preparation method thereof Download PDFInfo
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Abstract
The invention provides a proton exchange membrane fuel cell membrane electrode, wherein a cathode catalyst layer is coated on one surface of a proton exchange membrane, an anode inner catalyst layer and an anode outer catalyst layer are sequentially coated on the other surface of the proton exchange membrane, gas diffusion layers are respectively hot-pressed on the outer sides of the cathode catalyst layer and the anode outer catalyst layer, the anode inner catalyst layer comprises a catalyst and proton exchange resin, and the mass of the proton exchange resin is 30-50% of the mass of the catalyst; the anode outer catalyst layer comprises a catalyst, proton exchange resin and PTFE, wherein the mass of the proton exchange resin is 5-15% of that of the catalyst, and the mass of the PTFE is 3-6% of that of the catalyst. Also provides a preparation method of the membrane electrode of the proton exchange membrane fuel cell. The membrane electrode has good stability and simple preparation method.
Description
Technical Field
The invention relates to a membrane electrode of a proton exchange membrane fuel cell and a preparation method thereof.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) is a high-efficiency and environment-friendly power generation mode, the energy efficiency conversion rate of the PEMFC exceeds 60 percent and is far higher than the energy conversion efficiency of an internal combustion engine by 30 to 35 percent; in addition, the fuel cell uses hydrogen as fuel, the fuel is renewable and widely available, and the emission is only water, which is of particular importance to national energy strategy and environmental protection. As a core component of a fuel cell, a Membrane Electrode Assembly (MEA) directly affects output performance and service life of the fuel cell; moreover, membrane electrodes constitute a major portion of the cost of fuel cells, currently accounting for about 69%. Therefore, how to improve the performance of the membrane electrode and reduce the production cost thereof is very important for the development and popularization of the PEMFC.
Current MEAs basically use a Proton Exchange Membrane (PEM) as the solid electrolyte, and the water content of the PEM is a major factor affecting the conductivity of the PEM. Therefore, in order for the PEMFC to have good performance, the water content in the PEM must be maintained. It is common practice to humidify the reactant gases, i.e., externally humidify, but this requires additional humidifiers, easily causes flooding of the system, and increases the manufacturing cost and the water-heating management difficulty of the fuel cell system. In fact, during the operation of the PEMFC, the cathode of the MEA also generates a large amount of reaction water and can be transferred to the anode side of the MEA by reverse diffusion, and the proton exchange resin such as Nafion molecules added to the catalyst layer also have hydrophilicity per se, so that humidification, i.e., self-humidification, can be performed using the water generated by the operation of the MEA per se. On one hand, the resistance of water diffusing from the MEA cathode to the anode is large, and the process is slow; on the other hand, the proton exchange resin has a relatively high resistance, so that the content of the proton exchange resin is limited (generally less than 30% of the mass of the catalyst) in order to reduce the resistance of the catalyst layer, so that the anode catalyst layer has poor moisture retention performance and is easily in a dry and dehydrated state under the purging of hydrogen. Therefore, the membrane electrode prepared by the traditional method can not meet the normal working requirement of the fuel cell on the premise of no external humidification.
At present, measures for improving the self-humidifying capability of the MEA mainly include the following measures: (1) using self-humidifying PEMs, such membranes can be self-humidified by adding Pt-containing catalyst particles to the membrane to generate reaction water within the membrane structure, or by adding SiO2Hydrophilic particles to enhance the moisture retention of the PEM itself; (2) the method adopts a self-humidifying anode catalyst layer, namely hydrophilic inorganic particles or hydrophilic polymers are added into the catalyst layer to achieve the aim of moisturizing the membrane electrode; (3) a moisture retention layer may also be incorporated on the anode side of the MEA to achieve self-humidification. However, in view of the current development, these measures have certain defects, and the ideal self-humidifying effect cannot be achieved. Inorganic particles, such as those added to the MEA components, tend to agglomerate or lose after long periods of operation, thereby reducing the performance stability and service life of the fuel cell; the polymer additives can increase the resistance of the membrane electrode, and the compatibility problem of the polymer can also increase the difficulty of the preparation process of the membrane electrode. As for the additionally added moisturizing layer, it may also be peeled off or damaged after a long time of work. In addition, the conventional MEA anode catalyst is generally of a single-layer structure, the amount of reaction water generated in the cell under high current density operating conditions will increase rapidly, and if the anode catalyst layer does not have good water management measures, flooding will easily occur, especially after humidification modification.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a proton exchange membrane fuel cell membrane electrode with a gradient anode catalyst layer, which has better self-humidification effect, anode water management capability and gas diffusion capability. Also provides a preparation method of the membrane electrode of the proton exchange membrane fuel cell.
The invention is realized by the following scheme:
a proton exchange membrane fuel cell membrane electrode is characterized in that one surface of a proton exchange membrane is coated with a cathode catalyst layer, the other surface of the proton exchange membrane is sequentially coated with an anode inner catalyst layer and an anode outer catalyst layer, gas diffusion layers are respectively hot-pressed on the outer sides of the cathode catalyst layer and the anode outer catalyst layer, the anode inner catalyst layer comprises a catalyst and proton exchange resin, and the mass of the proton exchange resin is 30-50% of the mass of the catalyst; the anode outer catalyst layer comprises a catalyst, proton exchange resin and PTFE, wherein the mass of the proton exchange resin is 5-15% of that of the catalyst, and the mass of the PTFE is 3-6% of that of the catalyst.
Further, the Pt loading ratio of the anode inner catalyst layer to the anode outer catalyst layer is 4: 1-1: 1, the total Pt loading capacity of the anode inner catalyst layer and the anode outer catalyst layer is 0.05-0.3 mg/cm2The Pt loading capacity of the cathode catalyst layer is 0.2-0.6 mg/cm2。
Further, the catalyst is one or more of Pt/C, Pt-M/C, wherein the content of Pt is 5-60%, and M is one or more of Co, Mo, W, Ru and Pd; the proton exchange resin is preferably Nafion.
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the steps of spraying cathode catalyst slurry on one surface of a proton exchange membrane and drying to form a cathode catalyst layer, spraying anode inner layer catalyst slurry on the other surface of the proton exchange membrane and drying to form an anode inner catalyst layer, spraying anode outer layer catalyst slurry on the surface of the anode inner catalyst layer and drying to form an anode outer catalyst layer, and finally hot-pressing gas diffusion layers on the outer sides of the cathode catalyst layer and the anode outer catalyst layer respectively to finish the preparation of the membrane electrode; what is needed isThe Pt loading ratio of the anode inner catalyst layer to the anode outer catalyst layer is controlled to be 4: 1-1: 1, controlling the total Pt loading capacity of the anode inner catalyst layer and the anode outer catalyst layer to be 0.05-0.3 mg/cm2The Pt loading capacity of the cathode catalyst layer is controlled to be 0.2-0.6 mg/cm 2; generally, the Pt loading capacity of the catalyst layer in the anode is controlled to be 0.03-0.2 mg/cm2, and the Pt loading capacity of the catalyst layer outside the anode is controlled to be 0.03-0.1 mg/cm2(ii) a In actual manufacturing, the spraying sequence of the cathode catalyst layer, the anode inner catalyst layer and the anode outer catalyst layer can be adjusted.
The preparation process of the anode inner layer catalyst slurry comprises the following specific steps: putting a weighed catalyst into deionized water, adding a proton exchange resin solution with the mass concentration of 5-10% into the deionized water, stirring and dispersing (in a magnetic stirring and ultrasonic oscillation mode, the time is controlled to be 5-10 min respectively), adding a dispersing agent and a thickening agent into the deionized water, stirring at a high rotating speed for a certain time after dispersing (in a magnetic stirring and ultrasonic oscillation mode, the time is controlled to be 10-60 min respectively), controlling the stirring rotating speed to be 5000-20000 rpm, controlling the stirring time to be 10-30 min, controlling the solid content of catalyst slurry in an inner layer of an anode to be 1-2%, wherein the mass of the proton exchange resin is 30-50% of the mass of the catalyst, and the volume ratio of the deionized water, the dispersing agent and the thickening agent is 1: (10-16): (1-2). The catalyst is one or more of Pt/C, Pt-M/C, wherein the content of Pt is 5-60%, and M is one or more of Co, Mo, W, Ru and Pd; the proton exchange resin is preferably Nafion; the dispersing agent is one or two of absolute ethyl alcohol and isopropanol; the thickener is one or two of ethylene glycol and butyl acetate.
The preparation process of the anode outer layer catalyst slurry comprises the following specific steps: putting a weighed catalyst into deionized water, adding a proton exchange resin solution with the mass concentration of 5-10% and a PTFE emulsion with the mass concentration of 5-10% into the deionized water, stirring and dispersing (in a magnetic stirring and ultrasonic oscillation mode, the time is controlled to be 5-10 min respectively), then adding a dispersing agent and a thickening agent into the deionized water, stirring at a high rotating speed for a certain time after dispersing (in a magnetic stirring and ultrasonic oscillation mode, the time is controlled to be 10-60 min respectively), controlling the stirring rotating speed to be 5000-20000 rpm, controlling the stirring time to be 10-30 min, controlling the solid content of catalyst slurry on the outer layer of an anode to be 0.5-1%, wherein the mass of the proton exchange resin is 5-15% of the mass of the catalyst, the mass of PTFE is 3-6% of the mass of the catalyst, and the volume ratio of the deionized water, the dispersing agent and the thickening agent is: (10-16): (1-4). The catalyst is one or more of Pt/C, Pt-M/C, wherein the content of Pt is 5-60%, and M is one or more of Co, Mo, W, Ru and Pd; the proton exchange resin is preferably Nafion; the dispersing agent is one or two of absolute ethyl alcohol and isopropanol; the thickener is one or two of ethylene glycol and butyl acetate.
The cathode catalyst slurry is prepared according to the prior conventional technology, and the specific preparation process is as follows: putting a weighed catalyst into deionized water, adding a proton exchange resin solution with the mass concentration of 5-10% into the deionized water, stirring and dispersing (in a magnetic stirring and ultrasonic oscillation mode, the time is controlled to be 5-10 min respectively), then adding a dispersing agent into the deionized water, dispersing (in a magnetic stirring and ultrasonic oscillation mode, the time is controlled to be 10-60 min respectively), stirring at a high rotating speed for a certain time, wherein the stirring rotating speed is controlled to be 5000-20000 rpm, the stirring time is controlled to be 10-30 min, the solid content of cathode catalyst slurry is controlled to be 1-2%, the mass of the proton exchange resin is 10-30% of the mass of the catalyst, and the volume ratio of the deionized water to the dispersing agent is 1: (5-16). The catalyst is one or more of Pt/C, Pt-M/C, wherein the content of Pt is 5-60%, and M is one or more of Co, Mo, W, Ru and Pd; the proton exchange resin is preferably Nafion; the dispersing agent is one or two of absolute ethyl alcohol and isopropanol.
In the process of preparing the anode inner layer catalyst slurry, the anode outer layer catalyst slurry and the cathode catalyst slurry, the mass of liquid substances such as deionized water, a dispersing agent and a thickening agent can be converted and measured according to the corresponding volume ratio and the corresponding required solid content.
The spraying speed of the catalyst slurry on the inner layer of the anode is 0.4-1 ml/min, and the spraying speed of the catalyst slurry on the outer layer of the anode is 0.3-0.6 ml/min.
And drying processes of the cathode catalyst slurry, the anode inner layer catalyst slurry and the anode outer layer catalyst slurry are all drying for 1-2 hours at the temperature of 60-80 ℃.
The process for hot gas diffusion layers is generally: and respectively hot-pressing the gas diffusion layers on the outer sides of the cathode catalyst layer and the anode outer catalyst layer by using a hot press, wherein the mold temperature of the hot press is 120-140 ℃, the hot-pressing pressure is 3-5 MPa, and the hot-pressing time is 1-2 min.
Generally, the proton exchange membrane is pretreated, specifically: soaking the proton exchange membrane in hydrogen peroxide with the temperature of 70-80 ℃ and the mass concentration of 3-5% for 1-2 h, washing with deionized water, soaking in sulfuric acid solution with the temperature of 70-80 ℃ and the molar concentration of 0.5-1 mol/L for 1-2 h, and finally washing with deionized water.
Compared with the prior art, the membrane electrode of the proton exchange membrane fuel cell has the following advantages:
1. no additional hydrophilic agent is added, so that the stability of the performance of the MEA is improved, and the difficulty of the preparation process is reduced; 2. the anode inner catalyst layer and the anode outer catalyst layer jointly form a gradient anode catalyst layer, the content of proton exchange resin in the anode inner catalyst layer is increased (by 30-50%) on the premise of not increasing the total content of proton exchange resin in the anode catalyst layer, the hydrophilicity of the anode inner catalyst layer is favorably improved, and the self-humidifying effect is good; the catalyst layer outside the anode has low content (5-15%) of proton exchange resin and contains hydrophobic PTFE component, so that the hydrophobicity of the catalyst layer outside the anode is increased, the catalyst layer is beneficial to discharging excessive water, flooding is prevented, and the catalyst layer has good anode water management capability.
3. The preparation method is simple, the solid content of the anode outer layer catalyst slurry is lower than that of the anode inner layer catalyst slurry, and the spraying speed of the anode outer layer catalyst slurry is also lower than that of the anode inner layer catalyst slurry, so that the porosity of the anode outer layer catalyst layer is higher than that of the anode inner layer catalyst layer, reaction water is discharged from one side of a Proton Exchange Membrane (PEM) to one side of a gas diffusion layer, and the diffusion of reaction gas is facilitated.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the description of the examples.
Example 1
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
pretreatment of a proton exchange membrane: soaking a Nafion212 proton exchange membrane in hydrogen peroxide with the temperature of 80 ℃ and the mass concentration of 5% for 1h, washing with deionized water, soaking in sulfuric acid with the temperature of 80 ℃ and the molar concentration of 1mol/L for 1h, and finally washing with deionized water;
II, preparing anode inner layer catalyst slurry: weighing the mass of the catalyst, 5% Nafion solution, deionized water, isopropanol and ethylene glycol according to the proportion, wherein the catalyst is Pt/C with the Pt content of 40%, the mass of Nafion is 30% of the mass of the catalyst, and the mass of the deionized water, the isopropanol and the ethylene glycol is determined according to the volume ratio of the deionized water, the isopropanol and the ethylene glycol of 1: 10: 1, measuring and calculating the solid content of catalyst slurry in the inner layer of the anode by controlling the solid content to be 2%, then adding a catalyst into deionized water, then adding a 5% Nafion solution, magnetically stirring for 5min, ultrasonically oscillating for 5min, then adding isopropanol and ethylene glycol, magnetically stirring for 20min, ultrasonically oscillating for 40min, and finally stirring and dispersing for 20min at the rotation speed of 10000 rpm;
III, preparation of catalyst slurry on the outer layer of the anode: weighing the mass of a catalyst, a 5% Nafion solution, a 5% PTFE emulsion, deionized water, isopropanol and ethylene glycol according to a proportion, wherein the catalyst is Pt/C with a Pt content of 40%, the mass of Nafion is 5% of the mass of the catalyst, the mass of PTFE is 3% of the mass of the catalyst, and the mass of the deionized water, the isopropanol and the ethylene glycol is determined according to the volume ratio of the deionized water, the isopropanol and the ethylene glycol of 1: 10: 1, measuring and calculating the solid content of catalyst slurry on the outer layer of the anode by controlling the solid content to be 1%, then adding a catalyst into deionized water, then adding a 5% Nafion solution and a 5% PTFE emulsion, magnetically stirring for 5min, ultrasonically oscillating for 5min, then adding isopropanol and ethylene glycol, magnetically stirring for 20min, ultrasonically oscillating for 40min, and finally stirring and dispersing for 20min at the rotation speed of 10000 rpm;
IV, preparation of cathode catalyst slurry: weighing the mass of the catalyst, 5% Nafion solution, deionized water and isopropanol according to the proportion, wherein the catalyst is Pt/C with the Pt content of 40%, the mass of Nafion is 20% of the mass of the catalyst, and the mass of the deionized water and the isopropanol is determined according to the volume ratio of 1: 10, measuring and calculating the solid content of cathode catalyst slurry by 2%, then adding a catalyst into deionized water, then adding a 5% Nafion solution, magnetically stirring for 5min, ultrasonically oscillating for 5min, then adding isopropanol, magnetically stirring for 20min, ultrasonically oscillating for 40min, and finally stirring and dispersing for 20min at the rotation speed of 10000 rpm;
flatly paving and adsorbing the Nafion212 proton exchange membrane treated in the step I on a vacuumizing heating table, setting the temperature of the heating table to be 80 ℃, and then spraying cathode catalyst slurry on one surface of the proton exchange membrane at a spraying speed of 0.8ml/min, wherein the moving speed of a spray head is 100mm/min, and the moving speed of the spray head is 0.5mg/cm2The Pt loading amount of the catalyst is sprayed with cathode catalyst slurry, and then the catalyst slurry is placed for 1 hour to form a cathode catalyst layer; then turning over the proton exchange membrane, spraying the anode inner layer catalyst slurry on the other surface of the proton exchange membrane at a spraying speed of 0.8ml/min, wherein the moving speed of a spray head is 100mm/min and is 0.1mg/cm2The Pt loading amount of the anode inner layer catalyst slurry is sprayed, and then the anode inner layer catalyst slurry is placed for 1 hour to form an anode inner catalyst layer; then spraying the catalyst slurry on the outer layer of the anode on the catalyst layer in the anode at the spraying speed of 0.4ml/min, wherein the moving speed of a spray head is 100mm/min and is according to 0.1mg/cm2The Pt loading amount of the anode is sprayed with anode outer layer catalyst slurry, and then the anode outer layer catalyst slurry is placed for 1 hour to form an anode outer catalyst layer;
and VI, finally, respectively hot-pressing the product obtained in the step V on the outer sides of the cathode catalyst layer and the anode outer catalyst layer by using a hot press to form gas diffusion layers (TGP-H-60, produced by Tolliy Japan), wherein the mold temperature of the hot press is 140 ℃, the hot-pressing pressure is 5MPa, and the hot-pressing time is controlled to be 1min, thus finishing the manufacture of the membrane electrode of the proton exchange membrane fuel cell.
Example 2
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
pretreatment of a proton exchange membrane: soaking a Nafion212 proton exchange membrane in hydrogen peroxide with the temperature of 70 ℃ and the mass concentration of 5% for 2h, washing with deionized water, soaking in sulfuric acid solution with the temperature of 70 ℃ and the molar concentration of 0.5mol/L for 2h, and finally washing with deionized water;
II, preparing anode inner layer catalyst slurry: weighing the mass of the catalyst, 5% Nafion solution, deionized water, isopropanol and ethylene glycol according to the proportion, wherein the catalyst is Pt/C with the Pt content of 60%, the mass of Nafion is 50% of the mass of the catalyst, and the mass of the deionized water, the isopropanol and the ethylene glycol is determined according to the volume ratio of the deionized water, the isopropanol and the ethylene glycol of 1: 14: 2, measuring and calculating the solid content of the catalyst slurry in the inner layer of the anode by controlling the solid content to be 1.5%, then adding a catalyst into deionized water, then adding a 5% Nafion solution, magnetically stirring for 10min, ultrasonically oscillating for 10min, then adding isopropanol and ethylene glycol, magnetically stirring for 30min, ultrasonically oscillating for 30min, and finally stirring and dispersing for 30min at the rotation speed of 8000 rpm;
III, preparation of catalyst slurry on the outer layer of the anode: weighing the mass of a catalyst, 5% of Nafion solution, 5% of PTFE emulsion, deionized water, isopropanol and ethylene glycol according to the proportion, wherein the catalyst is Pt/C with the Pt content of 60%, the mass of Nafion is 10% of the mass of the catalyst, the mass of PTFE is 5% of the mass of the catalyst, and the mass of the deionized water, the isopropanol and the ethylene glycol is determined according to the volume ratio of the deionized water, the isopropanol and the ethylene glycol of 1: 12: 3, measuring and calculating the solid content of the catalyst slurry on the outer layer of the anode by 0.8%, then adding a catalyst into deionized water, then adding a 5% Nafion solution and a 5% PTFE emulsion, magnetically stirring for 10min, ultrasonically oscillating for 10min, then adding isopropanol and ethylene glycol, magnetically stirring for 30min, ultrasonically oscillating for 30min, and finally stirring and dispersing for 30min at the rotation speed of 8000 rpm;
IV, preparation of cathode catalyst slurry: weighing the mass of the catalyst, 5% Nafion solution, deionized water and isopropanol according to the proportion, wherein the catalyst is Pt/C with the Pt content of 60%, the mass of Nafion is 30% of the mass of the catalyst, and the mass of the deionized water and the isopropanol is determined according to the volume ratio of 1: 16, measuring and calculating the solid content of the cathode catalyst slurry to be 1%, then adding a catalyst into deionized water, then adding a 5% Nafion solution, magnetically stirring for 10min, ultrasonically oscillating for 10min, then adding isopropanol, magnetically stirring for 30min, ultrasonically oscillating for 30min, and finally stirring and dispersing for 30min at the rotation speed of 8000 rpm;
flatly paving and adsorbing the Nafion212 proton exchange membrane treated in the step I on a vacuumizing heating table, setting the temperature of the heating table to be 70 ℃, spraying anode inner layer catalyst slurry on one surface of the proton exchange membrane at a spraying speed of 0.6ml/min, wherein the moving speed of a spray head is 80mm/min, and the moving speed of the spray head is 0.1mg/cm2The Pt loading amount of the anode inner layer catalyst slurry is sprayed, and then the anode inner layer catalyst slurry is placed for 1.5 hours to form an anode inner catalyst layer; then spraying the anode outer layer catalyst slurry on the anode inner catalyst layer at the spraying speed of 0.3ml/min, wherein the moving speed of a spray head is 80mm/min and is 0.03mg/cm2The Pt loading amount of the anode is sprayed with catalyst slurry on the outer layer of the anode, and then the anode is placed for 1.5 hours to form a catalyst layer on the outer layer of the anode; then turning over the proton exchange membrane, spraying cathode catalyst slurry on the other surface of the proton exchange membrane at a spraying rate of 1.0ml/min, wherein the moving speed of a spray head is 80mm/min and is 0.4mg/cm2The Pt loading amount of the catalyst is sprayed with cathode catalyst slurry, and then the catalyst slurry is placed for 1.5 hours to form a cathode catalyst layer;
and VI, finally, respectively hot-pressing the product obtained in the step V on the outer sides of the cathode catalyst layer and the anode outer catalyst layer by using a hot press to form gas diffusion layers (TGP-H-60, produced by Tolliy Japan), wherein the mold temperature of the hot press is 120 ℃, the hot-pressing pressure is 3MPa, and the hot-pressing time is controlled to be 2min, thus finishing the manufacture of the membrane electrode of the proton exchange membrane fuel cell.
Example 3
A preparation method of a membrane electrode of a proton exchange membrane fuel cell comprises the following steps:
pretreatment of a proton exchange membrane: soaking a Nafion212 proton exchange membrane in hydrogen peroxide with the temperature of 75 ℃ and the mass concentration of 3% for 2h, washing with deionized water, soaking in sulfuric acid solution with the temperature of 75 ℃ and the molar concentration of 0.7mol/L for 2h, and finally washing with deionized water;
II, preparing anode inner layer catalyst slurry: weighing the mass of the catalyst, 5% Nafion solution, deionized water, absolute ethyl alcohol and butyl acetate according to the proportion, wherein the catalyst is Pt/C with the Pt content of 50%, the mass of Nafion is 40% of the mass of the catalyst, and the mass of the deionized water, the absolute ethyl alcohol and the butyl acetate is determined according to the volume ratio of the deionized water, the absolute ethyl alcohol and the butyl acetate of 1: 12: 2, measuring and calculating the solid content of the anode inner layer catalyst slurry to be 1%, then adding a catalyst into deionized water, then adding a 5% Nafion solution, magnetically stirring for 10min, ultrasonically oscillating for 10min, then adding absolute ethyl alcohol and butyl acetate, magnetically stirring for 20min, ultrasonically oscillating for 40min, and finally stirring and dispersing for 30min at the rotating speed of 6000 rpm;
III, preparation of catalyst slurry on the outer layer of the anode: weighing the mass of a catalyst, a 5% Nafion solution, a 5% PTFE emulsion, deionized water, absolute ethyl alcohol and butyl acetate according to a proportion, wherein the catalyst is Pt/C with the Pt content of 40%, the mass of Nafion is 15% of the mass of the catalyst, the mass of PTFE is 6% of the mass of the catalyst, and the mass of the deionized water, the absolute ethyl alcohol and the butyl acetate is determined according to the volume ratio of the deionized water, the absolute ethyl alcohol and the butyl acetate of 1: 16: 4, measuring and calculating the solid content of the catalyst slurry on the outer layer of the anode by controlling the solid content to be 0.5%, then adding a catalyst into deionized water, then adding a 5% Nafion solution and a 5% PTFE emulsion, magnetically stirring for 10min, ultrasonically oscillating for 10min, then adding absolute ethyl alcohol and butyl acetate, magnetically stirring for 30min, ultrasonically oscillating for 30min, and finally stirring and dispersing for 30min at the rotating speed of 6000 rpm;
IV, preparation of cathode catalyst slurry: weighing the mass of the catalyst, 5% Nafion solution, deionized water and absolute ethyl alcohol according to the proportion, wherein the catalyst is Pt/C with the Pt content of 40%, the mass of Nafion is 10% of the mass of the catalyst, and the mass of the deionized water and the absolute ethyl alcohol is determined according to the volume ratio of the deionized water to the absolute ethyl alcohol of 1: 14, measuring and calculating the solid content of the cathode catalyst slurry to be 1.5%, then adding a catalyst into deionized water, then adding a 5% Nafion solution, magnetically stirring for 10min, ultrasonically oscillating for 10min, then adding absolute ethyl alcohol, magnetically stirring for 20min, ultrasonically oscillating for 30min, and finally stirring and dispersing for 30min at the rotating speed of 6000 rpm;
flatly paving and adsorbing the Nafion212 proton exchange membrane treated in the step I on a vacuumizing heating table, setting the temperature of the heating table to be 70 ℃, and then spraying anode inner layer catalyst slurry on one surface of the proton exchange membrane at a spraying speed of 0.9ml/min, wherein the moving speed of a spray head is 80mm/min, and the moving speed of the spray head is 0.08mg/cm2The Pt loading amount of the anode inner layer catalyst slurry is sprayed, and then the anode inner layer catalyst slurry is placed for 1.5 hours to form an anode inner catalyst layer; then spraying the catalyst slurry on the outer layer of the anode on the catalyst layer in the anode at the spraying speed of 0.5ml/min, wherein the moving speed of a spray head is 80mm/min and is according to 0.04mg/cm2The Pt loading amount of the anode is sprayed with catalyst slurry on the outer layer of the anode, and then the anode is placed for 1.5 hours to form a catalyst layer on the outer layer of the anode; then turning over the proton exchange membrane, spraying cathode catalyst slurry on the other surface of the proton exchange membrane at a spraying speed of 0.9ml/min, wherein the moving speed of a spray head is 80mm/min and is 0.2mg/cm2The Pt loading amount of the catalyst is sprayed with cathode catalyst slurry, and then the catalyst slurry is placed for 1.5 hours to form a cathode catalyst layer;
and VI, finally, respectively hot-pressing the product obtained in the step V on the outer sides of the cathode catalyst layer and the anode outer catalyst layer by using a hot press to form gas diffusion layers (TGP-H-60, produced by Tolliy Japan), wherein the mold temperature of the hot press is 120 ℃, the hot-pressing pressure is 3MPa, and the hot-pressing time is controlled to be 2min, thus finishing the manufacture of the membrane electrode of the proton exchange membrane fuel cell.
Claims (3)
1. A preparation method of a membrane electrode of a proton exchange membrane fuel cell is characterized in that: spraying cathode catalyst slurry on one surface of a proton exchange membrane and drying to form a cathode catalyst layer, then spraying anode inner layer catalyst slurry on the other surface of the proton exchange membrane and drying to form an anode inner catalyst layer, then spraying anode outer layer catalyst slurry on the surface of the anode inner catalyst layer and drying to form an anode outer catalyst layer, and finally respectively hot-pressing gas diffusion layers on the outer sides of the cathode catalyst layer and the anode outer catalyst layer; the Pt loading ratio of the anode inner catalyst layer to the anode outer catalyst layer is controlled to be 2: 1-1: 1, total of anode inner catalyst layer and anode outer catalyst layerThe Pt loading capacity is controlled to be 0.05-0.3 mg/cm2The Pt loading capacity of the cathode catalyst layer is controlled to be 0.2-0.6 mg/cm2(ii) a The spraying rate of the catalyst slurry on the outer layer of the anode is lower than that of the catalyst slurry on the inner layer of the anode, the spraying rate of the catalyst slurry on the inner layer of the anode is 0.4-1 ml/min, and the spraying rate of the catalyst slurry on the outer layer of the anode is 0.3-0.6 ml/min;
the preparation process of the anode inner layer catalyst slurry comprises the following specific steps: putting a weighed catalyst into deionized water, adding a proton exchange resin solution with the mass concentration of 5-10%, stirring and dispersing, adding a dispersing agent and a thickening agent into the deionized water, dispersing, and stirring at a high rotating speed for a certain time, wherein the solid content of catalyst slurry in the inner layer of the anode is controlled to be 1-2%, the mass of the proton exchange resin is 40-50% of that of the catalyst, and the volume ratio of the deionized water to the dispersing agent to the thickening agent is 1: (10-16): (1-2);
the preparation process of the anode outer layer catalyst slurry comprises the following specific steps: putting a weighed catalyst into deionized water, adding a proton exchange resin solution with the mass concentration of 5-10% and a PTFE emulsion with the mass concentration of 5-10%, stirring and dispersing, then adding a dispersing agent and a thickening agent into the catalyst, dispersing, stirring at a high speed for a certain time, controlling the solid content of the catalyst slurry on the outer layer of the anode to be 0.5-1%, controlling the solid content of the catalyst slurry on the outer layer of the anode to be lower than that of the catalyst slurry on the inner layer of the anode, wherein the mass of the proton exchange resin is 5-15% of the mass of the catalyst, the mass of the PTFE is 3-6% of the mass of the catalyst, and controlling the volume ratio of the deionized water, the dispersing agent and the thickening agent to be: (10-16): (1-4);
the prepared proton exchange membrane fuel cell membrane electrode is characterized in that a cathode catalyst layer is coated on one surface of a proton exchange membrane, an anode inner catalyst layer and an anode outer catalyst layer are sequentially coated on the other surface of the proton exchange membrane, gas diffusion layers are respectively hot-pressed on the outer sides of the cathode catalyst layer and the anode outer catalyst layer, the anode inner catalyst layer comprises a catalyst and proton exchange resin, and the mass of the proton exchange resin is 40-50% of that of the catalyst; the anode outer catalyst layer comprises a catalyst, proton exchange resin and PTFE, wherein the mass of the proton exchange resin is 5-15% of that of the catalyst, and the mass of the PTFE is 3-6% of that of the catalyst.
2. The method of making a proton exchange membrane fuel cell membrane electrode of claim 1, wherein: and drying processes of the cathode catalyst slurry, the anode inner layer catalyst slurry and the anode outer layer catalyst slurry are all drying for 1-2 hours at the temperature of 60-80 ℃.
3. The method of making a proton exchange membrane fuel cell membrane electrode of claim 1, wherein: the catalyst is one or more of Pt/C, Pt-M/C, wherein the content of Pt is 5-60%, and M is one or more of Co, Mo, W, Ru and Pd; the proton exchange resin is Nafion.
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| CN109256565A (en) * | 2018-08-27 | 2019-01-22 | 先进储能材料国家工程研究中心有限责任公司 | Low internal resistance membrane electrode of fuel batter with proton exchange film and preparation method thereof |
| CN109950593A (en) * | 2019-04-04 | 2019-06-28 | 武汉雄韬氢雄燃料电池科技有限公司 | A kind of fuel cell pack and preparation method thereof based on modularized design |
| CN110649291B (en) * | 2019-09-27 | 2022-08-02 | 先进储能材料国家工程研究中心有限责任公司 | Rapid activation method for proton exchange membrane fuel cell |
| CN111244478B (en) * | 2020-01-20 | 2021-08-31 | 鸿基创能科技(广州)有限公司 | Method for preparing crack-free catalyst coating film, catalyst coating film and membrane electrode |
| CN112599799A (en) * | 2020-12-16 | 2021-04-02 | 浙江博氢新能源有限公司 | Preparation method of HT-PEMFC gas diffusion electrode, membrane electrode and preparation method thereof |
| CN113851658A (en) * | 2021-05-10 | 2021-12-28 | 鸿基创能科技(广州)有限公司 | Anode catalyst layer with high anti-reversal pole capability, preparation thereof, membrane electrode and fuel cell application |
| JP7443417B2 (en) * | 2021-05-17 | 2024-03-05 | ブルーム エネルギー コーポレイション | Catalyst ink composition and method for forming a hydrogen pumping proton exchange membrane electrochemical cell |
| CN113793962B (en) * | 2021-08-11 | 2023-09-19 | 广州市乐基智能科技有限公司 | Fuel cell adhesive and preparation method and application thereof |
| CN113745551B (en) * | 2021-08-13 | 2023-03-31 | 国家电投集团氢能科技发展有限公司 | Anode catalysis layer slurry and preparation method thereof |
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