CN101777654A - Fuel cell composite catalyst, high-durability membrane electrode and preparation method - Google Patents
Fuel cell composite catalyst, high-durability membrane electrode and preparation method Download PDFInfo
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Abstract
The invention relates to fuel cell composite catalyst, a high-durability membrane electrode and a preparation method, and is characterized in that porous materials with high specific surface area and high adsorption characteristics are added in the catalyst. The weight percent of the porous materials in the catalyst is 0.01-10 percent. The porous materials are palygorskite-sepiolite mineral fiber, montmorillonite, kieselguhr, active carbon, molecular sieve and silica gel. Different from the background technology, the porous adsorbing materials are added in the traditional catalyst and have the functions that migratory catalyst ions or particles can be adsorbed and catalyst activity reduction caused by catalyst loss can be alleviated; CO, NH3 or sulfide can be adsorbed, the toxic effect on the catalyst is reduced and the work efficiency of the catalyst is improved; and the porous materials can adsorb impurities such as metal ions produced during cell operation, the impurities are prevented from attacking a proton exchange membrane in a membrane electrode and the service life of the proton exchange membrane is improved.
Description
Technical field
The present invention relates to a kind of catalyst, particularly be applied to the catalyst of fuel cell, be characterized in being doped with in the catalyst porous adsorbing material.The invention still further relates to this kind Preparation of catalysts method and use the high-performance of this kind Preparation of Catalyst, the membrane electrode of high-durability.
Background technology
Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) be the energy conversion device that a kind of chemical energy that will be stored in the fuel is converted into electric energy, have that environmental friendliness, energy conversion efficiency height, life-span are long, characteristics such as startup fast under the room temperature, become one of research focus of new energy field.
The performance of catalyst and proton exchange membrane and life-span are one of most important indexs that influences fuel battery performance and life-span.Because fuel cell is in running, the running environment very severe of catalyst and film can cause dissolving, migration and the loss of catalyst granules, reduces catalyst performance and durability.In addition, the foreign gas in fuel and the oxidant such as CO, SO
2, NH
3Have poisoning effect Deng to catalyst, reduce the performance of catalyst.And the foreign metal ion such as the Fe that produce in the battery operation process
2+, Cr
3+, Cu
2+Deng attacking to keys such as the C-C in the resin material in the film, C-F, destroy the structure of film, cause the inefficacy of film.
Patent CN1917261A proposes to utilize conductivity ceramics to prepare noble metal catalyst as catalyst carrier.Compare with the conventional carbon carrier, conductivity ceramics possesses good chemical stability and excellent corrosion resistance, and the various holes in conductivity ceramics surface are few, and the noble metal catalyst particulate can be anchored on carrier surface.Patent CN1917260A utilizes proton superpolymer modified nanometer noble metal microparticles, has improved the adhesion between noble metal and carrier, fine particle of noble metal grappling and carrier surface can be improved catalyst utilization.Patent US2008/003476A1 proposes to add NH in noble metal catalyst
4I, NH
4Cl, NH
4Materials such as Br are to suppress growing up and dissolving loss of noble metal.But above several method all can't slow down the attack of foreign metal ion pair proton exchange membrane.Patent US2008/0070094 A1 utilizes hydrophilic molecular sieve to replace conventional carbon carrier as catalyst carrier, and molecular sieve can also replace proton superpolymer and play the effect of leading proton, utilize the membrane electrode of this molecular sieve supported Preparation of Catalyst not only to strengthen water retention property but also improved chemical stability, but the proton performance of leading of molecular sieve is compared and is still had big gap with proton superpolymer.
The present invention is intended to by add the porous material with high-specific surface area, high adsorption in catalyst.This porous material can adsorb the catalyst ion or the particle of migration, slows down the catalytic activity that causes because of catalyst loss and descends; CO absorption, NH
3Or sulfide, reduce its poisoning effect to catalyst, improve the operating efficiency of catalyst; And this porous material can adsorb the impurity such as metal ion that produce in the battery operation process, prevents the attack of impurity to the proton exchange membrane in the membrane electrode, thereby improves the useful life of proton exchange membrane.
The pertinent literature report that the type catalyst and membrane electrode are not arranged at present as yet.
Summary of the invention
The purpose of this invention is to provide a kind of composite catalyst and preparation method who is applied to fuel cell, feature is to comprise the porous adsorbing material pond in the described composite catalyst.Another object of the present invention provides membrane electrode and the preparation method who comprises described composite catalyst.
The present invention seeks to realize with following technical proposals.
A kind of fuel cell composite catalyst, it is characterized in that, added porous material in the catalyst with high-specific surface area, high characterization of adsorption, the mass fraction of this porous material in catalyst is 0.01%～10%, and described porous material is palygorskite-sepiolite group mineral fibres, montmorillonite, diatomite, active carbon, molecular sieve or silica gel.
In the technical scheme of the present invention, described palygorskite-sepiolite group mineral fibres is palygorskite (attapulgite) or sepiolite.
Described molecular sieve is natural zeolite, carbon molecular sieve or artificial synthetic zeolite.
Described natural zeolite is modenite or clinoptilolite, and the artificial synthetic zeolite is 3A type molecular sieve, 4A type molecular sieve, 5A type molecular sieve, 10X type molecular sieve, 13X type molecular sieve, sodium Y zeolite or calcium Y zeolite.
Catalyst of the present invention is meant Pt, Pd, Ru, Rh, Ir or Os noble metal, bianry alloy PtPd, PtRu, PtRh, PtIr or the PtOs of Pt and Pd, Ru, Rh, Ir or Os; The alloy of platinum and other metals is meant the bianry alloy NM that Pt, Pd, Ru, Rh, Ir or Os noble metal and Fe, Cr, Ni, Co, Au or Bi form, and N is Pt, Pd, Ru, Rh, Ir or Os, and M is Fe, Cr, Ni, Co, Au or Bi; The ternary alloy three-partalloy NM that Pt, Pd, Ru, Rh, Ir or Os noble metal and Fe, Cr, Ni, Co form
1M
2, the definition of N is with aforementioned, M
1, M
2Be the composition of any two metallic elements among Fe, Cr, Ni and the Co, as FeCo etc., wherein Bi, Fe, Cr, Ni and Co are base metal.
The used catalyst carrier of the present invention is carbon carrier, ceramic monolith, nanometer SiO
2Or nano-TiO
2
Carbon carrier of the present invention is nanometer carbon black, nano-graphite ball, carbon nano-fiber, CNT (carbon nano-tube) or mesoporous carbon microballoon, described nanometer carbon black and nano-graphite ball, its particle grain size is 10～100 nanometers, described Nano carbon fibers peacekeeping CNT (carbon nano-tube), its diameter is 2～200 nanometers, length is 100～10000 nanometers, and the pore size of described mesoporous carbon microballoon is the 2-50 nanometer.
CNT (carbon nano-tube) of the present invention is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Ceramic monolith of the present invention is TiSi
2, TiB
2, TiN, TiC, TiO
2, SiC, PbTiO
3, Ti
3SiC, BaPbO
3, LaCrO
3, TiC/Si
3N
4Or TiAl/TiB
2, its particle diameter is 10～200 nanometers.
Proton exchange membrane of the present invention is meant the perfluorinated sulfonic acid proton exchange membrane with sulfonic acid group, and partially fluorinated proton exchange membrane is as the BAM3G film of Ballard company production; The proton exchange resins casting film of nonfluorinated is as SPSF resinoid, sulfonated polyphenyl sulfide resin, sulfonated polyphenyl and imidazoles, sulfonation polyphosphazene, sulfonated polyimide resin, sulfonated polystyrene ion exchange resin or sulfonated polyether-ether-ketone resin casting film.
Membrane electrode of the present invention (membrane electrode assembly, MEA) according to two kinds of the different divisions of catalyst layer and other combination of components mode, a kind of is with gas diffusion layers electrode (the gas diffusion layer electrode of catalyst coated in the gas diffusion layers surface preparation, GDE) membrane electrode that obtains, the present invention is referred to as GDE-MEA, another kind is that catalyst is coated in proton exchange membrane both sides (catalyst coated membrane, CCM) membrane electrode of Huo Deing, the present invention is referred to as CCM-MEA.
The preparation method of composite catalyst of the present invention evenly spreads to porous adsorbing material in the catalyst, makes composite catalyst.Detailed process is:
The general catalyst of fuel cell is scattered in deionized water or alcohol or the alcohol solution, add porous adsorbing material, wherein the mass ratio of porous adsorbing material and general catalyst is 0.01～10: 100, after utilizing methods such as ultrasonic, high-speed stirred fully to disperse, in vacuum or atmosphere of inert gases,, make the composite catalyst that contains porous adsorbing material with 50～150 ℃ of temperature oven dry.
Alcohol of the present invention is any in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol and the polyalcohol, and polyalcohol is ethylene glycol, glycerol or butanediol; Alcohol solution is the mixed solution of alcohol and water, and wherein Chun volume fraction is 5%～95%.
Membrane electrode of the present invention is a kind of fuel cell membrane electrode, it is characterized in that, this membrane electrode contains described fuel cell composite catalyst.
Membrane electrode preparation method of the present invention is that the material that contains composite catalyst, proton exchange resins, solvent is made slip (slurry) or prepared Chinese ink (ink), be coated in the gaseous diffusion laminar surface and make the gas diffusion layers electrode, then with gas diffusion layers electrode and proton exchange membrane hot pressing, obtain membrane electrode, i.e. GDE-MEA; Or slip or prepared Chinese ink be coated in the proton exchange membrane both sides, and to make fuel cell chip, or be called CCM (catalyst coated membrane), and then gas diffusion layers carried out cold and hot pressure with CCM or contact, the membrane electrode of acquisition is CCM-MEA.Concrete preparation process is:
1) the above-mentioned composite catalyst that contains porous adsorbing material is prepared into slip, it is composite catalyst that the mass fraction of the various compositions of slip closes: proton exchange resins: solvent=5～1: 1: 5～30, and described solvent is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, 1-methoxyl group 2-propyl alcohol (MOP); Ether, benzinum; Ethyl acetate or acetone;
2) the fuel cell composite catalyst slip with step 1 preparation is coated on through pretreated gaseous diffusion laminar surface, and 80-100 ℃ of following vacuumize, makes the gas diffusion layers electrode;
The preprocess method of wherein said gas diffusion layers is, carbon paper is immersed in the polytetrafluoroethylene water-repelling agent, time is 5～10 minutes, and under 340-350 ℃, calcined 20-30 minute, the content 20wt%-30wt% of polytetrafluoroethylene water-repelling agent afterwards, applies the composite layer that one deck is made up of polytetrafluoroethylene and conductive carbon black in the one side again, wherein polytetrafluoroethylene content is 20wt%-30wt%, calcines 20-30 minute aftershaping down through 340-350 ℃;
3) with the gas diffusion layers electrode and the proton exchange membrane hot pressing of step 2 preparation, obtain fuel cell membrane electrode, the pressure 1～4MPa of hot pressing, temperature 90-120 ℃, 60～120 seconds time;
Or the composite catalyst slip of step 1 preparation is coated in the both sides of proton exchange membrane, make fuel cell chip, afterwards, carry out hot pressing or cold joint touches again with through pretreated gas diffusion layers, obtain fuel cell membrane electrode, pressure 1～the 4MPa of hot pressing, temperature 90-120 ℃, 60～120 seconds time.
The composite catalyst of preparation is assembled into monocell, and it is as follows to carry out the electric performance test test process:
Monocell assembling and test; The employing graphite cake is a collector plate, has parallel slot in a side, and end plate is gold-plated corrosion resistant plate.Membrane electrode, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is:
(1) direct hydrogen fuel cell (PEMFC): H
2/ air, air back pressure are 0; Anode humidification, humidification degree are 0～100%; The monocell working temperature is 60～80 ℃, and the humidification temperature is 60～75 ℃; In the anodic gas.
(2) direct methanol fuel cell (DMFC): the anode methanol concentration is 2 moles, and flow is 5 ml/min, and negative electrode is an air, and back pressure is 0.
Compare with existing background technology, composite catalyst of the present invention has following advantage:
1, employing has adsorbing porous material, has stopped the migration of catalyst, has slowed down the loss of catalyst, makes the durability of catalyst be improved;
2, porous adsorbing material energy CO absorption, NH
3Or sulfide, reduce its poisoning effect to catalyst, the operating efficiency of catalyst is improved;
3, porous adsorbing material has stoped the metal ion that produces in the battery operation process and other impurity to the migration of proton exchange membrane, prevents metal ion and other impurity destruction to proton exchange membrane, and life-span of proton exchange membrane is improved.
Test shows adopts composite catalyst of the present invention, fuel cell membrane electrode life-span can improve more than 10%.
Description of drawings
Fig. 1 Pt ion wastage
Among the figure: 1, normal film electrode, 2, add the membrane electrode of porous adsorbing material.
Figure 22 monocell performance test in 00 hour
Among the figure: 1, normal film electrode, 2, add the membrane electrode of porous adsorbing material.
Embodiment
Below by embodiment in detail the present invention is described in detail.
1, contains the preparation of palygorskite composite catalyst
Get 0.95gPt/C and join in 50 ml deionized water with the 0.05g palygorskite, sonicated 20 minutes leaves standstill oven dry in 5 hours with even mixed palygorskite/catalyst for following 80 ℃ in vacuum, makes the composite catalyst that contains the 5wt% palygorskite;
2, the preparation of catalyst slurry
According to composite catalyst: proton exchange resins: the ratio of solvent=5: 1: 30 prepares catalyst slurry, and wherein proton exchange resins is
Resin solution (E.I.Du Pont Company's production), solvent is a methyl alcohol;
3, the preliminary treatment of gas diffusion layers
Carbon paper be impregnated in the polytetrafluoroethylene water-repelling agent to be handled 5 minutes, and under 350 ℃, calcined 20 minutes, the content 20wt% of polytetrafluoroethylene water-repelling agent, afterwards, apply the composite layer that one deck is made up of polytetrafluoroethylene and conductive carbon black particle in the one side again, wherein polytetrafluoroethylene content is 30wt%, calcines 30 minutes aftershapings down, the formation water management layer through 350 ℃;
4, the preparation of membrane electrode
Catalyst slurry is applied to a side of passing through pretreated gas diffusion layers, and 100 ℃ of following vacuumizes make the gas diffusion layers electrode;
With perfluorinated sulfonic acid proton exchange tree film (NRE212CS,
Du pont company is produced) place hot pressing between two gas diffusion layers electrodes, wherein, catalyst layer contacts with proton exchange membrane, the pressure 2MPa of hot pressing, 120 ℃ of temperature, 90 seconds time, the catalyst loading of membrane electrode is 0.60mg/cm
2
5, monocell assembling and test
The membrane electrode and the component groups such as graphite collector plate, gold-plated end plate and teflin ring of preparation are dressed up monocell.The monocell operating condition is: hydrogen/sky, and normal pressure, the equal humidification of cathode and anode, adding humidity is 100%, working temperature is 70 ℃.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 15%.
1, contains the preparation of sepiolite composite catalyst
Getting 0.93gPtPd/SCNTs (SCNTs is a Single Walled Carbon Nanotube) joins in 50 ml deionized water with the 0.07g sepiolite, sonicated 20 minutes, even mixed sepiolite/catalyst is left standstill oven dry in 10 hours for following 80 ℃ in vacuum, make the composite catalyst that contains 7wt% sepiolite slope;
2, the preparation of catalyst slurry
According to composite catalyst: proton exchange resins: the ratio of solvent=2: 1: 20 prepares catalyst slurry, and wherein proton exchange resins is
Resin solution (E.I.Du Pont Company's production), solvent is an ethanol;
3, the preliminary treatment of gas diffusion layers
Carbon paper be impregnated in the polytetrafluoroethylene water-repelling agent to be handled 10 minutes, and under 340 ℃, calcined 20 minutes, the content 25wt% of polytetrafluoroethylene water-repelling agent, afterwards, apply the composite layer that one deck is made up of polytetrafluoroethylene and conductive carbon black particle in the one side again, wherein polytetrafluoroethylene content is 30wt%, calcines 30 minutes aftershapings down, the formation water management layer through 350 ℃;
4, the preparation of membrane electrode
Identical with embodiment 1, just the pressure of hot pressing is 3MPa, 110 ℃ of temperature, and the time is 90 seconds;
5, monocell assembling and test
The monocell assembling is identical with embodiment 1.
Monocell test operation condition is: hydrogen/sky, and normal pressure, the equal humidification of cathode and anode, adding humidity is 70%, and humidification temperature is 75 ℃, and working temperature is 65 ℃.In anode hydrogen gas, added the CO of 100ppm.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell has improved 5 times to the tolerance of CO, and the monocell durability has improved 13%.
Embodiment 3
1, contains the preparation of montmorillonite composite catalyst
Get 0.94gPtRuNi/SiO
2Join in 50 ml deionized water sonicated 20 minutes with the 0.06gXK high-purity montmorillonite.Even mixed montmorillonite/catalyst is left standstill oven dry in 8 hours for following 80 ℃ in vacuum, make the composite catalyst that contains the 6wt% montmorillonite;
2, the preparation of catalyst slurry
According to the composite catalyst proton exchange resins: the ratio of solvent=3: 1: 5 prepares catalyst slurry, and wherein proton exchange resins is
Resin solution (du pont company production), solvent is an ethylene glycol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 1;
4, the preparation of membrane electrode
With the composite catalyst slip be coated in the perfluorinated sulfonic acid proton exchange membrane (NRE 212CS,
Du pont company production) both sides make fuel cell chip, afterwards, carry out hot pressing again with through pretreated gas diffusion layers, and the pressure of hot pressing is 3MPa, 100 ℃ of temperature, 100 seconds time;
5, monocell assembling and test:
The monocell assembling is identical with embodiment 1.
The monocell test condition: the anode methanol concentration is 2 moles, and flow is 5 ml/min, and negative electrode is an air, and back pressure is 0.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 12.5%.
Embodiment 4
1, contains the preparation of tripolite composite catalyst
Getting the IrFe/CF (CF is a carbon nano-fiber) that the 0.97g carbon fiber supports joins in 50 ml deionized water with 0.03g diatomite (Celite 545), sonicated 20 minutes, even mixed diatomite/catalyst is left standstill oven dry in 8 hours for following 80 ℃ in vacuum, make and contain the diatomaceous composite catalyst of 6wt%;
2, the preparation of catalyst slurry
According to composite catalyst: proton exchange resins: the ratio of solvent=3: 1: 25 prepares catalyst slurry, and wherein proton exchange resins is sulfonated polyphenyl and imidazoles resin solution (self-control), and solvent is different ethanol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 1.
4, the preparation of membrane electrode
Identical with embodiment 1, just the proton exchange membrane that adopts is sulfonated polyphenyl and imidazoles resin casting film (self-control, 100 microns of thickness);
5, monocell assembling and test:
The monocell assembling is identical with embodiment 1.
Monocell test operation condition is: hydrogen/sky, and normal pressure, the equal humidification of cathode and anode, adding humidity is 70%, and humidification temperature is 65 ℃, and working temperature is 65 ℃.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 13.5%.
Embodiment 5
1, contains the preparation of active carbon composite catalyst
Get 0.98gOsAu/TiO
2With 0.02g active carbon (JL-1600T, specific area 1500m
2/ g) joining together in 50 ml deionized water, sonicated 30 minutes leaves standstill oven dry in 6 hours with even mixed active carbon/catalyst for following 80 ℃ in vacuum, makes the composite catalyst that contains the 2wt% active carbon;
2, the preparation of catalyst slurry
According to composite catalyst: proton exchange resins: the ratio of solvent=4: 1: 15 prepares catalyst slurry, and wherein proton exchange resins is sulfonated polyether-ether-ketone resin solution (self-control), and solvent is different ethanol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 2;
4, the preparation of membrane electrode
Identical with embodiment 2, just the proton exchange membrane that adopts is sulfonated polyether-ether-ketone resin casting film (self-control, 80 microns of a thickness);
5, monocell assembling and test
The monocell assembling is identical with embodiment 1.
Monocell test operation condition: hydrogen/sky, normal pressure, the equal humidification of cathode and anode, adding humidity is 30%, and humidification temperature is 60 ℃, and working temperature is 80 ℃.Added the H of 150ppm in the anode hydrogen gas
2S.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell is to H
2The tolerance of S has improved 4 times, and the monocell durability has improved 20%.
Embodiment 6
1, contains the preparation of modenite composite catalyst
Getting the PtRhNi/C catalyst that 0.98g nano-graphite ball supports joins in 50 ml deionized water with the 0.02g modenite, sonicated 20 minutes, even mixed modenite/catalyst is left standstill oven dry in 6 hours for following 80 ℃ in vacuum, make the composite catalyst that contains the 2wt% modenite;
2, the preparation of catalyst slurry
According to composite catalyst: proton exchange resins: the ratio of solvent=5: 1: 10 prepares catalyst slurry, and wherein proton exchange resins is sulfonated polyimide resin solution (self-control), and solvent is a propyl alcohol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 2;
4, the preparation of membrane electrode
Identical with embodiment 2, just the proton exchange membrane that adopts is sulfonated polyimide resin casting film (self-control, 80 microns of a thickness);
5, monocell assembling and test
Identical with embodiment 2, just in anode hydrogen gas, added the NH of 120ppm
3
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell is to NH
3Tolerance improved 2 times, the monocell durability has improved 18%.
Embodiment 7
1, contains the preparation of clinoptilolite composite catalyst
Get 0.95gPtAu/TiSi
2Join in 50 ml deionized water with the 0.05g clinoptilolite, sonicated 20 minutes leaves standstill oven dry in 7 hours with even mixed clinoptilolite/catalyst for following 80 ℃ in vacuum, makes the composite catalyst that contains the 5wt% clinoptilolite;
2, the preparation of catalyst slurry
Identical with embodiment 2, just wherein proton exchange resins is sulfonated polyimide resin solution (self-control), and solvent is a propyl alcohol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 2;
4, the preparation of membrane electrode
Identical with embodiment 3;
5, monocell assembling and test
Identical with embodiment 3.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 17%.
Embodiment 8
1, the preparation of carbon-containing molecules sieve composite catalyst
Getting 0.95gRuCo/TiN joins in 50 ml deionized water with 0.05g185 type carbon molecular sieve, sonicated 20 minutes, even mixed carbon molecular sieve/catalyst is left standstill oven dry in 7 hours for following 80 ℃ in vacuum, make the composite catalyst that contains the 5wt% carbon molecular sieve;
2, the preparation of catalyst slurry
Identical with embodiment 1, just wherein proton exchange resins is a sulfonated polyphenyl sulfide resin solution (self-control), and solvent is a propyl alcohol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 1;
4, the preparation of membrane electrode
Identical with embodiment 3, just wherein proton exchange membrane is sulfonated polyphenyl sulfide resin casting film (self-control, 100 microns of a thickness);
5, monocell assembling and test
Identical with embodiment 3.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 16%.
Embodiment 9
1, contains the preparation of 3A type molecular sieve composite catalyst
Getting 0.91gPt joins in 50 ml deionized water with 0.09g 3A type molecular sieve, sonicated 30 minutes, even mixed 3A type molecular sieve/catalyst is left standstill oven dry in 10 hours for following 80 ℃ in vacuum, make the composite catalyst that contains 9wt%3A type molecular sieve;
2, the preparation of catalyst slurry
Identical with embodiment 7, just solvent is a glycerol;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 3;
4, the preparation of membrane electrode
Identical with embodiment 4;
5, monocell assembling and test
Identical with embodiment 6.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell is to NH
3Tolerance improved 3 times, the monocell durability has improved 16%.
1, contains the preparation of 4A type molecular sieve composite catalyst
Identical with embodiment 9, just catalyst is PtPd, and porous adsorbing material is a 4A type molecular sieve;
2, the preparation of catalyst slurry
Identical with embodiment 3, just proton exchange membrane is a sulfonation polyphosphazene resin (self-control), and solvent is MOP;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 2;
4, the preparation of membrane electrode
Identical with embodiment 5, just proton exchange membrane is sulfonation polyphosphazene resin casting film (self-control, 50 microns of a thickness);
5, monocell assembling and test
Identical with embodiment 6.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell is to NH
3Tolerance improved 5 times, the monocell durability has improved 15%.
Embodiment 11
1, contains 5A type molecular sieve and close Preparation of catalysts
Identical with embodiment 5, just catalyst is Pt/SiC, and porous adsorbing material is a 5A type molecular sieve;
2, the preparation of catalyst slurry
Identical with embodiment 5, just proton exchange membrane is sulfonated polystyrene ion exchange resin (self-control), and solvent is MOP;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 2;
4, the preparation of membrane electrode
Identical with embodiment 2, just proton exchange membrane is sulfonated polystyrene ion exchange resin casting film (self-control, 60 microns of a thickness);
5, monocell assembling and test
Identical with embodiment 5.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell is to H
2The tolerance of S has improved 2 times, and the monocell durability has improved 15%.
Embodiment 12
1, contains the preparation of 10X type molecular sieve composite catalyst
Identical with embodiment 9, just catalyst is Pt/MCNTs (MCNTs is a multi-walled carbon nano-tubes), and porous adsorbing material is a 10X type molecular sieve;
2, the preparation of catalyst slurry
Identical with embodiment 1, just proton exchange resins is SPSF resinoid (self-control), and solvent is an ether;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 1;
4, the preparation of membrane electrode
Identical with embodiment 1, just proton exchange membrane is SPSF resinoid casting film (self-control, 80 microns of a thickness);
5, monocell assembling and test
Identical with embodiment 2.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell has improved 3 times to the tolerance of CO, and the monocell durability has improved 18%.
Embodiment 13
1, contains the preparation of 13X type molecular sieve composite catalyst
Identical with embodiment 5, just catalyst is PtPd/C, and porous adsorbing material is a 13X type molecular sieve;
2, the preparation of catalyst slurry
Identical with embodiment 1, just solvent is a benzinum;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 1;
4, the preparation of membrane electrode
Identical with embodiment 10;
5, monocell assembling and test
Identical with embodiment 2.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, monocell has improved 5 times to the tolerance of CO, and the monocell durability has improved 18%.
Embodiment 14
1, contains the preparation of sodium Y zeolite composite catalyst
Identical with embodiment 2, just porous adsorbing material is the sodium Y zeolite;
2, the preparation of catalyst slurry
Identical with embodiment 1, just solvent is an ethyl acetate;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 1;
4, the preparation of membrane electrode
Identical with embodiment 3;
5, monocell assembling and test
Identical with embodiment 3.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 12%.
Embodiment 15
1, the preparation of calcic Y zeolite composite catalyst
Identical with embodiment 6, just porous adsorbing material is the calcium Y zeolite;
2, the preparation of catalyst slurry
Identical with embodiment 1, just solvent is an acetone;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 3;
4, the preparation of membrane electrode
Identical with embodiment 1, just proton exchange membrane is
1135 films;
5, monocell assembling and test
Identical with embodiment 1.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 11%.
Embodiment 16
1, contains the preparation of silica gel composite catalyst
Identical with embodiment 6, just porous adsorbing material is a silica gel;
2, the preparation of catalyst slurry
Identical with embodiment 1;
3, the preliminary treatment of gas diffusion layers
Identical with embodiment 3;
4, the preparation of membrane electrode
Identical with embodiment 3, just proton exchange membrane is
1135 films;
5, monocell assembling and test
Identical with embodiment 3.
Test and showed that the discharge of catalyst stream vector and foreign metal ion obviously reduced in 200 hours, the monocell durability has improved 13%.
Claims (7)
1. fuel cell composite catalyst, it is characterized in that, added porous material in the catalyst with high-specific surface area, high characterization of adsorption, the mass fraction of this porous material in catalyst is 0.01%～10%, and described porous material is palygorskite-sepiolite group mineral fibres, montmorillonite, diatomite, active carbon, molecular sieve or silica gel.
2. fuel cell composite catalyst as claimed in claim 1 is characterized in that, described palygorskite-sepiolite group mineral fibres is palygorskite or sepiolite.
3. fuel cell composite catalyst as claimed in claim 1 is characterized in that, described molecular sieve is natural zeolite, carbon molecular sieve or artificial synthetic zeolite.
4. fuel cell composite catalyst as claimed in claim 3, it is characterized in that, described natural zeolite is modenite or clinoptilolite, and the artificial synthetic zeolite is 3A type molecular sieve, 4A type molecular sieve, 5A type molecular sieve, 10X type molecular sieve, 13X type molecular sieve, sodium Y zeolite or calcium Y zeolite.
5. the preparation method of the described fuel cell composite catalyst of claim 1 is characterized in that, preparation process is:
The general catalyst of fuel cell is scattered in deionized water or alcohol or the alcohol solution, after the stirring, add porous adsorbing material, wherein the mass ratio of porous adsorbing material and general catalyst is 0.01～10: 100, fully after dispersion and the oven dry, make the composite catalyst that contains porous adsorbing material.
6. a fuel cell membrane electrode is characterized in that, this membrane electrode contains the described fuel cell composite catalyst of claim 1.
7. the preparation method of the described a kind of fuel cell membrane electrode of claim 6 is characterized in that, the preparation method is:
1) the described composite catalyst of claim 1 is prepared into slip, it is composite catalyst that the mass fraction of the various compositions of slip closes: proton exchange resins: solvent=5～1: 1: 5～30, and wherein said solvent is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, 1-methoxyl group 2-propyl alcohol (MOP), ether, benzinum, ethyl acetate or acetone;
2) the fuel cell composite catalyst slip with step 1 preparation is coated on through pretreated gaseous diffusion laminar surface, and 80-100 ℃ of following vacuumize, makes the gas diffusion layers electrode;
The preprocess method of wherein said gas diffusion layers is, carbon paper is immersed in the polytetrafluoroethylene water-repelling agent, time is 5～10 minutes, and under 340-350 ℃, calcined 20-30 minute, the content 20wt%-30wt% of polytetrafluoroethylene water-repelling agent afterwards, applies the composite layer that one deck is made up of polytetrafluoroethylene and conductive carbon black in the one side again, wherein polytetrafluoroethylene content is 20wt%-30wt%, calcines 20-30 minute aftershaping down through 340-350 ℃;
3) with the gas diffusion layers electrode and the proton exchange membrane hot pressing of step 2 preparation, obtain fuel cell membrane electrode, the pressure 1～4MPa of hot pressing, temperature 90-120 ℃, 60～120 seconds time;
Or the composite catalyst slip of step 1 preparation is coated in the both sides of proton exchange membrane, make fuel cell chip, afterwards, carry out hot pressing or cold joint touches again with through pretreated gas diffusion layers, obtain fuel cell membrane electrode, pressure 1～the 4MPa of hot pressing, temperature 90-120 ℃, 60～120 seconds time.
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| CN102723509A (en) * | 2012-06-15 | 2012-10-10 | 武汉理工大学 | Nanofiber array structure based three-dimensional proton conductor based on and membrane electrode and preparation thereof |
| WO2012003954A3 (en) * | 2010-07-09 | 2012-10-18 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V. | New phosphate- and silicate-based electrode materials, more particularly for lithium ion batteries and lithium capacitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012003954A3 (en) * | 2010-07-09 | 2012-10-18 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V. | New phosphate- and silicate-based electrode materials, more particularly for lithium ion batteries and lithium capacitors |
| US9196902B2 (en) | 2010-07-09 | 2015-11-24 | Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E. V. | Phosphate- and silicate-based electrode materials, more particularly for lithium ion batteries and lithium capacitors |
| CN102723509A (en) * | 2012-06-15 | 2012-10-10 | 武汉理工大学 | Nanofiber array structure based three-dimensional proton conductor based on and membrane electrode and preparation thereof |
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