CN102683725B - Preparation method of membrane electrode assembly for direct-methanol fuel cell - Google Patents
Preparation method of membrane electrode assembly for direct-methanol fuel cell Download PDFInfo
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Abstract
The invention provides a preparation method of a high-performance membrane electrode assembly for a direct-methanol fuel cell. A noble metal catalyst is added into mixed solution of isopropyl alcohol and water, then Nafion solution is added into the mixed solution, the proportion between isopropyl alcohol and the water and the temperature of the solution are controlled, mixed slurry is frozen to form solid after ultrasonic processing, then freeze drying processing is carried out, and a mixture of Nafion resin and the dry catalyst can be obtained. The dry catalyst mixture is directly pressed on a gas diffusion electrode or a proton transmission film in a dry pressing mode by adopting a template method, and the membrane electrode assembly is prepared by hot pressing. According to the direct-methanol fuel cell, test results of a membrane electrode prove that the performance of the membrane electrode is slightly higher than a membrane electrode assembly prepared in a CCM method and a traditional GDL method. The preparation method is convenient, efficient, easy to operate and low in cost, can meet development and utilization in the fields of direct-methanol fuel cells and the like, and has a certain practical application value.
Description
Technical field
The present invention relates to direct methanol fuel cell, relate in particular to a kind of preparation method of direct methanol fuel cell membrane electrode assembly.
Background technology
Direct methanol fuel cell (DMFCs) is due to simple in structure, and energy storage density is high, easy to operate, at energy circle, has caused and has studied widely interest.It is to take solid polymer proton exchange membrane as electrolyte, directly take liquid methanol as fuel, and Electrocatalytic Oxidation of Methanol produces CO
2device with electric current.Have that energy conversion efficiency is high, pollution-free, noiselessness, system configuration is simple, energy density is high and fuel carries and supplements the advantages such as convenient.Therefore, direct methanol fuel cell is particularly suitable for the movable power source as various uses.
As the core component of fuel cell, membrane electrode assembly (MEA) is the place that material transferring, electrochemical reaction, electronics and proton transfer and energy shift, and its quality has directly determined the height of whole battery performance.In order to improve the performance of battery, researcher has carried out large quantity research at aspects such as the optimization of MEA structure, each component and technologies of preparing.At present, the preparation method of MEA is mainly divided into following several: (1) GDL method [Lindermeir A, Rosenthal G, Kunz U, Hoffmann U (2004) J.Power Sources 129:180; Seiler T, Savinova E R, Friedrich K A, Stimming U (2004) Electrochim.Acta 49:3927], the most frequently used method of preparing membrane electrode, directly by catalyst and Nafion solution and dispersion solvent, the ultrasonic slurries that are mixed into, then adopt the mode of blade coating or the mode of spraying directly Catalytic Layer to be coated onto to diffusion layer (GDL) upper, be then hot-pressed onto on proton transmission film.The method easily causes the waste of catalyst, and in Catalytic Layer, the utilance of catalyst is low, and the decentralization of Nafion resin in carrier is low etc., has affected the optimum performance of MEA.(2) CCM method (heat turns platen press) [Ren X, Wilson M S and Gottesfeld S (1996) J.Electrochem.Soc.143:L12], the mixed serum of first being prepared by catalyst and Nafion solution and dispersion solvent is sprayed onto on PTFE thin plate, dry at 100 ℃, and then by being loaded with PTFE thin plate and the hot pressing of Nafion film of Catalytic Layer, Catalytic Layer is transferred on Nafion film under hot pressing condition.And then diffusion layer being placed in to the both sides of film, hot pressing becomes membrane electrode assembly.But in the method, the hot transition temperature of Catalytic Layer substantially will be at 160-200 ℃, very easily cause breaking of Catalytic Layer, can not transfer on Nafion film completely, and preparation manipulation process is complicated, and then cause the waste of catalyst and the reduction of catalyst utilization, thereby further affected the performance of direct methanol fuel cell.
Summary of the invention
In view of the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of direct methanol fuel cell membrane electrode assembly, low to solve in fuel cell membrane electrode catalyst activity, the technical problem of preparation process complexity.
To achieve these goals and other relevant objects, the present invention adopts following technical scheme:
The preparation method of direct methanol fuel cell membrane electrode assembly of the present invention, with respect to other method, the method has simple, convenient and practical, by cryodesiccated mode, make catalyst and Nafion resin after ultrasonic processing remain uniform dispersity, can, because of the sedimentation of mixed serum, not cause the reunion of Nafion resin.Prepared dry Nafion resin and the powder of catalyst can directly pass through template synthesis membrane electrode, have avoided the waste of catalyst in spraying process or heat turn pressure process, and the performance of prepared membrane electrode has significantly and improves.And the content of the carrying capacity of Catalytic Layer and Nafion resin has the advantages such as controlled.
The preparation method of direct methanol fuel cell membrane electrode assembly of the present invention, comprises the steps:
(1) carbon supported noble metal catalyst is joined in the drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, wherein, carbon supported noble metal catalyst is carbon supported noble metal cathod catalyst or carbon supported noble metal anode catalyst;
(2) in the system obtaining in step (1), add Nafion solution, making in Nafion solution the weight ratio of carbon carrier in Nafion resin and carbon supported noble metal catalyst is (0.3～1.4): 1, Ultrasonic Heating to 60～80 ℃, obtain catalyst slurry after ultrasonic;
(3) catalyst slurry step (2) being obtained adopts liquid nitrogen frozen, makes catalyst slurry be frozen into solid;
(4) solid step (3) being obtained freeze drying under freezing-condition of vacuumizing, obtains the solid after freeze drying;
(5) after being passed into nitrogen, takes out the drying bottle that fills the solid after freeze drying, obtain the uniform powder of dry catalyst and Nafion resin, the uniform powder of described dry catalyst and Nafion resin is uniform powder or dry anode catalyst and the uniform powder of Nafion resin of dry cathod catalyst and Nafion resin;
(6) dry cathod catalyst step (5) being obtained and the uniform powder of Nafion resin and dry anode catalyst and the uniform powder of Nafion resin are put into respectively on the Nafion film of protecting with frame, and dispersed respectively, compacting respectively, remove the catalysis tunic that obtains dry-pressing after frame, described catalysis tunic, in the middle of it, be Nafion rete, a side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer;
(7) gas diffusion layers is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 130-145 ℃ and pressure be 75-115kgcm
-2lower hot pressing 3-5 minute, obtains high performance direct methanol fuel cell membrane electrode assembly.Or,
(6-2) cathod catalyst step (5) being obtained is put on the gas diffusion layers with frame protection with the uniform powder of Nafion resin, dispersed, and the cathode diffusion electrode that obtains containing cathode catalysis layer after frame is removed in compacting; The uniform powder of anode catalyst and Nafion resin is put on the gas diffusion layers with frame protection, and dispersed, compacting, obtains the anode diffusion electrode containing anode catalyst layer after removing frame;
(7-2) cathode diffusion electrode and anode diffusion electrode are placed on respectively to the both sides of Nafion film, and gas diffusion layers is away from Nafion film, at 130-145 ℃ and pressure be 75-115kgcm
-2lower hot pressing 3-5 minute, obtains high performance direct methanol fuel cell membrane electrode assembly.
Preferably, in step (1), the volume ratio of deionized water and isopropyl alcohol is 20% ~ 80%.
Preferably, in step (1), described carbon supported noble metal catalyst is Pt/C or PtRu/C.Described carbon supported noble metal cathod catalyst is selected from Pt/C; Described carbon supported noble metal anode catalyst is selected from PtRu/C.Pt/C represents carbon supported noble metal Pt, and PtRu/C represents carbon supported noble metal Pt and Ru.Above-mentioned carbon supported noble metal catalyst can all adopt the commercial catalysts of John Matthey company.
Nafion solution in above-mentioned steps (2) represents Nafion resin solution, and its solvent is low carbon chain alcohol and water.The Nafion solution adding in step (2), Nafion resin content wherein can be the Nafion solution of the commercial criterion of 5wt% or 20wt%, and in the weight that makes dry Nafion resin contained in added Nafion solution and added catalyst, the ratio of the weight of carbon carrier is (0.3～1.4): 1.This Nafion solution can directly be bought and obtain from the market, as the present invention is directly purchased from the Nafion resin solution that the Nafion of company of Du Pont (Dupont) weight resin percentage composition is respectively 5wt.% and two kinds of models of 20wt.%.
Preferably, in step (2), in the Nafion solution adding, the quality percentage composition of Nafion resin is 5wt%-20wt%.
Preferably, in step (2), the ultrasonic time is 2-4 hour.
Preferably, in step (3), the freezing time is 10-20 minute.
Preferably, in step (4), described freezing temperature is-60～-15 ℃.
Preferably, in step (4), the cryodesiccated time is 12-24 hour.
In above-mentioned steps (4) freezing-freeze drying that vacuumizes under condition can adopt freeze drier to process; Its vacuum condition can adopt oil pump to vacuumize the vacuum degree condition that can reach.
Preferably, in the cathode catalysis layer in step (6) and step (6-2), the carrying capacity of noble metal catalyst is 0.5～4mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 0.5～4mg/cm
2.
Preferably, the gas diffusion layers in step (7) and step (6-2) is selected from carbon fiber paper TGPH-060 and the carbon fiber paper TGPH-030 of toray company (Toray), and German SGL company
gas diffusion layers GDL24BC carbon fiber paper, GDL 25BC carbon fiber paper and GDL34BC carbon fiber paper.
The high performance direct methanol fuel cell membrane electrode assembly obtaining in step (7) and step (7-2), its intermediate layer is Nafion rete, one side of Nafion rete is cathode catalysis layer, opposite side is anode catalyst layer, and the outside of cathode catalysis layer and anode catalyst layer is gas diffusion layers.
The present invention further provides a kind of direct methanol fuel cell membrane electrode assembly, for making according to the preparation method of above-mentioned direct methanol fuel cell membrane electrode assembly.
The present invention also provides a kind of monomer direct methanol fuel cell, and described monomer direct methanol fuel cell comprises above-mentioned high performance direct methanol fuel cell membrane electrode assembly.
The present invention also provides a kind of direct methanol fuel cell group, comprises above-mentioned a plurality of monomer direct methanol fuel cell.
The membrane electrode assembly that the present invention is made is assembled into monomer direct methanol fuel cell, utilize Arbin fuel battery test system to carry out performance test to monomer direct methanol fuel cell, test result shows, aspect peak power output density, the direct methanol fuel cell of the membrane electrode joint body assembling that the present invention is prepared has reached respectively 58.9mW/cm
2and 57.2mW/cm
2, and adopt, the performance of traditional CCM and the prepared membrane electrode assembly of GDL method is respectively 38.9,25.2mW/cm
2and 41.2mW/cm
2.
As can be seen here, the prepared membrane electrode assembly of the present invention has very high electro-chemical activity and stability, has improved the utilance of catalyst, has reduced the carrying capacity of catalyst.The preparation method of this direct methanol fuel cell membrane electrode assembly is convenient, efficient, easy operating, and with low cost, can meet the development and utilization in electro-catalysis fuel cell, Proton Exchange Membrane Fuel Cells field, and application, exploitation are worth greatly.
Accompanying drawing explanation
Fig. 1 freeze drying-template synthesis membrane electrode schematic diagram;
Fig. 2 different batches freeze drying-template synthesis membrane electrode assembly performance comparison (in embodiment 5 in triplicate the performance comparison of prepared membrane electrode)
Fig. 3 membrane electrode assembly provided by the invention and heat turn the discharge performance figure of the direct methanol fuel cell of membrane electrode assembly assembling prepared by platen press (CCM method) and traditional GDL method.
Embodiment
Below, by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Embodiment 1
By a certain amount of carbon supported noble metal cathod catalyst or anode catalyst (cathod catalyst: 30wt.%Pt/C catalyst, anode catalyst: 30wt.%PtRu/C, all from Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 40%, then the Nafion solution that adds the business-like 5wt%Nafion of the containing resin of E.I.Du Pont Company, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating to 60～80 ℃, ultrasonic 2-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 10 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 12-24 hour, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; Gas diffusion layers (Toray TGPH-030) is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 0.5mg/cm
2; The carrying capacity of the middle noble metal catalyst of anode catalyst layer is 1.0mg/cm
2.
Freeze drying-template synthesis membrane electrode of the present invention as shown in Figure 1, the first step fixes gas diffusion layers carbon fiber paper or Nafion film with the frame of suitable dimension, second step takes the catalyst of a certain amount of freeze drying acquisition and the uniform powder of Nafion resin, on Nafion film or on carbon fiber paper, be uniformly dispersed, the carrying capacity of cathode and anode Catalytic Layer catalyst is controlled at respectively 0.5～4mg/cm
2, the 3rd step, is pressed in the module of suitable dimension in Catalytic Layer, and the 4th step can obtain the membrane electrode containing Catalytic Layer.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, the discharge performance figure of the direct methanol fuel cell of assembling as shown in Figure 3, as can be seen from Figure 3 membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
Embodiment 2
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 60wt.%Pt/C catalyst, anode catalyst: 60wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 40%, then add the Nafion solution that contains 5wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating to 60～80 ℃, ultrasonic 2-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 10 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 12 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; Gas diffusion layers Toray TGPH-060 is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 1mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 2mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
Embodiment 3
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 80 wt.%Pt/C catalyst, anode catalyst: 60 wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 40%, then add the Nafion solution that contains 5wt% Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating to 70 ℃, ultrasonic 2-3 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 10 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 12 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; The gas diffusion layers GDL24BC carbon paper of company (German SGL) is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 2mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 4mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
Embodiment 4
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 60wt.%Pt/C catalyst, anode catalyst: 30wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 50%, then add the Nafion solution that contains 20wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating to 70 ℃, ultrasonic 2-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 15 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 24 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; German SGL gas diffusion layers GDL 25BC is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 130 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 1.5mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 3mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
Embodiment 5
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 60 wt.%Pt/C catalyst, anode catalyst: 30wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 60%, then add the Nafion solution that contains 5wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating to 70 ℃, ultrasonic 3-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 10 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 24 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; Toray TGPH-060 gas diffusion layers is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 140 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 1mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 2mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
According to the step of the present embodiment, repeat again twice, obtain the membrane electrode assembly of three batches altogether.Different batches freeze drying-template synthesis membrane electrode assembly is carried out to performance comparison, as shown in Figure 2, by this diagram data, can be illustrated, the prepared membrane electrode assembly of the present invention has extraordinary homogeneity and stability, and the reappearance of different batches is very good, therefore can be conducive to Practical Project or suitability for industrialized production.
Embodiment 6
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 60 wt.%Pt/C catalyst, anode catalyst: 60wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 50%, then add the Nafion solution that contains 5wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating is to 65-75 ℃, ultrasonic 2-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 20 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 24 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; GDL34BC gas diffusion layers is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 140 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 1.5mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 2mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
According to the step of the present embodiment, repeat again twice, obtain the membrane electrode assembly of three batches altogether.Different batches freeze drying-template synthesis membrane electrode assembly is carried out to performance comparison known, the prepared membrane electrode assembly of the present invention has extraordinary homogeneity and stability, and the reappearance of different batches is very good, therefore can be conducive to Practical Project or suitability for industrialized production.
Embodiment 7
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 20 wt.%Pt/C catalyst, anode catalyst: 30wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 60%, then add the Nafion solution that contains 20wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating is to 65-75 ℃, ultrasonic 4 hours, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 15 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 24 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; Toray TGPH-060 gas diffusion layers is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 1.5mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 2.5mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
According to the step of the present embodiment, repeat again twice, obtain the membrane electrode assembly of three batches altogether.Different batches freeze drying-template synthesis membrane electrode assembly is carried out to performance comparison known, the prepared membrane electrode assembly of the present invention has extraordinary homogeneity and stability, and the reappearance of different batches is very good, therefore can be conducive to Practical Project or suitability for industrialized production.
Embodiment 8
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 20wt.%Pt/C catalyst, anode catalyst: 60wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 50%, then add the Nafion solution that contains 20wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.7(N/C=0.7), Ultrasonic Heating is to 65-75 ℃, ultrasonic 4 hours, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 15 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 51 degrees Celsius, freezing-to vacuumize dry 24 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; TGPH 030 gas diffusion layers is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 140 ℃, pressure 95kg cm
-2, hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 2mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 2mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
According to the step of the present embodiment, repeat again twice, obtain the membrane electrode assembly of three batches altogether.Different batches freeze drying-template synthesis membrane electrode assembly is carried out to performance comparison known, the prepared membrane electrode assembly of the present invention has extraordinary homogeneity and stability, and the reappearance of different batches is very good, therefore can be conducive to Practical Project or suitability for industrialized production.
Embodiment 9
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 80wt.%Pt/C catalyst, anode catalyst: 60wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 40%, then add the Nafion solution that contains 5wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 1.4(N/C=1.4), Ultrasonic Heating is to 65-75 ℃, ultrasonic 2-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 10 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 40 degrees Celsius, freezing-to vacuumize dry 18 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; The gas diffusion layers GDL 24BC carbon paper of company (German SGL) is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 135 ℃, pressure 95kg cm
-2hot pressing 5min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 4mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 1.5mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
According to the step of the present embodiment, repeat again twice, obtain the membrane electrode assembly of three batches altogether.Different batches freeze drying-template synthesis membrane electrode assembly is carried out to performance comparison known, the prepared membrane electrode assembly of the present invention has extraordinary homogeneity and stability, and the reappearance of different batches is very good, therefore can be conducive to Practical Project or suitability for industrialized production.
Embodiment 10
By a certain amount of carbon supported noble metal negative electrode or anode commercial catalysts (cathod catalyst: 60wt.%Pt/C catalyst, anode catalyst: 60wt.%PtRu/C, Britain John Matthey company) join in the freeze drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, the volume ratio of deionized water and isopropyl alcohol is 40%, then add the Nafion solution that contains 5wt%Nafion resin, the weight ratio that makes carbon carrier in Nafion resin and carried catalyst is 0.3(N/C=0.3), Ultrasonic Heating is to 65-75 ℃, ultrasonic 2-4 hour, obtain catalyst slurry, then the freeze drying bottle that fills catalyst slurry is used to liquid nitrogen frozen 10 minutes, make catalyst slurry be frozen into solid, then freeze drying bottle graft is entered to freeze drier, at constant temperature subzero 20 degrees Celsius, freezing-to vacuumize dry 24 hours, pass into nitrogen, take out drying bottle, obtain the uniform powder of dry catalyst and Nafion resin, be respectively uniform cathode powder and uniform anode powder.Then the cathode powder and the positive powder that take constant weight are put into respectively on the Nafion film with frame protection, dispersed respectively, compacting respectively, remove the catalysis tunic of dry-pressing after frame, the centre of this catalysis tunic is Nafion rete, one side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer; Gas diffusion layers Toray TGPH-060 is placed on respectively to the both sides of the catalysis tunic of dry-pressing, at 135 ℃, pressure 95kg cm
-2, hot pressing 3-4min, obtains high performance direct methanol fuel electrode membrane electrode aggregate.In the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained, the carrying capacity of noble metal catalyst is 3mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 1.5mg/cm
2.
The membrane electrode assembly that the present embodiment is obtained and heat turn membrane electrode assembly prepared by platen press (CCM) and traditional GDL method and are assembled into respectively direct methanol fuel cell, from the discharge performance test of assembled direct methanol fuel cell, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all turns membrane electrode assembly prepared by platen press (CCM) and traditional GDL method higher than heat.
According to the step of the present embodiment, repeat again twice, obtain the membrane electrode assembly of three batches altogether.Different batches freeze drying-template synthesis membrane electrode assembly is carried out to performance comparison known, the prepared membrane electrode assembly of the present invention has extraordinary homogeneity and stability, and the reappearance of different batches is very good, therefore can be conducive to Practical Project or suitability for industrialized production.
The above; it is only preferred embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of the inventive method, also can make some improvement and supplement, these improvement and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change of making when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be equivalent embodiment of the present invention; Meanwhile, the change of any equivalent variations that all foundations essence technology of the present invention is done above-described embodiment, modification and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (14)
1. a preparation method for direct methanol fuel cell membrane electrode assembly, comprises the steps:
1 joins carbon supported noble metal catalyst in the drying bottle of the mixed solvent that fills deionized water and isopropyl alcohol, and wherein, carbon supported noble metal catalyst is carbon supported noble metal cathod catalyst or carbon supported noble metal anode catalyst;
2 add Nafion solution in the systems that step 1 obtains, and making in Nafion solution the weight ratio of carbon carrier in Nafion resin and carbon supported noble metal catalyst is (0.3～1.4): 1, and Ultrasonic Heating to 60～80 ℃, obtain catalyst slurry after ultrasonic;
3 catalyst slurries that step 2 is obtained adopt liquid nitrogen frozen, make catalyst slurry be frozen into solid;
The freeze drying under freezing-condition of vacuumizing of 4 solids that step 3 is obtained, obtains the solid after freeze drying;
5 take out after the drying bottle that fills the solid after freeze drying is passed into nitrogen, obtain the uniform powder of dry catalyst and Nafion resin, the uniform powder of described dry catalyst and Nafion resin is uniform powder or dry anode catalyst and the uniform powder of Nafion resin of dry cathod catalyst and Nafion resin;
The dry anode catalyst obtaining in the uniform powder of the 6 dry cathod catalysts that step 5 is obtained and Nafion resin and step 5 and the uniform powder of Nafion resin are put into respectively on the Nafion film with frame protection, and dispersed respectively, respectively compacting, removes the catalysis tunic that obtains dry-pressing after frame; Described catalysis tunic, is Nafion rete in the middle of it, and a side of Nafion rete is cathode catalysis layer, and opposite side is anode catalyst layer;
7 are placed on respectively the both sides of the catalysis tunic of dry-pressing by gas diffusion layers, at 130-145 ℃ and pressure be 75-115kgcm
-2lower hot pressing 3-5 minute, obtains described direct methanol fuel cell membrane electrode assembly;
Or,
The cathod catalyst that 6-2 obtains step 5 is put on the gas diffusion layers with frame protection with the uniform powder of Nafion resin, dispersed, and the cathode diffusion electrode that obtains containing cathode catalysis layer after frame is removed in compacting; The anode catalyst that step 5 is obtained is put on the gas diffusion layers with frame protection with the uniform powder of Nafion resin, dispersed, and the anode diffusion electrode that obtains containing anode catalyst layer after frame is removed in compacting;
7-2 is placed on cathode diffusion electrode and anode diffusion electrode respectively the both sides of Nafion film, and gas diffusion layers is away from Nafion film, at 130-145 ℃ and pressure be 75-115kgcm
-2lower hot pressing 3-5 minute, obtains described direct methanol fuel cell membrane electrode assembly.
2. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in step 1, described carbon supported noble metal cathod catalyst is selected from Pt/C; Described carbon supported noble metal anode catalyst is selected from PtRu/C.
3. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in step 1, the volume ratio of deionized water and isopropyl alcohol is 20%～80%.
4. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in step 2, in the Nafion solution adding, the quality percentage composition of Nafion resin is 5wt%-20wt%.
5. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in step 2, in step 2, the ultrasonic time is 2-4 hour.
6. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in step 2, in step 3, the freezing time is 10-20 minute.
7. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in step 4, described freezing temperature is-60～-15 ℃; The cryodesiccated time is 12-24 hour.
8. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, is characterized in that, in the cathode catalysis layer in step 6 and step 6-2, the carrying capacity of noble metal catalyst is 0.5～4mg/cm
2; In anode catalyst layer, the carrying capacity of noble metal catalyst is 0.5～4mg/cm
2.
9. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, it is characterized in that, the gas diffusion layers in step 7 and step 6-2 is selected from carbon fiber paper TGPH-060, carbon fiber paper TGPH-030, GDL24BC carbon fiber paper, GDL25BC carbon fiber paper and GDL34BC carbon fiber paper.
10. the preparation method of direct methanol fuel cell membrane electrode assembly as claimed in claim 1, it is characterized in that, the direct methanol fuel cell membrane electrode assembly obtaining in step 7 and step 7-2, its intermediate layer is Nafion rete, one side of Nafion rete is cathode catalysis layer, opposite side is anode catalyst layer, and the outside of cathode catalysis layer and anode catalyst layer is gas diffusion layers.
11. 1 kinds of direct methanol fuel cell membrane electrode assemblies, for making according to the preparation method of the direct methanol fuel cell membrane electrode assembly described in claim 1-10 any one.
12. 1 kinds of monomer direct methanol fuel cell, is characterized in that, described monomer direct methanol fuel cell comprises the direct methanol fuel cell membrane electrode assembly described in claim 11.
13. 1 kinds of direct methanol fuel cell groups, comprise the monomer direct methanol fuel cell described in a plurality of claims 12.
14. application of direct methanol fuel cell membrane electrode assembly as claimed in claim 11 in electro-catalysis fuel cell and Proton Exchange Membrane Fuel Cells.
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| CN105762374A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Fuel cell catalyst layer and membrane electrode subassembly and preparation method thereof |
| CN106410246B (en) * | 2016-11-15 | 2019-04-16 | 浙江大学 | A kind of preparation method of the alkaline anion-exchange membrane for fuel cell |
| CN109524676A (en) * | 2018-11-20 | 2019-03-26 | 安徽明天氢能科技股份有限公司 | A kind of fuel cell catalyst layer electrode of three-dimensional and preparation method thereof |
| CN113921831B (en) * | 2021-09-22 | 2023-02-21 | 一汽解放汽车有限公司 | Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell |
| CN116581308B (en) * | 2023-07-12 | 2023-10-20 | 苏州氢澜科技有限公司 | Dry membrane electrode preparation method of membrane fuel cell |
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| CN101908645A (en) * | 2010-07-30 | 2010-12-08 | 哈尔滨工业大学 | Ceramic/solid polymer electrolyte composite material with continuously and directionally-distributed wild phases and preparation method thereof |
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