CN102683725A - 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 DMFC, relate in particular to a kind of preparation method of DMFC membrane electrode assembly.
Background technology
DMFC (DMFCs) is because simple in structure, and energy storage density is high, and is easy to operate, caused extensive studies interest at energy circle.It is to be electrolyte with the solid polymer PEM, directly is fuel with the liquid methanol, and catalytic oxidation methyl alcohol produces CO
2Device with electric current.Have energy conversion efficiency height, pollution-free, noiselessness, system configuration is simple, energy density is high and fuel carries and replenishes advantages such as convenient.Therefore, DMFC is suitable for the removable power supply as various uses especially.
The act as a fuel core component of battery, membrane electrode assembly (MEA) is the place that material transmission, electrochemical reaction, electronics and proton transfer and energy shift, its quality has directly determined the height of entire cell performance.In order to improve the performance of battery, the researcher has carried out big quantity research at aspects such as the optimization of MEA structure, each component and technologies of preparing.At present, the preparation method of MEA mainly is divided into following several kinds: (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]; Be the most frequently used method of preparation membrane electrode, promptly directly with catalyst and Nafion solution and dispersion solvent, the ultrasonic slurries that are mixed into; Adopt the mode of blade coating or the mode of spraying directly Catalytic Layer to be coated onto on the diffusion layer (GDL) then, be hot-pressed onto on the proton transmission film then.The method is prone to cause the waste of catalyst, and the utilance of catalyst is low in the Catalytic Layer, and the decentralization of Nafion resin in carrier is low etc., has influenced the optimum performance of MEA.(2) CCM method (heat is changeed platen press) [Ren X; Wilson M S and Gottesfeld S (1996) J.Electrochem.Soc.143:L12]; Promptly elder generation is sprayed onto the mixed serum of catalyst and Nafion solution and dispersion solvent preparation on the PTFE thin plate; 100 ℃ of dryings, and then will be loaded with the PTFE thin plate and the hot pressing of Nafion film of Catalytic Layer, Catalytic Layer is transferred on the Nafion film under hot pressing condition.And then diffusion layer placed the both sides of film, hot pressing prepares the film forming electrode aggregate.But the hot transition temperature of Catalytic Layer basically will be at 160-200 ℃ in this method; Very easily cause breaking of Catalytic Layer; Can not transfer on the Nafion film fully; And the preparation manipulation process is complicated, and then causes the waste of catalyst and the reduction of catalyst utilization, thereby has further influenced the performance of DMFC.
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 DMFC membrane electrode assembly, low with catalyst activity in the solution fuel cell membrane electrode, preparation process complicated technology problem.
Reach other relevant purposes to achieve these goals, the present invention adopts following technical scheme:
The preparation method of DMFC membrane electrode assembly of the present invention; With respect to other method; The method has simple, convenient and practical; Make catalyst and Nafion resin after the sonicated remain uniform dispersity through cryodesiccated mode, can not cause the reunion of Nafion resin because of the sedimentation of mixed serum.The prepared Nafion resin of doing and the powder of catalyst can directly prepare membrane electrode through template, avoided the waste of catalyst in spraying process or heat commentaries on classics pressure process, and the performance of prepared membrane electrode have significantly raising.And the content of the carrying capacity of Catalytic Layer and Nafion resin has advantages such as controlled.
The preparation method of DMFC 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 that step (1) obtains, add Nafion solution; Make in the Nafion solution that the weight ratio of carbon carrier is (0.3～1.4) in the Nafion resin and carbon supported noble metal catalyst: 1; Ultrasonicly be heated to 60～80 ℃, obtain catalyst slurry after ultrasonic;
(3) catalyst slurry that step (2) is obtained adopts liquid nitrogen frozen, makes catalyst slurry be frozen into solid;
(4) solid that step (3) is obtained freeze drying under freezing-condition of vacuumizing obtains the solid after the freeze drying;
After feeding nitrogen, takes out the drying bottle that (5) will fill the solid after the freeze drying; Obtain the dry catalyst and the uniform powder of Nafion resin, the uniform powder of the catalyst of said drying and Nafion resin is the dry cathod catalyst and uniform powder or the anode catalyst of drying and the uniform powder of Nafion resin of Nafion resin;
The uniform powder of the cathod catalyst of the drying that (6) step (5) is obtained and the uniform powder of Nafion resin and dry anode catalyst and Nafion resin is put into respectively and has on the Nafion film that frame protects; And disperse respectively evenly, the catalysis tunic that obtains dry-pressing behind the frame is removed in compacting respectively; Said catalysis tunic; Be the Nafion rete wherein, a side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer;
(7) gas diffusion layers is placed on the both sides of the catalysis tunic of dry-pressing respectively, 130-145 ℃ down and pressure be 75-115kgcm
-2Following hot pressing 3-5 minute, obtain high performance DMFC membrane electrode assembly.Perhaps,
The cathod catalyst that (6-2) step (5) is obtained is put on the gas diffusion layers that has the frame protection with the uniform powder of Nafion resin, evenly dispersion, and the cathode diffusion electrode that obtains containing cathode catalysis layer behind the frame is removed in compacting; The uniform powder of anode catalyst and Nafion resin is put on the gas diffusion layers that has the frame protection, evenly disperses, the anode diffusion electrode that obtains containing the anode Catalytic Layer behind the frame is removed in compacting;
(7-2) cathode diffusion electrode and anode diffusion electrode are placed on the both sides of Nafion film respectively, and gas diffusion layers is away from the Nafion film, 130-145 ℃ down and pressure be 75-115kgcm
-2Following hot pressing 3-5 minute, obtain high performance DMFC membrane electrode assembly.
Preferably, in the step (1), the volume ratio of deionized water and isopropyl alcohol is 20% ~ 80%.
Preferably, in the step (1), said carbon supported noble metal catalyst is Pt/C or PtRu/C.Said carbon supported noble metal cathod catalyst is selected from Pt/C; Said 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 the above-mentioned steps (2) is represented the Nafion resin solution, and its solvent is the low carbon chain alcohol and water.The Nafion solution that adds in the step (2); Nafion resin content wherein can be the Nafion solution of the commercial criterion of 5wt% or 20wt%, and the ratio of the weight of carbon carrier is (0.3～1.4) in the weight that makes dried Nafion resin contained in the Nafion solution that is added and the adding catalyst: 1.This Nafion solution can directly be bought from market and obtain, and directly purchases the Nafion resin solution that is respectively 5wt.% and two kinds of models of 20wt.% in the Nafion of company of Du Pont (Dupont) weight resin percentage composition like the present invention.
Preferably, in the step (2), the quality percentage composition of Nafion resin is 5wt%-20wt% in the Nafion solution that is added.
Preferably, in the step (2), the ultrasonic time is 2-4 hour.
Preferably, in the step (3), the freezing time is 10-20 minute.
Preferably, in the step (4), said freezing temperature is-60～-15 ℃.
Preferably, in the step (4), the cryodesiccated time is 12-24 hour.
Freezing-freeze drying of vacuumizing under the condition in the above-mentioned steps (4) can adopt freeze drier to handle; Its vacuum condition can adopt oil pump to vacuumize the vacuum degree condition that can reach and get final product.
Preferably, the carrying capacity of noble metal catalyst is 0.5～4mg/cm in the cathode catalysis layer in step (6) and the step (6-2)
2The carrying capacity of noble metal catalyst is 0.5～4mg/cm in the anode catalyst layer
2
Preferably; Gas diffusion layers in step (7) and the step (6-2) is selected from the carbon fiber paper TGPH-060 and the carbon fiber paper TGPH-030 of toray company (Toray), and
gas diffusion layers GDL24BC carbon fiber paper, GDL 25BC carbon fiber paper and the GDL34BC carbon fiber paper of German SGL company.
The high performance DMFC membrane electrode assembly that obtains in step (7) and the step (7-2); Its intermediate layer is the Nafion rete; One side of Nafion rete is a cathode catalysis layer; Opposite side is an 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 DMFC membrane electrode assembly, for the preparation method according to above-mentioned DMFC membrane electrode assembly makes.
The present invention also provides a kind of monomer DMFC, and said monomer DMFC comprises above-mentioned high performance DMFC membrane electrode assembly.
The present invention also provides a kind of DMFC group, comprises above-mentioned a plurality of monomer DMFC.
The membrane electrode assembly that the present invention is made is assembled into the monomer DMFC; Utilize the Arbin fuel battery test system that the monomer DMFC has been carried out performance test; Test result shows; Aspect peak power output density, the DMFC of the membrane electrode joint body assembling that the present invention is prepared has reached 58.9mW/cm respectively
2And 57.2mW/cm
2, the performance of the prepared membrane electrode assembly of traditional CCM and GDL method is respectively 38.9,25.2mW/cm and adopt
2And 41.2mW/cm
2
This shows that 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 DMFC membrane electrode assembly is convenient, efficient, easy operating, and with low cost, can satisfy the development and utilization in electro-catalysis fuel cell, Proton Exchange Membrane Fuel Cells field, uses, develops value greatly.
Description of drawings
Fig. 1 freeze drying-template prepares the membrane electrode sketch map;
Fig. 2 different batches freeze drying-template prepares membrane electrode assembly performance comparison (performance comparison of the prepared membrane electrode of triplicate among the embodiment 5)
The discharge performance figure of the DMFC of the membrane electrode assembly assembling of Fig. 3 membrane electrode assembly provided by the invention and heat commentaries on classics platen press (CCM method) and the preparation of traditional G DL method.
Embodiment
Below through specific instantiation execution mode of the present invention is described, those skilled in the art can understand other advantages of the present invention and effect easily by the content that this specification disclosed.The present invention can also implement or use through other different embodiment, and each item details in this specification also can be based on different viewpoints and application, carries out various modifications or change under the spirit of the present invention not deviating from.
With 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%, adds the Nafion solution of the business-like 5wt%Nafion of the containing resin of E.I.Du Pont Company then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 60～80 ℃, ultrasonic 2-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 10 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 12-24 hour, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; Gas diffusion layers (Toray TGPH-030) is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 0.5mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of the middle noble metal catalyst of anode catalyst layer is 1.0mg/cm
2
It is as shown in Figure 1 that freeze drying-template of the present invention prepares membrane electrode; The first step fixes gas diffusion layers carbon fiber paper or the Nafion film frame with suitable dimension; Second step took by weighing the catalyst of a certain amount of freeze drying acquisition and the uniform powder of Nafion resin; Be uniformly dispersed on the Nafion film or on the carbon fiber paper, the carrying capacity of cathode and anode Catalytic Layer catalyst is controlled at 0.5～4mg/cm respectively
2, the 3rd step, the module of suitable dimension is pressed on the Catalytic Layer, the 4th step can obtain containing the membrane electrode of Catalytic Layer.
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; The discharge performance figure of the DMFC of being assembled is as shown in Figure 3; Membrane electrode assembly as can be seen from Figure 3 provided by the invention, the battery performance of assembling all are higher than the membrane electrode assembly that heat is changeed platen press (CCM) and the preparation of traditional G DL method.
With 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%, adds the Nafion solution that contains the 5wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 60～80 ℃, ultrasonic 2-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 10 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 12 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; Gas diffusion layers Toray TGPH-060 is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 1mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 2mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
With 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%, adds the Nafion solution that contains 5wt% Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 70 ℃, ultrasonic 2-3 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 10 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 12 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; The gas diffusion layers GDL24BC carbon paper of company (German SGL) is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 2mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 4mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Embodiment 4
With 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%, adds the Nafion solution that contains the 20wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 70 ℃, ultrasonic 2-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 15 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 24 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; German SGL gas diffusion layers GDL 25BC is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 130 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 1.5mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 3mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Embodiment 5
With 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%, adds the Nafion solution that contains the 5wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 70 ℃, ultrasonic 3-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 10 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 24 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; Toray TGPH-060 gas diffusion layers is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 140 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 1mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 2mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Step according to present embodiment repeats twice again, obtains three batches membrane electrode assembly altogether.Different batches freeze drying-template is prepared membrane electrode assembly carry out performance comparison; As shown in Figure 2; Can explain by this diagram data; 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 help actual through engineering approaches or suitability for industrialized production.
Embodiment 6
With 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%, adds the Nafion solution that contains the 5wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 65-75 ℃, ultrasonic 2-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 20 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 24 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; The GDL34BC gas diffusion layers is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 140 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 1.5mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 2mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Step according to present embodiment repeats twice again, obtains three batches membrane electrode assembly altogether.Different batches freeze drying-template is prepared membrane electrode assembly carries out performance comparison and can know; 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 help actual through engineering approaches or suitability for industrialized production.
Embodiment 7
With 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%, adds the Nafion solution that contains the 20wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 65-75 ℃, ultrasonic 4 hours, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 15 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 24 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; Toray TGPH-060 gas diffusion layers is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 135 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 1.5mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 2.5mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Step according to present embodiment repeats twice again, obtains three batches membrane electrode assembly altogether.Different batches freeze drying-template is prepared membrane electrode assembly carries out performance comparison and can know; 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 help actual through engineering approaches or suitability for industrialized production.
Embodiment 8
With 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%, adds the Nafion solution that contains the 20wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.7 (N/C=0.7); Ultrasonicly be heated to 65-75 ℃, ultrasonic 4 hours, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 15 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 51 degrees centigrade; Freezing-as to vacuumize dry 24 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; TGPH 030 gas diffusion layers is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 140 ℃, pressure 95kg cm
-2, hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 2mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 2mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Step according to present embodiment repeats twice again, obtains three batches membrane electrode assembly altogether.Different batches freeze drying-template is prepared membrane electrode assembly carries out performance comparison and can know; 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 help actual through engineering approaches or suitability for industrialized production.
Embodiment 9
With 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%, adds the Nafion solution that contains the 5wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 1.4 (N/C=1.4); Ultrasonicly be heated to 65-75 ℃, ultrasonic 2-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 10 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 40 degrees centigrade; Freezing-as to vacuumize dry 18 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; The gas diffusion layers GDL 24BC carbon paper of company (German SGL) is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 135 ℃, pressure 95kg cm
-2Hot pressing 5min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 4mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 1.5mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Step according to present embodiment repeats twice again, obtains three batches membrane electrode assembly altogether.Different batches freeze drying-template is prepared membrane electrode assembly carries out performance comparison and can know; 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 help actual through engineering approaches or suitability for industrialized production.
With 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%, adds the Nafion solution that contains the 5wt%Nafion resin then; The weight ratio that makes carbon carrier in Nafion resin and the carried catalyst is 0.3 (N/C=0.3); Ultrasonicly be heated to 65-75 ℃, ultrasonic 2-4 hour, obtain catalyst slurry; The freeze drying bottle that will fill catalyst slurry then makes catalyst slurry be frozen into solid with liquid nitrogen frozen 10 minutes, then the freeze drying bottle graft is gone into freeze drier; At constant temperature subzero 20 degrees centigrade; Freezing-as to vacuumize dry 24 hours, feed nitrogen, take out drying bottle; Obtain the dry catalyst and the uniform powder of Nafion resin, be respectively uniform cathode powder and uniform anode powder.The cathode powder and the positive powder that take by weighing constant weight then are put into respectively on the Nafion film that has the frame protection; Evenly disperse respectively; The catalysis tunic of dry-pressing behind the frame is removed in respectively compacting, and the centre of this catalysis tunic is the Nafion rete; One side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer; Gas diffusion layers Toray TGPH-060 is placed on the both sides of the catalysis tunic of dry-pressing respectively, at 135 ℃, pressure 95kg cm
-2, hot pressing 3-4min promptly obtains high performance direct methanol fuel electrode membrane electrode aggregate.The carrying capacity of noble metal catalyst is 3mg/cm in the cathode catalysis layer of the high performance direct methanol fuel electrode membrane electrode aggregate of gained
2The carrying capacity of noble metal catalyst is 1.5mg/cm in the anode catalyst layer
2
Present embodiment membrane electrode assembly that obtains and the membrane electrode assembly that heat commentaries on classics platen press (CCM) and traditional G DL method prepare are assembled into DMFC respectively; From the discharge performance test of the DMFC assembled, can find out membrane electrode assembly provided by the invention, the battery performance of assembling all is higher than heat changes the membrane electrode assembly that platen press (CCM) and traditional G DL method prepare.
Step according to present embodiment repeats twice again, obtains three batches membrane electrode assembly altogether.Different batches freeze drying-template is prepared membrane electrode assembly carries out performance comparison and can know; 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 help actual through engineering approaches or suitability for industrialized production.
The above; Being merely preferred embodiment of the present invention, is not to any formal and substantial restriction of the present invention, should be understood that; For those skilled in the art; Under the prerequisite that does not break away from the inventive method, also can make some improvement and replenish, these improvement and replenish and also should be regarded as protection scope of the present invention.Allly be familiar with the professional and technical personnel, under the situation that does not break away from the spirit and scope of the present invention, the technology contents that is disclosed more than capable of using and a little change of making, modify the equivalent variations with differentiation, be equivalent embodiment of the present invention; Simultaneously, the change of any equivalent variations that all foundations essence technology of the present invention is done the foregoing description, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (14)
1. the preparation method of a DMFC membrane electrode assembly 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 that step (1) obtains, add Nafion solution; Make in the Nafion solution that the weight ratio of carbon carrier is (0.3～1.4) in the Nafion resin and carbon supported noble metal catalyst: 1; Ultrasonicly be heated to 60～80 ℃, obtain catalyst slurry after ultrasonic;
(3) catalyst slurry that step (2) is obtained adopts liquid nitrogen frozen, makes catalyst slurry be frozen into solid;
(4) solid that step (3) is obtained freeze drying under freezing-condition of vacuumizing obtains the solid after the freeze drying;
After feeding nitrogen, takes out the drying bottle that (5) will fill the solid after the freeze drying; Obtain the dry catalyst and the uniform powder of Nafion resin, the uniform powder of the catalyst of said drying and Nafion resin is the dry cathod catalyst and uniform powder or the anode catalyst of drying and the uniform powder of Nafion resin of Nafion resin;
The uniform powder of the cathod catalyst of the drying that (6) step (5) is obtained and the uniform powder of Nafion resin and dry anode catalyst and Nafion resin is put into respectively and has on the Nafion film that frame protects; And evenly disperse respectively; The catalysis tunic that obtains dry-pressing behind the frame is removed in respectively compacting; Said catalysis tunic is the Nafion rete between wherein, and a side of Nafion rete is a cathode catalysis layer, and opposite side is an anode catalyst layer;
(7) gas diffusion layers is placed on the both sides of the catalysis tunic of dry-pressing respectively, 130-145 ℃ down and pressure be 75-115kgcm
-2Following hot pressing 3-5 minute, obtain said DMFC membrane electrode assembly;
Perhaps,
The cathod catalyst that (6-2) step (5) is obtained is put on the gas diffusion layers that has the frame protection with the uniform powder of Nafion resin, evenly dispersion, and the cathode diffusion electrode that obtains containing cathode catalysis layer behind the frame is removed in compacting; The uniform powder of anode catalyst and Nafion resin is put on the gas diffusion layers that has the frame protection, evenly disperses, the anode diffusion electrode that obtains containing the anode Catalytic Layer behind the frame is removed in compacting;
(7-2) cathode diffusion electrode and anode diffusion electrode are placed on the both sides of Nafion film respectively, and gas diffusion layers is away from the Nafion film, 130-145 ℃ down and pressure be 75-115kgcm
-2Following hot pressing 3-5 minute, obtain said DMFC membrane electrode assembly.
2. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, in the step (1), said carbon supported noble metal cathod catalyst is selected from Pt/C; Said carbon supported noble metal anode catalyst is selected from PtRu/C.
3. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, in the step (1), the volume ratio of deionized water and isopropyl alcohol is 20% ~ 80%.
4. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, in the step (2), the quality percentage composition of Nafion resin is 5wt%-20wt% in the Nafion solution that is added.
5. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, in the step (2), in the step (2), the ultrasonic time is 2-4 hour.
6. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, in the step (2), in the step (3), the freezing time is 10-20 minute.
7. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, in the step (4), said freezing temperature is-60～-15 ℃; The cryodesiccated time is 12-24 hour.
8. the preparation method of DMFC membrane electrode assembly as claimed in claim 1 is characterized in that, the carrying capacity of noble metal catalyst is 0.5～4mg/cm in the cathode catalysis layer in step (6) and the step (6-2)
2The carrying capacity of noble metal catalyst is 0.5～4mg/cm in the anode catalyst layer
2
9. the preparation method of DMFC membrane electrode assembly as claimed in claim 1; It is characterized in that the gas diffusion layers in step (7) and the step (6-2) is selected from carbon fiber paper TGPH-060, carbon fiber paper TGPH-030, GDL 24BC carbon fiber paper, GDL 25BC carbon fiber paper and GDL34BC carbon fiber paper.
10. the preparation method of DMFC membrane electrode assembly as claimed in claim 1; It is characterized in that; The DMFC membrane electrode assembly that obtains in step (7) and the step (7-2), its intermediate layer is the Nafion rete, a side of Nafion rete is a cathode catalysis layer; Opposite side is an anode catalyst layer, and the outside of cathode catalysis layer and anode catalyst layer is gas diffusion layers.
11. a DMFC membrane electrode assembly is for the preparation method according to each described DMFC membrane electrode assembly of claim 1-10 makes.
12. a monomer DMFC is characterized in that, said monomer DMFC comprises the described DMFC membrane electrode assembly of claim 11.
13. a DMFC group comprises the described monomer DMFC of a plurality of claims 12.
14. the application of DMFC membrane electrode assembly as claimed in claim 11 in electro-catalysis fuel cell and Proton Exchange Membrane Fuel Cells.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716333A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode, and production method and application thereof |
| 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 |
| CN106410246A (en) * | 2016-11-15 | 2017-02-15 | 浙江大学 | Preparation method of 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 |
| CN113921831A (en) * | 2021-09-22 | 2022-01-11 | 一汽解放汽车有限公司 | Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1971982A (en) * | 2005-11-26 | 2007-05-30 | 三星Sdi株式会社 | Anode for fuel cell, manufacturing method thereof, and fuel cell including the same |
| 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 |
-
2012
- 2012-06-07 CN CN201210187091.5A patent/CN102683725B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1971982A (en) * | 2005-11-26 | 2007-05-30 | 三星Sdi株式会社 | Anode for fuel cell, manufacturing method thereof, and fuel cell including the same |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716333A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode, and production method and application thereof |
| CN104716333B (en) * | 2013-12-15 | 2017-05-24 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode, and production method and application thereof |
| 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 |
| CN106410246A (en) * | 2016-11-15 | 2017-02-15 | 浙江大学 | Preparation method of alkaline anion-exchange membrane for fuel cell |
| 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 |
| CN113921831A (en) * | 2021-09-22 | 2022-01-11 | 一汽解放汽车有限公司 | Electrode catalyst slurry, method for producing the same, catalyst coated membrane, and fuel cell |
| CN116581308A (en) * | 2023-07-12 | 2023-08-11 | 苏州氢澜科技有限公司 | Dry membrane electrode preparation method of membrane 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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