CN1881667A - Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell - Google Patents
Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell Download PDFInfo
- Publication number
- CN1881667A CN1881667A CNA2005100467096A CN200510046709A CN1881667A CN 1881667 A CN1881667 A CN 1881667A CN A2005100467096 A CNA2005100467096 A CN A2005100467096A CN 200510046709 A CN200510046709 A CN 200510046709A CN 1881667 A CN1881667 A CN 1881667A
- Authority
- CN
- China
- Prior art keywords
- proton exchange
- membrane
- self
- humidifying
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a proton exchange film of fuel battery, especially providing a multilayer composite proton exchange film of self-increment wet fuel battery, wherein at one or two sides of dense base film, it arranges the functional film formed by carrier catalyst and macromolecule solid electrolyte. The invention has high compactness, high mechanical strength and low cost.
Description
Technical field
The present invention relates to the proton exchange membrane of fuel cell, specifically a kind of self-humidifying fuel cell (PTFE enhancing) multilayer composite proton exchange membrane and synthetic method.
Background technology
The use of fossil fuel causes a large amount of pollutant emissions, causes problem of environmental pollution, and the development of new clean energy resource has caused the great attention of countries in the world government and business circles.Proton Exchange Membrane Fuel Cells (PEMFC) is a kind ofly directly to change the chemical energy in fuel and the oxidant Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy into by electrochemical reaction, has high-energy conversion efficiency, advantages of environment protection.Fuel cell technology has entered demonstration phase at present.Yet, exist many obstacles in the fuel cell commercialization process: as infrastructure framework, hydrogen preparation and storage, cost, reliability, durability, operating flexibility etc.Fuel cell itself exists reliability and problems such as poor durability, cost height.Only depend on the fuel cell prior art, commercialization is very difficult to the propellant battery.Therefore, must carry out primary study to its critical material.
Proton exchange membrane is one of critical material of fuel cell, and its proton conducting needs water, and the water content of proton conductivity and film is almost linear.Therefore for high performance PEMFC, keep the sufficient water content of proton exchange membrane to seem very important.
Water transfer mode in Proton Exchange Membrane Fuel Cells has three kinds: follow proton electromigration water, negative electrode generate water under the concentration gradient effect by the back-diffusion water of negative electrode anode, negative electrode a little more than the pressure migration water under the barometric gradient effect of anodic gas.
The outer humidification auxiliary system humidification fuel and the reacting gas of conventional complexity are realized the humidification of proton exchange membrane, but increased fuel cell system complexity, improved cost and consumed a large amount of heat energy.Be with the fuel cell of outer humidification auxiliary system in running, to be prone to the water logging phenomenon, the outer humidification difficult problem of water freezing when existing external environment low temperature simultaneously.Therefore, exploratory development does not have outer humidification promptly from the self-humidifying fuel cell of humidification auxiliary system, with the complexity of simplified system, improves energy efficiency, reduces cost, and it is significant to promote the fuel cell commercialization.
No matter adopt the pre-humidifying technology of which kind of reacting gas, all can cause the quality and the volume of the complicated of battery system or increase battery system.Therefore optimal method is to utilize the generation water and the transmission characteristic of water in proton exchange membrane of cell reaction, realize film from humidification, guarantee the stability and safety operation of battery system.The thinking in this field is concentrated both ways at present: the one, adopt thin proton exchange membrane, and the counter-current flow of reaction gas realizes the stable operation of battery.The 2nd, utilize the Penetration Signature of the micro-reaction gas of film, make interpenetrative hydrogen, the compound generation water of oxidation, be the film humidification, reduce mixed potential simultaneously, improve open circuit voltage.
Patent and document about self-humidifying fuel cell are more, the method from humidification that realizes ionic exchange film for fuel cell can be classified as two classes: the one, utilize the concentration difference diffusion of water realize film from humidification, it is by designing suitable flow field, quickening negative electrode and generate the diffusion of water anode; The 2nd, H
2-O
2Compound from humidification, it is to introduce nanoscale Pt and hydrophilic oxide (not supporting Pt) in proton exchange membrane, and H interpenetrates
2, O
2Come humidification on the metallic catalyst surface through the chemical catalysis water generation reaction.
In United States Patent (USP) (U.S.5,472,799), adopt Nafion film sputter thin layer precious metals pt, and then casting last layer Nafion film, formation has the film that metal simple-substance is coated on intermediate structure, and this method has improved the open circuit voltage of fuel cell.But because sputtering method brings the complexity of film-forming method to be difficult to commercially produce.
Adopt in United States Patent (USP) (U.S.5,318,863 and U.S.5,242,764) that a certain amount of Nafion solution of spraying forms film on electrode, after be hot pressed into membrane electrode three-in-one (MEA).The water that negative electrode generates is used for humidification reacting gas and film.The shortcoming of this method is that the compactness of film is bad, and gas permeability is big.
Adopt the cross-flow of multichannel serpentine flow and reaction gas in the United States Patent (USP) (U.S.6,207,312), make the working off one's feeling vent one's spleen of the relative opposite side of a side entrance gas of film, rely on the concentration gradient effect of water to quicken the back-diffusion that negative electrode generates the water anode.The water concentration of going into implication is lower than the water concentration of working off one's feeling vent one's spleen.Operating procedure is simple, but battery performance is relatively poor, and commercial application value is not high.
In Chinese patent (CN 1181585C), adopt the Nafion solution that drips the supported catalyst that contains Pt on the voided polytetrafluoroethylene film surface, the preparation composite membrane.Catalyst is trapped in the inside of film, the interpenetrative H of chemical catalysis by porous PTFE
2, O
2Generate water and realize self-moistening function.Shortcoming is the distribution of the formation finite concentration gradient of supported catalyst Pt/C in film, and carrier carbon easily forms electrical short.And the open circuit voltage of battery is lower than 1.0V, fails to give full play to the effect that noble metal catalyst is eliminated mixed potential.Its battery performance is relatively poor.
Chinese patent (application number: 03140527.4), the blend solution casting film-forming that adopts sulfate resin and crystalline hydrate under high temperature, condition of high voltage, to dissolve.This film does not contain noble metal, the proton conductivity height of composite membrane, and controllable thickness is at 10～300 μ m.But there be separating of microfacies in organic membrane with the blend of inorganic particulate, easily causes the gas permeability of film big, and battery security is poor, and the open circuit voltage of its battery is lower than 1.0V.
At document (M.Watanabe, J.Electrochem.Soc, 143 (1996) 3847-3852; J.Electrochem.Soc, 145 (1998) 1137-1141; J.Phys.Chem.B, 102 (1998) 3129-3137) in, the employing chemical plating method forms the Pt of high dispersive or adopts nano level Pt and hydrophilic oxide and Nafion solution casting composite membrane in proton exchange membrane, make the H that penetrates into film
2, O
2Generate the water moistened membrane through chemical catalysis.Prevent that simultaneously hydrogen is penetrated into oxygen electrode and produces mixed potential, reach the purpose of the open circuit voltage that improves PEMFC.Adding hydrophilic oxide and absorb water when low current density, is to discharge water at high current density, to regulate the water balance in the film.But Pt chemical plating method complexity, the system film cycle is longer, and battery performance is relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of self-humidifying fuel cell with multilayer composite proton exchange membrane and synthetic method; The compactness of composite membrane is good, and mechanical strength is good, and simple to operate is to be suitable for the compound proton exchange membrane that self-humidifying fuel cell is used.
For achieving the above object, the technical solution used in the present invention is:
A kind of self-humidifying fuel cell multilayer composite proton exchange membrane adds the functional membrane of being made up of supported catalyst and polymer solid electrolyte in the one or both sides of the basilar memebrane of densification.
The mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～50: 1 in the described functional membrane, and polymer solid electrolyte can be sulfonated polyether-ether-ketone, SPSF or perfluorinated sulfonic resin etc.; The loading of the catalytic activity component of supported catalyst is 10
-5～1mg/cm
2The catalytic activity component is Pt, Au, Pd and/or Ag etc., and carrier is SiO
2, Al
2O
3, SiO
2-Al
2O
3, CeO
2, ZrO
2, TiO
2, one or more the compound in molecular sieve and the carbon; Basilar memebrane can be the polymer solid electrolyte homogeneous membrane or fills (or inlaying) porous with polymer solid electrolyte and strengthens film formed dense film; The porous reinforcing membrane can be porous Teflon (PTFE), porous Kynoar, porous polypropylene, porous polyethylene, porous polyimide or porous polysulfones etc., its thickness is 5～100 μ m, the aperture is 0.05～1 μ m, porosity is 60～95%, preferred thickness is 5～60 μ m, the aperture is 0.1～0.6 μ m, and porosity is 75～90%; Functional membrane thickness is 0.1～20 μ m; The load amount of the catalytic activity component of supported catalyst is preferably 10 in the functional membrane
-4～0.1mg/cm
2
Self-humidifying fuel cell is as follows with the synthetic method of multilayer composite proton exchange membrane:
1) polymer solid electrolyte is made polymer solid electrolyte solution with high boiling solvent dissolving back adding mid-boiling point or low boiling point solvent;
2) step 1) polymer solid electrolyte solution is prepared into the polymer solid electrolyte homogeneous membrane as basilar memebrane behind the solvent to the greatest extent by casting, spraying or casting method volatilization;
Or, became basilar memebrane behind the solvent flashing in 1～24 hour in 50～120 ℃ of heating at the top casting of porous reinforcing membrane, spraying or curtain coating step 1) polymer solid electrolyte solution;
3) with supported catalyst ultrasonic dispersion 0.1～24 hour in polymer solid electrolyte solution, form slurry;
A. slurry is adopted spraying, casting or curtain coating mode with functional membrane attached to step 2) volatilization of the one or both sides of basilar memebrane behind the solvent, promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization to the greatest extent;
B. or with slurry adopt spraying, casting or blade coating on flat board, volatilization forms functional membrane behind the solvent to the greatest extent, with it in step 2) one or both sides of basilar memebrane are in 0.5 minute～1 hour film forming of 100～200 ℃ of hot pressing, have promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
C. or with the polymer solid electrolyte solution of step 1) by casting, spraying or casting method attached to the side volatilization of above-mentioned steps b functional membrane to the greatest extent behind the solvent, on functional membrane, form basilar memebrane, promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
D. or with step 2) in slurry adopt on the basilar memebrane opposite side of spraying, casting or the self-humidifying composite proton exchange film of curtain coating in above-mentioned steps c, volatilization forms functional membrane behind the solvent to the greatest extent, has promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
E. or with the self-humidifying composite proton exchange film among the step c at the functional membrane of the opposite side of its basilar memebrane and step b in 0.5 minute～1 hour film forming of 100～200 ℃ of hot pressing, promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
The heat treated self-humidifying composite proton exchange film of crystallization is not handled 5 minutes～24 hours (being preferably 105～160 ℃ of crystallization heats handled 10 minutes～15 hours) in 100～180 ℃ of crystallization heats of vacuum, promptly gets the self-humidifying fuel cell compound proton exchange membrane; The thickness of self-humidifying composite proton exchange film is 10～150 μ m, is preferably 10～100 μ m.
The loading of the catalytic activity component of described supported catalyst is 10
-5～1mg/cm
2The catalytic activity component is Pt, Au, Pd or Ag etc., and carrier is SiO
2, Al
2O
3, SiO
2-Al
2O
3, CeO
2, ZrO
2, TiO
2, one or more the compound in molecular sieve and the carbon; The mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～50: 1 in the functional membrane; Described high boiling solvent is N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), N, dinethylformamide or N, N-dimethylacetylamide, medium-boiling solvent are n-butanol, butyl acetate or toluene, and low boiling point solvent is acetone, ether, propyl alcohol, isopropyl alcohol or ethanol.
In the moistened membrane technical research, have 3 important problem: first water-keeping material can keep moisture content under low current density, discharges water with wetting proton exchange membrane under high current density.It two is that the reacting gas that trace is interpenetrated generates water by the catalyst surface catalyzed chemical reaction, to reach the effect of moistened membrane.It three is that film water back-diffusion speed is very fast, improves battery performance to adapt to the variation of load with timely wetting film.
The present invention considers above-mentioned 3 major issues, and is as follows for the concrete principle explaination of two class self-humidifying composite proton exchange films:
The first is in conjunction with the compound reinforcing membrane of the polymer solid electrolyte/porous reinforcing membrane advantage as basilar memebrane, the H that permeates in the catalytic activity component chemical catalysis film in the functional membrane that contains supported catalyst in the one or both sides of basilar memebrane
2, O
2Generate the water moistened membrane, the existence of hydrophily catalytic activity component carrier simultaneously can effectively keep moisture content to make the wetting of film and in time provide the proton electromigration required water.This compound reinforcing membrane is that as the advantage of basilar memebrane machinery strengthens the thickness of back attenuate film, can reduce the internal resistance of film significantly, quickens the water back-diffusion coefficient of film, improves battery performance.Fig. 1 is the design schematic diagram from humidification PEMFC.Wherein the expression of (1-1) among Fig. 1 contains the self-humidifying fuel cell compound proton exchange membrane of one-sided functional membrane and basilar memebrane structure of composite membrane, and wherein the polymer solid electrolyte in the functional membrane part has cut off the electronics path of catalyst, H in the film
2O with infiltration
2Electrocatalytic reaction does not take place in the surface at the reactive metal component of supported catalyst, but generates the common humidifying proton exchange film of negative electrode back-diffusion water in the power and water pond through chemical catalysis; Wherein the expression of (1-2) among Fig. 1 contains the self-humidifying fuel cell compound proton exchange membrane of both sides functional membrane and basilar memebrane structure of composite membrane, interpenetrative H
2, O
2Generate the common humidifying proton exchange film of negative electrode back-diffusion water in the power and water pond on reactive metal surface in the humidification composite membrane through chemical catalysis near the supported catalyst of galvanic anode side, and near the reactive metal surface of the supported catalyst of cell cathode side with film in interpenetrative H
2, O
2Generate water through chemical catalysis, eliminate mixed potential, significantly reduce the polarization of oxygen electrode, improve the open circuit voltage (OCV) of battery.Wherein catalytic activity component carrier has water conservation and discharges water when needing to regulate water balance in the film and to prevent to form in the film effect of electrical short.Owing to can stop H from the humidification layer
2, O
2Infiltration diffusion in film effectively suppresses HO
2, oxidative free radical attack polymer film such as HO causes degraded, effectively eliminate and mix overpotential, thereby improve the open circuit voltage and the battery performance of battery.
Its two be with polymer solid electrolyte as basilar memebrane, the design principle of functional membrane is the same.Basilar memebrane can be selected directly to select the polymer solid electrolyte film, also polyelectrolyte can be adopted high boiling solvent dissolving to make the mode solvent flashing of polyelectrolyte solution by casting, spraying or blade coating and become homogeneous polymer solid electrolyte film as basilar memebrane.The type basilar memebrane is distinguished in being the heat of homogeneous membrane, the uniformity consistency of cold coefficient of dilatation with polymer solid electrolyte/porous reinforcing membrane composite membrane as the basilar memebrane part, and shortcoming is to be the difficult characteristics of taking into account mechanical performance and film of this homogeneous membrane.
Advantage of the present invention is as follows:
1. synthetic method is simple.With prior art United States Patent (USP) (U.S.5,472,799) and document (J.Electrochem.Soc, 143 (1996) 3847-3852; J.Electrochem.Soc, 145 (1998) 1137-1141; J.Phys.Chem.B, 102 (1998) 3129-3137) compare, the present invention need not loaded down with trivial details synthesis step from casting film process aspect, operates fairly simplely, and the present invention is easy to continuous commercially producing in the method for synthetic self-humidifying composite proton exchange film.
2. the compactness of self-humidifying composite proton exchange film is good.(application number: 03140527.4) compare, the compactness of film of the present invention is good, and the open circuit voltage that shows as the self-humidifying composite proton exchange film fuel cell is up to 1.032V with Chinese patent with United States Patent (USP) (U.S.5,318,863 and U.S.5,242,764).
3. adopt doping Pt/C catalyst in the inside of composite membrane with Chinese patent (CN 1181585C), the battery performance that is finite concentration Gradient distribution method gained is, it is that the power of battery density of the reaction gas of dry state is lower than 0.5W/cm from the humidification condition fully
2, open circuit voltage is lower than 1.0V, and the present invention has avoided the electronic loop of film inside at the both sides of composite membrane spraying supported catalyst, effectively reduce mixed potential simultaneously, and the compactness of film is good.The power density of the fuel cell from humidification of the present invention can reach 0.95W/cm
2Open circuit voltage is 1.032V.
4, good from humidification composite membrane application.The same United States Patent (USP) of composite membrane of the present invention (U.S.6,207,312) is compared stronger application.Owing to need not outer humidification subsystem, simplified the complexity of fuel cell system, need the fuel cell of outer humidification subsystem that bigger application prospect is arranged.
Description of drawings
Fig. 1 is the principle schematic of self-humidifying composite proton exchange film, and wherein 1-1 is one-sided functional membrane and basilar memebrane composite membrane, and 1-2 is both sides functional membrane and basilar memebrane composite membrane; I is a functional membrane, and II is a basilar memebrane; A is a supported catalyst, and B is the polymeric solid electrolysis;
Fig. 2 is the battery performance figure of the different pressures under the humidification condition outside the humidification composite membrane does not have;
Fig. 3 is the battery performance figure under the humidification condition different pressures of humidification composite membrane 120%;
Fig. 4 is the battery performance figure from the different operating temperature of humidification composite membrane;
Fig. 5 is the battery performance figure from the different humidifications of humidification composite membrane;
Fig. 6 is the battery performance comparison diagram of humidification outside humidification composite membrane and Nafion/PTFE composite membrane do not have.
Embodiment
The structure of the self-humidifying composite proton exchange film that the present invention synthesizes is made up of two parts, first basilar memebrane, and it two is functional membranes, functional membrane is attached to the one or both sides of basilar memebrane.The preparation process of this self-humidifying composite proton exchange film is divided into four processes: the preparation of supported catalyst, basilar memebrane selection or preparation, basilar memebrane one or both sides are adhered to the functional membrane and the crystallization heat that contain supported catalyst and polymer solid electrolyte and are handled.
The preparation of supported catalyst is to adopt immersion reduction method with nanoscale catalytic activity component supported carrier catalytic activity component, and wherein the effect of catalyst is interpenetrative H in the chemical catalysis film
2And O
2Generate water, with wetting proton exchange membrane.The effect of catalytic activity component carrier is that water conservation and film in time discharge water when needing and come wetting film.Can improve the open circuit voltage and the battery performance of battery in addition.
The selection of basilar memebrane or preparation for the raw material of polymer solid electrolyte material, can be sulfonated polyether-ether-ketone, SPSF, perfluorinated sulfonic resin.One, basilar memebrane can directly be selected the polymer solid electrolyte film, or adopts high boiling solvent dissolving to make the mode solvent flashing of polyelectrolyte solution by casting, spraying or blade coating polyelectrolyte to become homogeneous polymer solid electrolyte film as basilar memebrane; Its two be composite membrane with polymer solid electrolyte and porous reinforcing membrane as basilar memebrane, adopt high boiling solvent dissolving polymer solid electrolyte, add mid-boiling point or low boiling point solvent again.High boiling solvent dissolving polymer solid electrolyte, mid-boiling point and low boiling point solvent mainly play wetting porous reinforcing membrane, polymer solid electrolyte impels both compatibilities good soaking under high boiling solvent and mid-boiling point, the low boiling synergy inside and outside the hole of porous reinforcing membrane.Mode by casting, spraying or blade coating prepares in the process of basilar memebrane, be volatilize at a lower temperature mid-boiling point, low boiling point solvent, synchronous volatilization high boiling solvent, separate out with the position that guarantees the relative porous reinforcing membrane of polyelectrolyte when the dissolved state, thereby select suitable solvent to become the key issue of this process.Consistency problem is the key issue of Polymer Blending System.Surface modification for the porous reinforcing membrane is based on polymer blend interface compatibility principle, and promptly in the co-mixing system, the surface tension of polymer is close, both wetting with contact, compatibility is good; But because polymer solid electrolyte is (as perfluorinated sulfonic resin Nafion
) and porous reinforcing membrane (as voided polytetrafluoroethylene film) between surface tension differ greatly, thereby to the surface modification of porous reinforcing membrane, reach and reduce water contact angle, strengthen wetability and both compatibilities, impel the component surface tension trend in the co-mixing system approaching, compatibility is better.
The preparation method of functional membrane who is arranged in the one or both sides of basilar memebrane adopts the method for casting, spraying or blade coating will be at the homodisperse by a certain percentage supported catalyst pulp of polymer solid electrolyte solution, attached to the both sides of the basilar memebrane of polyelectrolyte/porous reinforcing membrane, film forming behind the solvent flashing.The effect of this functional membrane part has two: the first is that water-keeping material that interpenetrative hydrogen-oxygen direct chemical catalysis in the mwco membrane generates water and nanometer scale hydrophilic catalytic activity component carrier acts synergistically and regulates the interior water balance of film near the functional membrane of galvanic anode, guarantees the high performance operation that battery is stable.It two is H of the catalytic activity component microdialysis in the chemical catalysis film in the supported catalyst in the functional membrane
2, O
2, reduce the polarization of oxygen electrode, eliminate because the infiltration of micro-hydrogen causes the mixed potential of oxygen electrode side, improve the open circuit voltage of fuel cell.
The crystallization heat processing procedure is the major issue that the two-phase strong bonded that has influence on self-humidifying composite proton exchange film forms macroscopical homogeneous phase, in heat treatment process, the high polymer main chain of polymer solid electrolyte merges crystallization more again at the macromolecular chain of vitrification point and porous reinforcing membrane, has improved the mechanical strength of film.
Embodiment 1: with the H of 3.7mg/ml
2PtCl
6Solution and nanometer SiO
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 200 ℃
2Reduction 10h is prepared into supported catalyst Pt/SiO
2, the Pt loading is 0.1wt.%.
Embodiment 2: with the HAuCl of 3.7mg/ml
4Solution and nanometer SiO
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 120 ℃
2Reduction 10h is prepared into supported catalyst Au/SiO
2, the Au loading is 0.5wt.%.
Embodiment 3: with the PdCl of 10mg/ml
2Solution and nanometer Al
2O
3Flood 24h under equal-volume (50ml) room temperature, utilize H again at 300 ℃
2Reduction 10h is prepared into supported catalyst Pd/Al
2O
3, the Pd loading is 1wt.%.
Embodiment 4: with the AgNO of 20mg/ml
3Solution and nanometer SiO
2-Al
2O
3Flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Ag/SiO
2-Al
2O
3, the Ag loading is 5wt.%.
Embodiment 5: with the Pt (NH of 20mg/ml
3)
4Cl
2Solution and nano Ce O
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/CeO
2, the Pt loading is 10wt.%.
Embodiment 6: with the Pt (NH of 20mg/ml
3)
4Cl
2Solution and nanometer ZrO
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/ZrO
2, the Pt loading is 10wt.%.
Embodiment 7: with the Pt (NH of 20mg/ml
3)
4Cl
2Solution and nano-TiO
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/TiO
2, the Pt loading is 10wt.%.
Embodiment 8: with the Pt (NH of 20mg/ml
3)
4Cl
2Flood 24h under solution and molecular sieve equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/ molecular sieve, and the Pt loading is 10wt.%.
Embodiment 9: with the Pt (NH of 20mg/ml
3)
4Cl
2Flood 24h under solution and carbon dust equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/ carbon, and the Pt loading is 10wt.%.
Embodiment 10: take by weighing 5% Nafion (EW=1100g/mol
SO3H) solution 60 grams, add the N-N-methyl-2-2-pyrrolidone N-of 10ml and the ethanol heated sealed of 5ml and dissolve.With voided polytetrafluoroethylene film thickness at 5 μ m, the aperture is 0.05 μ m, porosity is tightened in 60% and is placed on the flat board on the stainless steel frame, pour perfluorinated sulfonic acid solution into, 50 ℃ of heating 1 hour, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 11: get Nafion1035 film (EW=1000g/mol
SO3H) 40cm
2, add the N-N-methyl-2-2-pyrrolidone N-of 10ml and the ethanol heating for dissolving of 5ml and make perfluorinated sulfonic acid solution.At 5 μ m, the aperture is 0.05 μ m with porous Kynoar film thickness, and it is 225cm that porosity is tightened in area 60%
2Stainless steel frame on be placed on the flat board, pour perfluorinated sulfonic acid solution into, 50 ℃ of heating 1 hour, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 12: get Nafion212 film (EW=1052g/mol
SO3H) 70cm
2, add the N-N-methyl-2-2-pyrrolidone N-of 10ml and the ethanol heating for dissolving of 5ml and make perfluorinated sulfonic acid solution.At 5 μ m, the aperture is 0.05 μ m with the porous polyethylene film thickness, and it is 225cm that porosity is tightened in area 60%
2Stainless steel frame on be placed on the flat board, pour perfluorinated sulfonic acid solution into, 60 ℃ of heating 5 hours, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 13: get perfluorinated sulfonic acid Nafion resin (EW=900g/mol
SO3H) solution 3 grams, add the N-N-methyl-2-2-pyrrolidone N-of 10ml and the ethanol heated sealed of 5ml and dissolve.With the porous polyimide film thickness at 5 μ m, the aperture is 0.05 μ m, porosity is tightened in 60% and is placed on the flat board on the stainless steel frame, spraying perfluorinated sulfonic acid solution on perforated membrane, 70 ℃ of heating 3 hours, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 14: take by weighing sulfonated polyether-ether-ketone (sulfonation degree is 70%) 60 grams, add the acetone heated sealed dissolving of dimethyl sulfoxide (DMSO) and the 5ml of 10ml.With the porous polypropylene film thickness between 100 μ m, the aperture is 1 μ m, porosity is tightened on the flat board 95%, curtain coating sulfonated polyether-ether-ketone solution on perforated membrane, 80 ℃ of heating 5 hours, be warming up to 75 ℃ of heating 10 hours again, after solvent volatilized substantially, 110 ℃ of heat treatments became basilar memebrane in 3 hours in vacuum drying oven.
Embodiment 15: take by weighing sulfonated polyether-ether-ketone (sulfonation degree is 50%) 60 grams, add the N of 10ml, the isopropyl alcohol of dinethylformamide and 5ml and the dissolving of toluene heated sealed.With porous polysulfone membrane thickness at 10 μ m, the aperture is 0.06 μ m, porosity is tightened on the stainless steel frame 70%, pour sulfonated polyether-ether-ketone solution into, 110 ℃ of heating 1 hour, be warming up to 75 ℃ of heating 10 hours again, after solvent volatilized substantially, 100 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 16: take by weighing SPSF (sulfonation degree is 50%) 60 grams, add the N of 10ml, the propyl alcohol of dinethylformamide and 5ml and the dissolving of butyl acetate heated sealed.With voided polytetrafluoroethylene film thickness at 50 μ m, the aperture is 0.07 μ m, porosity is tightened on the stainless steel frame 80%, pour SPSF solution into, 120 ℃ of heating 1 hour, be warming up to 75 ℃ of heating 10 hours again, after solvent volatilized substantially, 100 ℃ of heat treatments became basilar memebrane in 2 hours in vacuum drying oven.
Embodiment 17: take by weighing SPSF (sulfonation degree is 60%) 60 grams, add the N of 10ml, the ether of N-dimethylacetylamide and 5ml and the dissolving of n-butanol heated sealed.With voided polytetrafluoroethylene film thickness at 90 μ m, the aperture is 0.09 μ m, porosity is tightened on the stainless steel frame 90%, pour SPSF solution into, 60 ℃ of heating 24 hours, be warming up to 75 ℃ of heating 10 hours again, after solvent volatilized substantially, 100 ℃ of heat treatments became basilar memebrane in 2 hours in vacuum drying oven.
Embodiment 18: get Nafion212 film (EW=1052g/mol
SO3H) 70cm
2, add the N-N-methyl-2-2-pyrrolidone N-of 10ml and the ethanol heating for dissolving of 5ml and make perfluorinated sulfonic acid solution.The perfluorinated sulfonic acid solution-cast on flat board, 50 ℃ of heating 24 hours, is warming up to 77 ℃ of heating 10 hours again, and after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 19: get Nafion212 film (EW=1052g/mol
SO3H) 70cm
2, add the N-N-methyl-2-2-pyrrolidone N-of 10ml and the ethanol heating for dissolving of 5ml and make perfluorinated sulfonic acid solution.The perfluorinated sulfonic acid solution casting on flat board, 80 ℃ of heating 10 hours, is warming up to 77 ℃ of heating 10 hours again, and after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 20: get SPSF (sulfonation degree is 50%) 60 grams, add the N of 10ml, the dinethylformamide heating for dissolving obtains polymer solid electrolyte solution.Solution spraying on flat board, 70 ℃ of heating 12 hours, is warming up to 77 ℃ of heating 10 hours again, and after solvent volatilized substantially, 120 ℃ of heat treatments became basilar memebrane in 1 hour in vacuum drying oven.
Embodiment 21: get Nafion212 film (EW=1052g/mol
SO3H) 10cm
2, the N-N-methyl-2-2-pyrrolidone N-heating for dissolving that adds 10ml makes perfluorinated sulfonic acid solution.Supported catalyst (supported catalyst: the mass ratio of polymer solid electrolyte is 1: 50) in perfluorinated sulfonic acid solution and example 1, the example 2 is disperseed to form in 0.1 hour slurry in ultrasonic wave, again slurry is cast on the flat board, 50 ℃ of heating 1 hour, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became functional membrane in 1 hour in vacuum drying oven.
Embodiment 22: get Nafion211 film (EW=1052g/mol
SO3H) 20cm
2, the N-N-methyl-2-2-pyrrolidone N-heating for dissolving that adds 10ml makes perfluorinated sulfonic acid solution.Supported catalyst (supported catalyst: the mass ratio of polymer solid electrolyte is 1: 20) in perfluorinated sulfonic acid solution and example 3, the example 4 is disperseed to form in 1 hour slurry in ultrasonic wave, again slurry is sprayed on the flat board, 60 ℃ of heating 10 hours, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became functional membrane in 1 hour in vacuum drying oven.
Embodiment 23: get Nafion211 film (EW=1052g/mol
SO3H) 20cm
2, the N-N-methyl-2-2-pyrrolidone N-heating for dissolving that adds 10ml makes polymer solid electrolyte solution.Supported catalyst (supported catalyst: the mass ratio of polymer solid electrolyte is 1: 1) in perfluorinated sulfonic acid solution and example 5, the example 6 is disperseed to form in 5 hours slurry in ultrasonic wave, again with the slurry curtain coating on flat board, 100 ℃ of heating 1 hour, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became functional membrane in 1 hour in vacuum drying oven.
Embodiment 24: get sulfonated polyether-ether-ketone resin (sulfonation degree is 50%) 3g, the N-N-methyl-2-2-pyrrolidone N-heating for dissolving that adds 10ml makes polymer solid electrolyte solution.Supported catalyst (supported catalyst: the mass ratio of polymer solid electrolyte is 10: 1) in solution and example 7, the example 8 is disperseed to form in 10 hours slurry in ultrasonic wave, again with the slurry curtain coating on flat board, 120 ℃ of heating 1 hour, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became functional membrane in 1 hour in vacuum drying oven.
Embodiment 25: get sulfonated polysulfone resin (sulfonation degree is 50%) 3g, the N-N-methyl-2-2-pyrrolidone N-heating for dissolving that adds 10ml makes polymer solid electrolyte solution.Supported catalyst in solution and the example 9 (supported catalyst: the mass ratio of polymer solid electrolyte is 50: 1) is disperseed to form in 24 hours slurry in ultrasonic wave, again with the slurry curtain coating on flat board, 60 ℃ of heating 20 hours, be warming up to 77 ℃ of heating 10 hours again, after solvent volatilized substantially, 120 ℃ of heat treatments became functional membrane in 1 hour in vacuum drying oven.
Embodiment 26: with the Pt/SiO among the embodiment 1
2Supported catalyst and Nafion resin (EW=900g/mol
SO3H) to be made into mass ratio be 1: 50 and add the slurry of isopropyl alcohol through ultrasonic dispersion.Both sides spraying slurry at the basilar memebrane of embodiment 10 preparation behind the solvent flashing, obtains the functional membrane of thick 0.1 μ m on basilar memebrane, volatilization was handled 5 minutes in 100 ℃ of crystallization heats behind the solvent to the greatest extent.The load amount of Pt is 10
-5Mg/cm
2Self-humidifying fuel cell is 10 μ m with the thickness of compound proton exchange membrane.
Embodiment 27: with the Pt/SiO among the embodiment 1
2Supported catalyst and Nafion resin (EW=900g/mol
SO3H) to be made into mass ratio be 1: 50 and add the slurry of isopropyl alcohol through ultrasonic dispersion.The slurry of casting at twice in the both sides of the basilar memebrane of embodiment 11 preparation behind the solvent flashing, obtains the functional membrane of thick 0.1 μ m on basilar memebrane, volatilization was handled 10 minutes in 120 ℃ of crystallization heats behind the solvent to the greatest extent.The load amount of Pt is 10
-4Mg/cm
2Self-humidifying fuel cell is 20 μ m with the thickness of compound proton exchange membrane.
Embodiment 28: with the Pt/SiO among the embodiment 1
2Supported catalyst and Nafion resin (EW=900g/mol
SO3H) to be made into mass ratio be 1: 50 and add the slurry of isopropyl alcohol through ultrasonic dispersion.Side casting slurry at the basilar memebrane of embodiment 11 preparation behind the solvent flashing, obtains the functional membrane of thick 0.1 μ m on basilar memebrane, volatilization was handled 24 hours in 110 ℃ of crystallization heats behind the solvent to the greatest extent.The load amount of Pt is 10
-3Mg/cm
2Self-humidifying fuel cell is 30 μ m with the thickness of compound proton exchange membrane.
Embodiment 29: with the Pt/SiO among the embodiment 1
2Supported catalyst and Nafion resin (EW=900g/mol
SO3H) to be made into mass ratio be 1: 50 and add the slurry of isopropyl alcohol through ultrasonic dispersion.Both sides casting slurry at the basilar memebrane of embodiment 11 preparation behind the solvent flashing, obtains the functional membrane of thick 0.1 μ m on basilar memebrane, volatilization was handled 2 hours in 180 ℃ of crystallization heats behind the solvent to the greatest extent.The load amount of Pt is 1mg/cm
2Self-humidifying fuel cell is 30 μ m with the thickness of compound proton exchange membrane.
Embodiment 30: the functional membrane of embodiment 21 was become the self-humidifying fuel cell compound proton exchange membrane at 100 ℃ in 1 hour with the basilar memebrane hot pressing of embodiment 18.
Embodiment 31: the functional membrane of embodiment 22 was become the self-humidifying fuel cell compound proton exchange membrane at 120 ℃ in 10 minutes with the basilar memebrane hot pressing of embodiment 19.
Embodiment 32: the functional membrane of embodiment 24 was become the self-humidifying fuel cell compound proton exchange membrane at 200 ℃ in 0.5 minute with the basilar memebrane hot pressing of embodiment 10.
Embodiment 33: the functional membrane of embodiment 23 was become the self-humidifying fuel cell compound proton exchange membrane at 150 ℃ in 0.5 hour with the basilar memebrane hot pressing of embodiment 11.
Embodiment 34: the functional membrane of embodiment 25 was become the self-humidifying fuel cell compound proton exchange membrane at 180 ℃ in 0.5 hour with the basilar memebrane hot pressing of embodiment 12.
Embodiment 35: with the Pt/SiO among the embodiment 1
2Supported catalyst and Nafion resin (EW=1100g/mol
SO3H) to be made into mass ratio be 1: 30 and add the solution of isopropyl alcohol through ultrasonic dispersion.Slurry in the side spraying embodiment 24 of the basilar memebrane that embodiment 10 prepares, behind the solvent flashing, obtain the functional membrane attached to the thick 1 μ m on the basilar memebrane, handling the thickness that formed the compound proton exchange membrane that self-humidifying fuel cell uses in 0.5 hour in 140 ℃ of crystallization heats again is 20 μ m.Wherein the load amount of Pt is 10
-4Mg/cm
2
Self-humidifying fuel cell in this example is seen accompanying drawing 2,3,4,5 with the battery performance of self-humidifying composite proton exchange film, relatively sees Fig. 6 with the battery performance of the same battery appreciation condition of 10 basilar memebrane among the embodiment.
Adopt SGL carbon paper, ptfe emulsion, XC-72 carbon dust, 5%Nafion
(E.I.Du Pont Company) solution and 20%Pt/C Preparation of Catalyst electrode, anode Pt load amount is 0.3mg/cm
2, negative electrode Pt load amount is 0.5mg/cm
2Compacting 5cm
2The operating condition of the three-in-one hydraulic press of MEA be, 160 ℃, minute-pressure precompressed 1 minute improves pressure again to 2MPa, hot pressing 2 minutes, cooling promptly gets MEA.
The evaluating of fuel cell is as follows:
The H of dry state
2/ O
2Operating pressure, 0.02～0.2MPa; 30～80 ℃ of operating temperatures; m
Pt, MEA=0.7mg/cm
2The test of single pond; Hydrogen utilization ratio is＞90%, and oxygen utilization rate is 50%; Effective area is 5cm
2
The open circuit voltage of self-humidifying composite proton exchange film fuel cell reaches 1.032v, and power density is up to 0.95w/cm
2
Embodiment 36: with the Au/SiO among the embodiment 2
2Supported catalyst and Nafion resin are made into mass ratio to be 1: 1 and to add the solution of isopropyl alcohol through ultrasonic dispersion.Slurry in the both sides spraying embodiment 23 of the basilar memebrane of embodiment 10 preparation, behind the solvent flashing attached to the functional membrane of the thick 3 μ m on the basilar memebrane.The load amount of Au is 10
-3Mg/cm
2Handle in 110 ℃ of crystallization heats behind the final solvent flashing that to form self-humidifying fuel cell in 1 hour be 30 μ m with the thickness of compound proton exchange membrane.
Embodiment 37: with the Pd/Al among the embodiment 3
2O
3Supported catalyst and Nafion resin are made into mass ratio to be 10: 1 and to add the solution of isopropyl alcohol through ultrasonic dispersion.Slurry in the both sides spraying embodiment 22 of the basilar memebrane that embodiment 12 prepares obtains the functional membrane attached to the thick 10 μ m on the basilar memebrane behind the solvent flashing.The load amount of Pd is 10
-1Mg/cm
2Handle in 120 ℃ of crystallization heats behind the final solvent flashing that to form self-humidifying fuel cell in 0.5 hour be 100 μ m with the thickness of compound proton exchange membrane.
Embodiment 38: with the Pt/ZrO among the embodiment 6
2Supported catalyst and Nafion resin are made into mass ratio to be 50: 1 and to add the solution of isopropyl alcohol through ultrasonic dispersion.Slurry in the both sides spraying embodiment 21 of the composite membrane that embodiment 13 prepares obtains the functional membrane attached to the thick 20 μ m on the basilar memebrane behind the solvent flashing.The load amount of Pt is 10mg/cm
2Handle in 140 ℃ of crystallization heats behind the final solvent flashing that to form self-humidifying fuel cell in 0.5 hour be 150 μ m with the thickness of compound proton exchange membrane.
Claims (10)
1. self-humidifying fuel cell multilayer composite proton exchange membrane is characterized in that: the one or both sides at the basilar memebrane of densification add the functional membrane of being made up of supported catalyst and polymer solid electrolyte.
2. according to the described self-humidifying fuel cell multilayer composite proton exchange membrane of claim 1, it is characterized in that: the mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～50: 1 in the functional membrane.
3. according to the described self-humidifying fuel cell multilayer composite proton exchange membrane of claim 1, it is characterized in that: described polymer solid electrolyte is sulfonated polyether-ether-ketone, SPSF or perfluorinated sulfonic resin; The loading of the catalytic activity component of supported catalyst is 10
-5～1mg/cm
2The catalytic activity component is Pt, Au, Pd and/or Ag, and carrier is SiO
2, Al
2O
3, SiO
2-Al
2O
3, CeO
2, ZrO
2, TiO
2, one or more the compound in molecular sieve and the carbon.
4. according to the described self-humidifying fuel cell multilayer composite proton exchange membrane of claim 1, it is characterized in that: basilar memebrane is a polymer solid electrolyte homogeneous membrane or with the film formed dense film of the filling porous enhancing of polymer solid electrolyte.
5. according to the described self-humidifying fuel cell multilayer composite proton exchange membrane of claim 4, it is characterized in that: the porous reinforcing membrane is porous Teflon, porous Kynoar, porous polypropylene, porous polyethylene, porous polyimide or porous polysulfones, its thickness is 5～100 μ m, the aperture is 0.05～1 μ m, and porosity is 60～95%.
6. according to the described self-humidifying fuel cell multilayer composite proton exchange membrane of claim 4, it is characterized in that: porous reinforcing membrane thickness is 5～60 μ m, and the aperture is 0.1～0.6 μ m, and porosity is 75～90%.
7. according to the described self-humidifying fuel cell multilayer composite proton exchange membrane of claim 1, it is characterized in that: functional membrane thickness is 0.1～20 μ m; The load amount of the catalytic activity component of supported catalyst is preferably 10 in the functional membrane
-4～0.1mg/cm
2
8. according to the synthetic method of the described self-humidifying fuel cell of claim 1 with multilayer composite proton exchange membrane, it is characterized in that: step is as follows,
1) polymer solid electrolyte is made polymer solid electrolyte solution with high boiling solvent dissolving back adding mid-boiling point or low boiling point solvent;
2) step 1) polymer solid electrolyte solution is prepared into the polymer solid electrolyte homogeneous membrane as basilar memebrane behind the solvent to the greatest extent by casting, spraying or casting method volatilization;
Or, became basilar memebrane behind the solvent flashing in 1～24 hour in 50～120 ℃ of heating at the top casting of porous reinforcing membrane, spraying or curtain coating step 1) polymer solid electrolyte solution;
3) with supported catalyst ultrasonic dispersion 0.1～24 hour in polymer solid electrolyte solution, form slurry;
A. slurry is adopted spraying, casting or curtain coating mode with functional membrane attached to step 2) volatilization of the one or both sides of basilar memebrane behind the solvent, promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization to the greatest extent;
B. or with slurry adopt spraying, casting or blade coating on flat board, volatilization forms functional membrane behind the solvent to the greatest extent, with it in step 2) one or both sides of basilar memebrane are in 0.5 minute～1 hour film forming of 100～200 ℃ of hot pressing, have promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
C. or with the polymer solid electrolyte solution of step 1) by casting, spraying or casting method attached to the side volatilization of above-mentioned steps b functional membrane to the greatest extent behind the solvent, on functional membrane, form basilar memebrane, promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
D. or with step 2) in slurry adopt on the basilar memebrane opposite side of spraying, casting or the self-humidifying composite proton exchange film of curtain coating in above-mentioned steps c, volatilization forms functional membrane behind the solvent to the greatest extent, has promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
E. or with the self-humidifying composite proton exchange film among the step c at the functional membrane of the opposite side of its basilar memebrane and step b in 0.5 minute～1 hour film forming of 100～200 ℃ of hot pressing, promptly synthesized the not heat treated self-humidifying composite proton exchange film of crystallization;
The heat treated self-humidifying composite proton exchange film of crystallization was not handled 5 minutes～24 hours in 100～180 ℃ of crystallization heats of vacuum, promptly got the self-humidifying fuel cell compound proton exchange membrane, and the thickness of self-humidifying composite proton exchange film is 10～150 μ m.
9. according to the synthetic method of the described self-humidifying fuel cell of claim 8 with multilayer composite proton exchange membrane, it is characterized in that: the loading of the catalytic activity component of described supported catalyst is 10
-5～1mg/cm
2The catalytic activity component is Pt, Au, Pd or Ag, and carrier is SiO
2, Al
2O
3, SiO
2-Al
2O
3, CeO
2, ZrO
2, TiO
2, one or more the compound in molecular sieve and the carbon; The mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～50: 1 in the functional membrane; Described high boiling solvent is N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), N, dinethylformamide or N, N-dimethylacetylamide, medium-boiling solvent are n-butanol, butyl acetate or toluene, and low boiling point solvent is acetone, ether, propyl alcohol, isopropyl alcohol or ethanol.
10. according to the synthetic method of the described self-humidifying fuel cell of claim 8 with multilayer composite proton exchange membrane, it is characterized in that: the heat treated self-humidifying composite proton exchange film of crystallization was not handled 10 minutes～15 hours in 105～160 ℃ of crystallization heats of vacuum, and the thickness of self-humidifying composite proton exchange film is 10～100 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100467096A CN100446314C (en) | 2005-06-17 | 2005-06-17 | Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100467096A CN100446314C (en) | 2005-06-17 | 2005-06-17 | Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1881667A true CN1881667A (en) | 2006-12-20 |
| CN100446314C CN100446314C (en) | 2008-12-24 |
Family
ID=37519741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100467096A Active CN100446314C (en) | 2005-06-17 | 2005-06-17 | Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100446314C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101614626A (en) * | 2008-06-25 | 2009-12-30 | 通用汽车环球科技运作公司 | In situ fuel cell contamination sampling device |
| CN101254425B (en) * | 2007-12-06 | 2011-05-04 | 上海大学 | CeO2 modification sulphonation polyetheretherketone proton exchange film and method of preparing the same |
| CN102867930A (en) * | 2011-07-05 | 2013-01-09 | 中国科学院大连化学物理研究所 | Composite film for flow energy storage battery and application thereof |
| KR20140084052A (en) * | 2011-10-24 | 2014-07-04 | 존슨 맛쎄이 푸엘 셀스 리미티드 | Ion-conducting membrane |
| CN104300161A (en) * | 2014-09-28 | 2015-01-21 | 宁波大学 | Electrode catalytic material for polymer electrode membrane fuel cell |
| CN104716351A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell self-humidifying membrane electrode and preparation method thereof |
| CN107221693A (en) * | 2016-09-27 | 2017-09-29 | 黄河科技学院 | A kind of high temperature proton exchange film of polybenzimidazoles/ionic liquid MULTILAYER COMPOSITE and preparation method thereof |
| CN108110291A (en) * | 2017-12-28 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel cell refractory ceramics matrix proton exchange and preparation method thereof |
| CN111146482A (en) * | 2019-12-10 | 2020-05-12 | 一汽解放汽车有限公司 | Self-humidifying proton exchange membrane and preparation method and application thereof |
| CN111554955A (en) * | 2020-04-10 | 2020-08-18 | 珠海格力电器股份有限公司 | Self-humidifying composite proton exchange membrane preparation method, membrane electrode and fuel cell |
| CN111875825A (en) * | 2020-06-22 | 2020-11-03 | 山东东岳高分子材料有限公司 | High-proton-conductivity enhanced perfluorinated sulfonic acid composite ion exchange membrane and preparation method thereof |
| CN113169346A (en) * | 2019-01-17 | 2021-07-23 | 庄信万丰燃料电池有限公司 | Film |
| CN113937303A (en) * | 2021-10-14 | 2022-01-14 | 中汽创智科技有限公司 | Catalytic layer electrode composition, catalytic layer electrode comprising same and membrane electrode |
| CN114864989A (en) * | 2022-05-26 | 2022-08-05 | 一汽解放汽车有限公司 | Membrane electrode frame, preparation method thereof and membrane electrode |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849311A (en) * | 1986-09-24 | 1989-07-18 | Toa Nenryo Kogyo Kabushiki Kaisha | Immobilized electrolyte membrane |
| DE69425196T2 (en) * | 1993-06-18 | 2000-12-21 | Tanaka Precious Metal Ind | Electrochemical cell containing a polymeric solid electrolyte composition. |
| GB9822576D0 (en) * | 1998-10-16 | 1998-12-09 | Johnson Matthey Plc | Membrane |
| CN1224119C (en) * | 2002-03-29 | 2005-10-19 | 清华大学 | Humidity preservation composite film used for proton exchange film fuel battery and its preparation method |
-
2005
- 2005-06-17 CN CNB2005100467096A patent/CN100446314C/en active Active
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254425B (en) * | 2007-12-06 | 2011-05-04 | 上海大学 | CeO2 modification sulphonation polyetheretherketone proton exchange film and method of preparing the same |
| CN101614626A (en) * | 2008-06-25 | 2009-12-30 | 通用汽车环球科技运作公司 | In situ fuel cell contamination sampling device |
| CN101614626B (en) * | 2008-06-25 | 2013-08-21 | 通用汽车环球科技运作公司 | In situ fuel cell contamination sampling device |
| CN102867930A (en) * | 2011-07-05 | 2013-01-09 | 中国科学院大连化学物理研究所 | Composite film for flow energy storage battery and application thereof |
| KR20140084052A (en) * | 2011-10-24 | 2014-07-04 | 존슨 맛쎄이 푸엘 셀스 리미티드 | Ion-conducting membrane |
| CN104054201A (en) * | 2011-10-24 | 2014-09-17 | 庄信万丰燃料电池有限公司 | Ion-conducting membrane |
| US10530002B2 (en) | 2011-10-24 | 2020-01-07 | Johnson Matthey Fuel Cells Limited | Ion-conducting membrane |
| KR102037828B1 (en) * | 2011-10-24 | 2019-10-30 | 존슨 맛쎄이 푸엘 셀스 리미티드 | Ion-conducting membrane |
| CN104716351A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell self-humidifying membrane electrode and preparation method thereof |
| CN104300161A (en) * | 2014-09-28 | 2015-01-21 | 宁波大学 | Electrode catalytic material for polymer electrode membrane fuel cell |
| CN107221693B (en) * | 2016-09-27 | 2019-10-22 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | A kind of high temperature proton exchange film and preparation method thereof of polybenzimidazoles/ionic liquid MULTILAYER COMPOSITE |
| CN107221693A (en) * | 2016-09-27 | 2017-09-29 | 黄河科技学院 | A kind of high temperature proton exchange film of polybenzimidazoles/ionic liquid MULTILAYER COMPOSITE and preparation method thereof |
| CN108110291A (en) * | 2017-12-28 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel cell refractory ceramics matrix proton exchange and preparation method thereof |
| CN113169346A (en) * | 2019-01-17 | 2021-07-23 | 庄信万丰燃料电池有限公司 | Film |
| CN111146482A (en) * | 2019-12-10 | 2020-05-12 | 一汽解放汽车有限公司 | Self-humidifying proton exchange membrane and preparation method and application thereof |
| CN111554955A (en) * | 2020-04-10 | 2020-08-18 | 珠海格力电器股份有限公司 | Self-humidifying composite proton exchange membrane preparation method, membrane electrode and fuel cell |
| CN111875825A (en) * | 2020-06-22 | 2020-11-03 | 山东东岳高分子材料有限公司 | High-proton-conductivity enhanced perfluorinated sulfonic acid composite ion exchange membrane and preparation method thereof |
| CN113937303A (en) * | 2021-10-14 | 2022-01-14 | 中汽创智科技有限公司 | Catalytic layer electrode composition, catalytic layer electrode comprising same and membrane electrode |
| CN114864989A (en) * | 2022-05-26 | 2022-08-05 | 一汽解放汽车有限公司 | Membrane electrode frame, preparation method thereof and membrane electrode |
| CN114864989B (en) * | 2022-05-26 | 2024-01-19 | 一汽解放汽车有限公司 | Membrane electrode frame and preparation method thereof and membrane electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100446314C (en) | 2008-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100446314C (en) | Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell | |
| Abdelkareem et al. | Comparative analysis of liquid versus vapor-feed passive direct methanol fuel cells | |
| CN103493266B (en) | There is the fuel cell electrode of the Porous carbon core containing Macrocyclic metal chelate thereon | |
| KR100647296B1 (en) | Metal catalyst and a fuel cell employing an electrode including the same | |
| Ding et al. | Recent progress in proton-exchange membrane fuel cells based on metal-nitrogen-carbon catalysts | |
| CN1957492A (en) | Ruthenium-rhodium alloy electrode catalyst and fuel cell comprising the same | |
| CN101170181B (en) | A compound proton exchange film for self-humidity increase fuel battery and its making method | |
| CN1877890A (en) | Electrode substrate for a fuel cell, a method for preparing the same, and a membrane-electrode assembly comprising the same | |
| CN1691383A (en) | Anode for liquid fuel cell, membrane electrode assembly for liquid fuel cell, and liquid fuel cell | |
| CN1819314A (en) | Fuel cell electrode containing metal phosphate and fuel cell using the same | |
| CN1512611A (en) | Method for producing fuel cell electrode | |
| Baglio et al. | Investigation of the electrochemical behaviour in DMFCs of chabazite and clinoptilolite-based composite membranes | |
| CN1845363A (en) | Composite proton exchange membrane synthesizing method for fuel cell | |
| CN108110260B (en) | A kind of fuel-cell catalyst and preparation method of metal-organic framework modification | |
| CN1885599A (en) | Anti-carbon monoxide composite anode electrode catalyst layer structure and preparation method | |
| CN101034748A (en) | Making method for core component of water-reservation proton exchange film fuel battery | |
| CN1853296A (en) | Membrane-electrode unit for direct methanol fuel cells and method for the production thereof | |
| CN107146891A (en) | A kind of MEA preparation methods of noble metal catalyst particles distribution gradient | |
| CN102479959A (en) | Self-humidifying proton exchange film for fuel cell, and preparation method thereof | |
| CN1171671C (en) | Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube | |
| CN1251344C (en) | A cathode layer structure for solid polymer fuel cell and fuel cell incorporating such structure | |
| CN1921195A (en) | Proton superpolymer modified fuel cell catalyst using carbon as carrier and its preparation | |
| CN1967917A (en) | Electrocatalyst for fuel cell-electrode, membrane-electrode assembly using the same and fuel cell | |
| CN100483814C (en) | Method for preparation of membrane electrode of water-keeping proton exchange film fuel cells | |
| CN101041137A (en) | Cathode catalyst for fuel cell, membrane-electrode assembly for fuel cell comprising same and fuel cell system comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: XINYUAN POWER CO., LTD. Free format text: FORMER OWNER: DALIAN INST OF CHEMICOPHYSICS, CHINESE ACADEMY OF SCIENCES Effective date: 20071116 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20071116 Address after: Block 401# No. 1 A 116023 in Liaoning province Dalian City High-tech Park Qixianling Torch Road Applicant after: Sunrise Power Co., Ltd. Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Applicant before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |