CN101170181B - A compound proton exchange film for self-humidity increase fuel battery and its making method - Google Patents
A compound proton exchange film for self-humidity increase fuel battery and its making method Download PDFInfo
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- CN101170181B CN101170181B CN2006101340148A CN200610134014A CN101170181B CN 101170181 B CN101170181 B CN 101170181B CN 2006101340148 A CN2006101340148 A CN 2006101340148A CN 200610134014 A CN200610134014 A CN 200610134014A CN 101170181 B CN101170181 B CN 101170181B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a proton exchange membrane for a fuel cell, in particular to a combined self-humidifying proton exchange membrane for a self-humidifying fuel cell and a preparation method. The method comprises the steps of distributing loaded catalysts to organic solution of solid macromolecule electrolyte to form casting solution, then casting, coating, or tape casting are adopted to prepare the self-humidifying proton exchange membrane, or the casting solution is adopted with methods of casting, coating, or tape casting to be filled in a porous strengthening membrane to prepare the self-humidifying proton exchange membrane. The self-humidifying proton exchange membrane of the invention generates from non-electric short circuit in the whole membrane, and has the characteristics of good density, high proton conductivity, strong water retaining capacity, as well as 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 compound proton exchange membrane and synthetic method thereof.
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, its performance directly influences battery performance, energy efficiency and the useful life of PEMFC. the solid polymer dielectric film that generally adopts for present PEMFC, proton form with proton hydrate in film is transmitted to negative electrode from anode, water in film as the carrier of proton conduction.With a kind of polymer film, the high more film inner proton of the water content of film conduction velocity is just fast more, and the conductivity of film is big more. and therefore for PEMFC, keep the water content of proton exchange membrane abundance very important.
In present research and development, normally adopt the humidification auxiliary system that the reaction gas that enters battery pack is carried out humidification and handle the water content that keeps proton exchange membrane, this increased beyond doubt 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.
When outside fuel cell is not having, moving under the humidification condition, it is that proton exchange membrane is kept the unique water source of wetting state that the cathode side electrochemical reaction generates water. the hydrone that has dual mode to transmit in the proton exchange membrane: under electroosmosis, generate water at the back-diffusion water that is diffused into anode under the concentration gradient effect from negative electrode from anode to the electromigration water and the cathode side electrochemical reaction of cathodic migration with proton. when back-diffusion water can not in time replenish move to the electromigration water of cathode side from anode owing to electroosmosis in, thereby the anode-side of film then is in the decline significantly that dry state causes proton conductivity. the research at self-humidifying proton exchange film mainly concentrates on the micro-reaction impervious characteristic that two thinkings (I) are utilized film, makes interpenetrative hydrogen, chemical reaction takes place and generates the water common wetting film of cathode side electrochemical reaction generation water in addition in oxygen on platinum catalyst; (II) utilize battery to generate water, come the retrodiffusion of water in the strengthening membrane and the water content of increase film by adopting film or doping water conservation material.
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).This composite membrane guarantees the wetting state that film is enough by water strong retrodiffusion in film that negative electrode generates.But the shortcoming of this method is that the compactness of film is bad, and gas permeability is big.
At United States Patent (USP) (U.S.5,472,799) adopt Nafion film sputter thin layer precious metals pt in, and then casting last layer Nafion film, formation has the film that metal simple-substance is coated on intermediate structure, and this method is because the adding of Pt Catalytic Layer has improved the open circuit voltage of fuel cell.But the adding of Pt Catalytic Layer makes the combination interface that has duplicature in the composite membrane, can increase the internal resistance of cell like this, in addition because sputtering method brings the complexity of film-forming method to be difficult to commercially produce.
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.Though shortcoming is supported catalyst Pt/C forms the finite concentration gradient in film distribution, the internal resistance that can not avoid the adding of the carbon of electrical short and non-proton conductor to increase composite membrane fully, 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, adopt high temperature, high pressure in this composite membrane preparation process, cause cost than higher, and the open circuit voltage of 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 the oxide that adds the non-conducting proton in the composite membrane increased the internal resistance of film, and battery performance is relatively poor, and the adding of Pt produces electrical short easily in whole film in addition.
At document (L.Wang, D.M.Xing, Y.H.Liun, J.Power Sourse, in press.) in, silica supported platinum catalyst is joined in the Nafion/PTFE film preparation from the humidification composite membrane as additive, avoided in composite membrane, forming the phenomenon of electrical short because silicon dioxide is non-electronic conductor, but silicon dioxide is non-proton conductor simultaneously, and its adding has increased the internal resistance of film.
Summary of the invention
The object of the present invention is to provide a kind of self-humidifying fuel cell compound proton exchange membrane and synthetic method thereof; Nos electrical short generation in this composite membrane, have that compactness is good, proton conductivity is high, water holding capacity by force, characteristics cheaply.
For achieving the above object, the technical solution used in the present invention is:
A kind of self-humidifying fuel cell compound proton exchange membrane, supported catalyst is distributed in the organic solution of polymer solid electrolyte and forms casting solution, cast then, the method for spraying or curtain coating is prepared into self-humidifying composite proton exchange film or the method for casting solution by casting, spraying or curtain coating be filled in the porous reinforcing membrane be prepared into self-humidifying composite proton exchange film.
The mass ratio of supported catalyst and polymer solid electrolyte is 1: 100～20: 1 in the described casting solution, is preferably 1: 50～5: 1; Described polymer solid electrolyte is any in sulfonated polyether-ether-ketone, SPSF, sulfonated polyether sulfone, sulfonated polyimide, sulfonated polyphenyl and imidazoles, sulfonated polystyrene, sulfonated polyphenyl thioether, sulfonated poly (phenylene oxide), sulfonation poly quinoline, sulfonation polysilane or the perfluorinated sulfonic resin; The loading of the catalytic activity component of supported catalyst is 10
-3～20wt.%; The catalytic activity component is one or more the mixed catalyst component among Pt, Au, Pd, the Ag, and carrier is SO
-2 4/ Fe
2O
3, SO
-2 4/ ZrO
2, SO
-2 4/ TiO
2, SO
-2 4/ (WO
3-ZrO
2), SO
-2 4/ (SiO
2-Al
2O
3), SO
-2 4/ (SiO
2-TiO
2), SO
-2 4/ (SiO
2-ZrO
2), SO
-2 4/ (ZrO
2-TiO
2), SO
-2 4/ (ZrO
2-MoO
3), Zr (HPO
4)
2, Cs
XH
3-XBM
12O
40In one or more compound; X=0～3 wherein, B=P, Si or As, M=Mo, W or V; 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%; When compound proton exchange membrane had adopted the porous reinforcing membrane, wherein the supported catalyst of filling on every square centimeter of porous reinforcing membrane and the gross mass of polymer solid electrolyte were 10
-3～1g; From humidification composite membrane thickness is 10～150 μ m.
Self-humidifying fuel cell is as follows with the synthetic method of compound proton exchange membrane:
1) polymer solid electrolyte is made polymer solid electrolyte solution with the high boiling solvent dissolving, the weight concentration of polymer solid electrolyte is 3～15%; Or polymer solid electrolyte added mid-boiling point with high boiling solvent dissolving back or low boiling point solvent is made polymer solid electrolyte solution, the weight concentration of polymer solid electrolyte is 1～10%, the volume ratio of high boiler and mid-boiling point or low boiling point solvent 10: 1～1: 5;
2) with supported catalyst in polymer solid electrolyte solution ultrasonic 0.1～24 hour, stirred 0.1～24 hour, form casting solution; The mass ratio of supported catalyst and polymer solid electrolyte is 1: 100～20: 1 in the casting solution;
3) with step 2) in casting solution to the greatest extent be prepared into compound proton exchange membrane behind the solvent by casting, spraying or casting method in 50～120 ℃ of heating volatilization in 1～24 hour;
Or in the top casting of porous reinforcing membrane, spraying or curtain coating step 2) in casting solution, be prepared into compound proton exchange membrane behind the solvent flashing in 1～24 hour in 50～120 ℃ of heating; Wherein the gross mass of the casting solution of filling on every square centimeter of porous reinforcing membrane is 10
-2～10g;
4) compound proton exchange membrane of step 3) preparation is heat-treated under 120～200 ℃ and inert atmosphere, the processing time is 5 minutes～24 hours;
5) with the compound proton exchange membrane after the step 4) heat treatment in 3～5%H
2O
250～100 ℃ were boiled 30～100 minutes in the solution, took out the back and were placed on 0.5～2MH with washed with de-ionized water
2SO
4In 50～100 ℃ boiled 30～100 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last.
The loading of the catalytic activity component of described supported catalyst is 10
-3～20wt.%; The catalytic activity component is one or more the mixed catalyst component among Pt, Au, Pd, the Ag, and carrier is SO
-2 4/ Fe
2O
3, SO
-2 4/ ZrO
2, SO
-2 4/ TiO
2, SO
-2 4/ (WO
3-ZrO
2), SO
-2 4/ (SiO
2-Al
2O
3), SO
-2 4/ (SiO
2-TiO
2), SO
-2 4/ (SiO
2-ZrO
2), SO
-2 4/ (ZrO
2-TiO
2), SO
-2 4/ (ZrO
2-MoO
3), Zr (HPO
4)
2, Cs
XH
3-XBM
12O
40In one or more compound; X=0～3 wherein, B=P, Si or As, M=Mo, W or V; The mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～5: 1 in the casting solution; 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; Described preparation be 10～150 μ m from humidification composite membrane thickness.
In the moistened membrane technical research, have 4 important problem: first film water back-diffusion speed is very fast, improves battery performance to adapt to the variation of load with timely wetting film; It two is to add inorganic functional material to guarantee that fuel cell film under dry gas running environment still can keep good proton conductivity in film; It three is doped catalysts in film, and the reacting gas that trace is interpenetrated generates water by the catalyst surface catalyzed chemical reaction, with the effect that reaches moistened membrane and improve open circuit voltage; Its four be avoid since catalyst be added in the phenomenon that produces electrical short in the film.
Consider above-mentioned 4 major issues, the concrete principle explaination for the self-humidifying composite proton exchange film for preparing among the present invention is as follows:
The casting solution that will contain polymer solid electrolyte and supported catalyst among the present invention adopts the method for casting, spraying or curtain coating to be prepared into self-humidifying composite proton exchange film or casting solution is filled in the porous reinforcing membrane to be prepared into self-humidifying composite proton exchange film.Combine the advantage of the compound reinforcing membrane of polymer solid electrolyte/porous reinforcing membrane among the present invention,, reduce the internal resistance of film significantly, quicken the water back-diffusion coefficient of film, improve battery performance by the thickness of attenuate film.Moreover with supported catalyst as additive preparation from the humidification composite membrane, wherein the carrier of supported catalyst has good proton conducting ability simultaneously and keeps the inorganic functional material of moisture ability.Not only can in film, keep moisture in time to provide the proton electromigration required water effectively like this, and extra proton conduction path is provided in composite membrane, increase the proton conductivity of composite membrane, thereby improved battery performance; Carrier is the inorganic matter of non-electronic conductor in addition, has just avoided the generation of electrical short like this in composite membrane.The existence of supported catalyst makes interpenetrative H among the present invention
2, O
2Generate the water common humidifying proton exchange film of negative electrode back-diffusion water in the battery in addition on the reactive metal surface of supported catalyst through chemical catalysis, also effectively eliminated simultaneously the mixed potential that infiltration gas produces on electrode, significantly reduce the polarization of oxygen electrode, improve the open circuit voltage (OCV) of battery.Can stop H from the humidification composite membrane in addition
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.
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, is easy to continuous commercially producing; Preparation method from the humidification composite membrane among the present invention is simple, and no complex apparatus requirement is easy to operate, and is quick.
2. with Chinese patent (CN 1181585C) 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, adopting carrier among the present invention is the supported catalyst of electronic body, has avoided producing in the film phenomenon of electrical short fully.
3. membranous electron conductivity height.With document (L.Wang, D.M.Xing, Y.H.Liun, J.Power Sourse, in press.) compare, adopt the supported catalyst preparation from the humidification composite membrane among the present invention, wherein the carrier of supported catalyst has the ability of water retention property and proton conducting simultaneously, not only can absorb the wetting state that moisture keeps composite membrane, increase the approach of proton conduction simultaneously, increase the conductivity of composite membrane.
4. 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 higher with Chinese patent with United States Patent (USP) (U.S.5,318,863 and U.S.5,242,764).
5, 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, can realize fuel cell stable operation under the humidification condition outside not having, improved energy efficiency, reduced the cost of fuel cell, need the fuel cell of outer humidification subsystem that bigger application prospect is arranged, the present invention prepare from humidification composite membrane using value height.
Description of drawings
Fig. 1 is provided by the invention from the SEM of humidification composite membrane section figure;
Fig. 2 is provided by the invention from humidification composite membrane embodiment 8 and comparative example 8 monocell performance comparison diagram under the humidification condition outside nothing;
Fig. 3 is provided by the invention from humidification composite membrane embodiment 8 battery performance comparison diagram under the humidification condition outside full humidification condition and nothing;
Fig. 4 be provided by the invention outside humidification composite membrane embodiment 8 is not having the battery performance curve of stability under the humidification.
Embodiment
The present invention will contain the casting solution of polymer solid electrolyte and supported catalyst, and the method by casting, spraying or curtain coating is prepared into self-humidifying composite proton exchange film or the method for casting solution by casting, spraying or curtain coating be filled in the porous reinforcing membrane and is prepared into self-humidifying composite proton exchange film.
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 the water of absorbing catalyst active component surface generation and the water that cathode side electrochemistry generates, when film needs moisture, in time discharge water and come wetting film, carrier can provide extra proton conduction path in composite membrane in addition, thereby improve the conductivity of composite membrane, improve the open circuit voltage and the battery performance of battery.
Comprise two classes from the humidification composite membrane among the present invention, the first makes polyelectrolyte solution with polyelectrolyte with the high boiling solvent dissolving, then supported catalyst is carried out decentralized system in solution and get casting solution, become self-humidifying composite proton exchange film by casting, spraying or curtain coating mode solvent flashing; Its two employings higher boiling point dissolving polymer solid electrolyte, adding mid-boiling point or low boiling point solvent, then supported catalyst is carried out decentralized system in solution and get casting solution, the mode solvent flashing by casting, spraying or curtain coating becomes self-humidifying composite proton exchange film.Wherein high boiling solvent dissolves 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 curtain coating prepares in the process of composite membrane, be volatilize at a lower temperature mid-boiling point, low boiling point solvent, synchronous volatilization high boiling solvent is separated out with the position that guarantees the relative porous reinforcing membrane of polyelectrolyte when the dissolved state.Heat treatment process 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 macromolecular chain of the high polymer main chain of polymer solid electrolyte and porous reinforcing membrane merges crystallization more again, has improved the mechanical strength of film.
Also the invention will be further described in conjunction with the accompanying drawings below by embodiment, and technology of the present invention is not limited to embodiment.
Embodiment 1: with the H of 3.7mg/ml
2PtCl
6Solution and nanometer SO
-2 4/ ZrO
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 200 ℃
2Reduction 10h is prepared into supported catalyst Pt/ (SO
-2 4/ ZrO
2), the Pt loading is 0.2wt.%.
Embodiment 2: with the HAuCl of 3.7mg/ml
4Solution and nanometer SO
-2 4/ Fe
2O
3Flood 24h under equal-volume (50ml) room temperature, utilize H again at 120 ℃
2Reduction 10h is prepared into supported catalyst Au/ (SO
-2 4/ Fe
2O
3), the Au loading is 10
-3Wt.%.
Embodiment 3: with the PdCl of 10mg/ml
2Solution and nanometer SO
-2 4/ Fe
2O
3Flood 24h under equal-volume (50ml) room temperature, utilize H again at 300 ℃
2Reduction 10h is prepared into supported catalyst Pd/ (SO
-2 4/ Fe
2O
3), the Pd loading is 1wt.%.
Embodiment 4: with the AgNO of 20mg/ml
3Solution and nanometer SO
-2 4/ (ZrO
2-TiO
2) flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Ag/SO
-2 4/ (ZrO
2-TiO
2), the Ag loading is 5wt.%.
Embodiment 5: with the Pt (NH of 20mg/ml
3)
4Cl
2Solution and nanometer Cs
2.5H
0.5PW
12O
40Flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/Cs
2.5H
0.5PW
12O
40, the Pt loading is 20wt.%.
Embodiment 6: with the Pt (NH of 20mg/ml
3)
4Cl
2Solution and nanometer Zr (HPO
4)
2Flood 24h under equal-volume (50ml) room temperature, utilize H again at 250 ℃
2Reduction 10h is prepared into supported catalyst Pt/Zr (HPO
4)
2, the Pt loading is 10wt.%.
Embodiment 7: take by weighing Nafion resin (EW=1100g/mol
SO3H) 5 grams, forming Nafion resin quality concentration in N-N-methyl-2-2-pyrrolidone N-dissolving is 3% solution, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 1: 70) that adds then among the embodiment 2 disperseed 15 hours in ultrasonic wave, stir and formed casting solution in 10 hours, then casting solution is poured on the clean glass plate 70 ℃ of heating 10 hours, after solvent volatilized substantially, 120 ℃ of heat treatment was 1 hour in vacuum drying oven, places 3%H then
2 O
260 ℃ were boiled 100 minutes in the solution, took out the back then and were placed on 0.5MH with washed with de-ionized water
2SO
4In 70 ℃ boiled 80 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 50 μ m.
Embodiment 8: take by weighing sulfonated polyether-ether-ketone (SPEEK, sulfonation degree is 70%) 3 grams, at N, the dinethylformamide dissolving forms 13% solution, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 1: 10) that adds then among the embodiment 1 disperseed 5 hours in ultrasonic wave, stir and formed casting solution in 22 hours, curtain coating casting solution on the glass plate of cleaning then, 80 ℃ of heating 10 hours, after solvent volatilizees substantially, 180 ℃ of heat treatment is 1 hour in vacuum drying oven, places 5%H then
2 O
290 ℃ were boiled 50 minutes in the solution, took out the back then and were placed on 2MH with washed with de-ionized water
2SO
4In 90 ℃ boiled 100 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 25 μ m.
Comparing embodiment 8: take by weighing sulfonated polyether-ether-ketone (SPEEK, sulfonation degree is 70%) 3 grams, at N, the dinethylformamide dissolving forms 13% solution, curtain coating casting solution on the glass plate of cleaning heated 10 hours at 80 ℃, after solvent volatilizees substantially then, 180 ℃ of heat treatment is 1 hour in vacuum drying oven, places 5%H then
2 O
290 ℃ were boiled 50 minutes in the solution, took out the back then and were placed on 2MH with washed with de-ionized water
2SO
4In 90 ℃ boiled 100 minutes, promptly obtain comparative example SPEEK film with washed with de-ionized water at last, thickness is 25 μ m;
Preparation thickness is the comparative example SPEEK/Pt-SiO of 25 μ m
2Composite membrane, wherein Pt-SiO
2Method for preparing catalyst is consistent with embodiment 1 catalyst with the Pt loading, SPEEK/Pt-SiO
2The composite membrane preparation method is identical with embodiment 8.
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
As can be seen from Figure 1 existing from humidification composite membrane section pore-free of the present invention's preparation, compactness is good.
As can be seen from Figure 2, composite membrane of the present invention shows under the humidification condition outside not having and is better than comparative example SPEEK film and comparative example SPEEK/Pt-SiO
2The performance of composite membrane, its reason be in the composite membrane of the present invention supported catalyst can catalysis the reaction gas of infiltration generate water, and this catalyst carrier and comparative example SPEEK/Pt-SiO
2The SiO of middle catalyst
2Carrier is compared, and except having the ability that keeps moisture, thereby and has the ability of leading proton and shows good performance.
As can be seen from Figure 3, the battery performance of composite membrane of the present invention under full humidification and no humidification condition is very approaching;
As can be seen from Figure 4, composite membrane of the present invention outside not having under the humidification condition battery have good stable.
Embodiment 9: take by weighing sulfonated polyether sulfone (sulfonation degree is 40%) 2 grams, dissolving formation sulfonated polyether sulfone mass concentration is 8% solution in the N-N-methyl-2-2-pyrrolidone N-, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 1: 100) that adds then among the embodiment 6 disperseed 10 hours in ultrasonic wave, stir and formed casting solution in 10 hours, then casting solution is poured on the clean glass plate 80 ℃ of heating 10 hours, after solvent volatilizees substantially, 200 ℃ of heat treatment is 1 hour in vacuum drying oven, places 3%H then
2 O
250 ℃ were boiled 30 minutes in the solution, took out the back then and were placed on 0.5MH with washed with de-ionized water
2SO
4In 70 ℃ boiled 100 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 150 μ m.
Embodiment 10: take by weighing Nafion resin (EW=1100g/mol
SO3H) 1 gram, mixed solution (the volume ratio that adds N-N-methyl-2-2-pyrrolidone N-and ethanol, the N-N-methyl-2-2-pyrrolidone N-: ethanol=9: 1) formation Nafion mass concentration is 1% solution, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 1: 20) that adds among embodiment 1 and the embodiment 2 disperseed 10 hours in ultrasonic wave, stirred to form casting solution in 8 hours.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 casting solution into, the gross mass 2g of the casting solution of filling on every square centimeter of porous reinforcing membrane wherein is 77 ℃ of heating 10 hours, after solvent volatilizees substantially, 120 ℃ of heat treatment is 1 hour in vacuum drying oven, places 5%H then
2O
2100 ℃ were boiled 60 minutes in the solution, took out the back then and were placed on 1MH with washed with de-ionized water
2SO
4In 90 ℃ boiled 80 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 100 μ m.
Embodiment 11: get sulfonated polystyrene ion exchange resin (sulfonation degree is 70%) 0.5 gram, mixed solution dissolving (the volume ratio that adds dimethyl sulfoxide (DMSO) and n-butanol, dimethyl sulfoxide (DMSO): n-butanol=1: 1) making the sulfonated polystyrene mass concentration is 10% solution, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 1: 100) that adds among embodiment 3 and the embodiment 4 disperseed 0.5 hour in ultrasonic wave, stirred to form casting solution in 20 hours.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, casting solution is sprayed on the polyimide film of hole, the gross mass 0.03g of the casting solution of filling on every square centimeter of porous reinforcing membrane wherein is 80 ℃ of heating 10 hours, after solvent volatilizees substantially, 150 ℃ of heat treatment is 4 hours in vacuum drying oven, places 5%H then
2O
2100 ℃ were boiled 60 minutes in the solution, took out the back then and were placed on 1.5MH with washed with de-ionized water
2SO
4In 80 ℃ boiled 60 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 10 μ m.
Embodiment 12: take by weighing sulfonated polyimide (sulfonation degree is 50%) 2 grams, add N, mixed solution (the volume ratio of N-dimethylacetylamide and propyl alcohol, N, the N-dimethylacetylamide: propyl alcohol=1: 5) to make the sulfonated polyimide mass concentration be 1% solution in dissolving, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 20: 1) that adds among embodiment 5 and the embodiment 6 disperseed 0.5 hour in ultrasonic wave, stirred to form casting solution in 1 hour.With the porous polypropylene film thickness at 70 μ m, the aperture is 0.7 μ m, porosity is tightened on the flat board 65%, curtain coating casting solution on perforated membrane, the gross mass 9g of the casting solution of filling on every square centimeter of porous reinforcing membrane wherein is 100 ℃ of heating 10 hours, after solvent volatilizees substantially, 150 ℃ of heat treatment is 4 hours in vacuum drying oven, places 4%H then
2O
260 ℃ were boiled 60 minutes in the solution, took out the back then and were placed on 1.5MH with washed with de-ionized water
2SO
4In 80 ℃ boiled 100 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 150 μ m.
Embodiment 13: take by weighing sulfonated poly (phenylene oxide) (sulfonation degree is 60%) 1 gram, add N, mixed solution (the volume ratio of dinethylformamide and isopropyl alcohol, N, dinethylformamide: isopropyl alcohol=2: 1) to make the sulfonated poly (phenylene oxide) mass concentration be 6% solution in dissolving, the supported catalyst (supported catalyst: the mass ratio of high score solid electrolyte is 1: 1) that adds among embodiment 3 and the embodiment 6 disperseed 0.7 hour in ultrasonic wave, stirred to form casting solution in 2 hours.With porous polysulfone membrane thickness between 40 μ m, the aperture is 1 μ m, porosity is tightened on the flat board 95%, curtain coating casting solution on perforated membrane, the gross mass 1g of the casting solution of filling on every square centimeter of porous reinforcing membrane wherein is 60 ℃ of heating 10 hours, after solvent volatilizees substantially, 170 ℃ of heat treatment is 24 hours in vacuum drying oven, places 4%H then
2O
270 ℃ were boiled 60 minutes in the solution, took out the back then and were placed on 1.5MH with washed with de-ionized water
2SO
4In 80 ℃ boiled 100 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last, thickness is 50 μ m.
Claims (9)
1. self-humidifying fuel cell compound proton exchange membrane, it is characterized in that: described composite membrane is to contain the casting solution of polymer solid electrolyte and supported catalyst, adopts casting, spraying or casting method to be prepared into self-humidifying composite proton exchange film or to adopt casting, spraying or casting method to be filled in the porous reinforcing membrane casting solution and is prepared into self-humidifying composite proton exchange film;
The mass ratio of supported catalyst and polymer solid electrolyte is 1: 100～20: 1 in the casting solution; The loading of supported catalyst catalytic activity component is 10
-3～20wt.%; The catalytic activity component is one or more the mixed catalyst component among Pt, Au, Pd, the Ag, and carrier is SO
-2 4/ Fe
2O
3, SO
-2 4/ ZrO
2, SO
-2 4/ TiO
2, SO
-2 4/ (SiO
2-Al
2O
3), SO
-2 4/ (SiO
2-TiO
2), SO
-2 4/ (WO
3-ZrO
2), SO
-2 4/ (SiO
2-ZrO
2), SO
-2 4/ (ZrO
2-TiO
2), SO
-2 4/ (ZrO
2-MoO
3), Zr (HPO
4)
2, Cs
XH
3-XBM
12O
40In one or more compound; X=0～3 wherein, B=P, Si or As, M=Mo, W or V.
2. according to the described self-humidifying fuel cell compound proton exchange membrane of claim 1, it is characterized in that: described polymer solid electrolyte is any in sulfonated polyether-ether-ketone, SPSF, sulfonated polyether sulfone, sulfonated polyimide, sulfonated polyphenyl and imidazoles, sulfonated polystyrene, sulfonated polyphenyl thioether, sulfonated poly (phenylene oxide), sulfonation poly quinoline, sulfonation polysilane or the perfluorinated sulfonic resin.
3. according to the described self-humidifying fuel cell compound proton exchange membrane of claim 1, it is characterized in that: the mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～5: 1 in the casting solution.
4. according to the described self-humidifying fuel cell compound proton exchange membrane of claim 1, 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%;
When compound proton exchange membrane has adopted the porous reinforcing membrane, the wherein supported catalyst of filling on every square centimeter of porous reinforcing membrane and the gross mass 10 of polymer solid electrolyte
-3～1g.
5. according to the described self-humidifying fuel cell compound 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%.
6. according to the described self-humidifying fuel cell compound proton exchange membrane of claim 1, it is characterized in that: prepared is 10～150 μ m from humidification composite membrane thickness.
7. the described self-humidifying fuel cell of a claim 1 is with the synthetic method of compound proton exchange membrane, and it is characterized in that: the concrete operations step is as follows,
1) polymer solid electrolyte is made polymer solid electrolyte solution with the high boiling solvent dissolving, the weight concentration of polymer solid electrolyte is 3～15%; Or polymer solid electrolyte added mid-boiling point with high boiling solvent dissolving back or low boiling point solvent is made polymer solid electrolyte solution, the weight concentration of polymer solid electrolyte is 1～10%, the volume ratio of high boiler and mid-boiling point or low boiling point solvent 10: 1～1: 5;
2) with supported catalyst in polymer solid electrolyte solution ultrasonic 0.1～24 hour, stirred 0.1～24 hour, form casting solution; The mass ratio of supported catalyst and polymer solid electrolyte is 1: 100～20: 1 in the casting solution;
3) with step 2) in casting solution to the greatest extent be prepared into compound proton exchange membrane behind the solvent by casting, spraying or casting method in 50～120 ℃ of heating volatilization in 1～24 hour;
Or in the top casting of porous reinforcing membrane, spraying or curtain coating step 2) in casting solution, be prepared into compound proton exchange membrane behind the solvent flashing in 1～24 hour in 50～120 ℃ of heating; The gross mass 10 of the casting solution of filling on every square centimeter of porous reinforcing membrane wherein
-2～10g;
4) compound proton exchange membrane of step 3) preparation is heat-treated under 120～200 ℃ and inert atmosphere, the processing time is 5 minutes～24 hours;
5) with the compound proton exchange membrane after the step 4) heat treatment in 3～5%H
2O
250～100 ℃ were boiled 30～100 minutes in the solution, took out the back and were placed on 0.5～2MH with washed with de-ionized water
2SO
4In 50～100 ℃ boiled 30～100 minutes, promptly obtain self-humidifying composite proton exchange film with washed with de-ionized water at last.
8. according to the synthetic method of the described self-humidifying fuel cell of claim 7 with compound proton exchange membrane, it is characterized in that: the loading of the catalytic activity component of supported catalyst is 10
-3～20wt.%; The catalytic activity component is one or more the mixed catalyst component among Pt, Au, Pd, the Ag, and carrier is SO
-2 4/ Fe
2O
3, SO
-2 4/ ZrO
2, SO
-2 4/ TiO
2, SO
-2 4/ (SiO
2-Al
2O
3), SO
-2 4/ (SiO
2-TiO
2), SO
-2 4/ (WO
3-ZrO
2), SO
-2 4/ (SiO
2-ZrO
2), SO
-2 4/ (ZrO
2-TiO
2), SO
-2 4/ (ZrO
2-MoO
3), Zr (HPO
4)
2, Cs
XH
3-XBM
12O
40In one or more compound, X=0～3 wherein, B=P, Si or As, M=Mo, W or V; The mass ratio of supported catalyst and polymer solid electrolyte is 1: 50～5: 1 in the casting solution; 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.
9. according to the synthetic method of the described self-humidifying fuel cell of claim 7, it is characterized in that with compound proton exchange membrane: described preparation be 10～150 μ m from humidification composite membrane thickness.
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| CN101706485B (en) * | 2009-11-23 | 2013-06-26 | 北京联合大学生物化学工程学院 | Doped nano sensitive material for monitoring benzene |
| CN102479959A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Self-humidifying proton exchange film for fuel cell, and preparation method thereof |
| CN104558649B (en) * | 2015-01-10 | 2017-10-20 | 复旦大学 | Polyvinylidene fluoride modified perfluorinated sulfonic acid class PEM and preparation method thereof |
| CN106876757B (en) * | 2015-12-12 | 2020-02-21 | 中国科学院大连化学物理研究所 | Functional enhanced proton exchange membrane and preparation method thereof |
| CN108511777A (en) * | 2018-04-04 | 2018-09-07 | 华南理工大学 | The construction method of proton exchange membrane with three-dimensional high-specific surface area surface and its high-performance membrane electrode based on this proton exchange membrane |
| CN109755614A (en) * | 2019-03-18 | 2019-05-14 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone load non-platinum catalyst proton exchange membrane |
| CN110444793B (en) * | 2019-08-16 | 2021-02-05 | 上海元城汽车技术有限公司 | Durable proton exchange membrane, 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 |
| CN115441025B (en) * | 2022-11-09 | 2023-04-18 | 国家电投集团氢能科技发展有限公司 | Colorless proton exchange membrane, preparation method thereof and fuel cell |
| CN118127564B (en) * | 2024-05-08 | 2024-08-20 | 山东东岳未来氢能材料股份有限公司 | Hypotonic hydrogen proton exchange membrane and preparation method and application thereof |
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