CN100386367C - Preparation process of composite proton exchanging member based on hydrophilic porous poly tetrafluoro ethylene matrix - Google Patents
Preparation process of composite proton exchanging member based on hydrophilic porous poly tetrafluoro ethylene matrix Download PDFInfo
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- CN100386367C CN100386367C CNB2006100193866A CN200610019386A CN100386367C CN 100386367 C CN100386367 C CN 100386367C CN B2006100193866 A CNB2006100193866 A CN B2006100193866A CN 200610019386 A CN200610019386 A CN 200610019386A CN 100386367 C CN100386367 C CN 100386367C
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- 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
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- Y02E60/30—Hydrogen technology
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Abstract
The present invention provides the preparation method of a composite proton exchanging membrane based on hydrophilic porous polytetrafluoroethylene base body, which is characterized in that hydrophilic treatment is firstly provided for porous polytetrafluoroethylene, proton conducting resin is filled into the porous polytetrafluoroethylene after treatment, and then the composite proton exchanging membrane with reinforced hydrophilic porous polytetrafluorethylene is obtained by heat treatment and protonation. The porous polytetrafluoroethylene base body after the hydrophilic treatment and the proton conducting resin can be excellently combined. The prepared composite proton exchanging membrane has the advantages of good proton conductivity, high mechanical strength, good gas permeability, and excellent applying effect in the fuel batter with the proton exchanging membrane.
Description
Technical field
The present invention relates in Proton Exchange Membrane Fuel Cells,, isolate the preparation method of the proton exchange membrane of polarization response gas simultaneously again as barrier film for ionogen provides the hydrogen ion passage.Be specifically related to a kind of preparation method of the compound proton exchange membrane based on hydrophilic porous poly tetrafluoro ethylene matrix.
Background technology
(Proton exchange membrane is that (output performance of its performance characteristic and fuel cell is closely related for Proton exchangemembrane fuel cell, critical material PEMFC) for Proton Exchange Membrane Fuel Cells PEM) to proton exchange membrane.The ideal proton exchange membrane not only will have proton conductivity and chemical stability preferably, also need low gas permeability, enough physical strengths and dimensional stability [Fuel Cells and Their Applications, 1996, Chapter 4] preferably.
What Proton Exchange Membrane Fuel Cells mainly adopted at present is perfluorinated sulfonic acid type proton exchange membrane, the Nafion series membranes of du pont company for example, this class film has good proton conductivity and chemical stability, but its complete processing comparatively complicated, cost an arm and a leg.Its inherent strength of what is more important is not that very high, pure perfluorinated sulfonic acid type proton exchange membrane must have certain thickness, and its intensity could satisfy the actual needs (it is generally acknowledged that dry state thickness should be more than the 50um) of fuel cell; Because almost linear dependence, the i.e. thicker ohm voltage drop [Journal ofMembrane Science 237,2004,1-7, US Patent 5,547,551] greatly that causes of film of the thickness of ohm voltage drop and film in the battery operation.
In order to solve the contradiction between proton exchange film toughness and the ohm voltage drop, the investigator has carried out fiber reinforcement [Key Engineering Materials to proton exchange membrane, 249,2003,385-390] or porous Teflon [Handbook of Fuel Cells, Volume 3, and Part 3, pp 566-575] enhancement process, and obtain more satisfactory result.The wherein most representative porous Teflon that is Ge Er (Gore) company produces strengthens perfluoro sulfonic acid membrane, they adopt the EW value is that the film physical strength of 1100 resins is 2～3 times of pure perfluoro sulfonic acid membrane, therefore its thickness that satisfies the fuel cell needs can be reduced to 20um, this moment, the longitudinal conductance rate of proton exchange membrane was about 1.5 times of Nafion112 (dry state thickness 51um), battery performance is corresponding to improve a lot, because reduced the usage quantity of expensive perfluorinated sulfonic resin, its cost also decreases.
The preparation method that porous Teflon strengthens perfluoro sulfonic acid membrane directly is placed on porous Teflon dipping [US Patent 5 in the proton conductive resin, 547,551, US5,599,614, US5,635,041, US 6,613,203], perhaps place electrode on the porous Teflon both sides, adopt electrophoretic method to allow perfluorinated sulfonic resin pass porous Teflon [WOPatent 00/78850A1] then, perhaps high boiling organic solvent dissolved perfluor sulfoacid resin solution is added drop-wise to [the Chinese patent CN1416186 of solvent flashing on the porous Teflon, Journal of Membrane Science 212,2003,213-223] be prepared from.Yet because porous Teflon intensive hydrophobic nature and aperture are only about 1 micron, and perfluorinated sulfonic resin is actually a kind of strong hydrophilicity material, even added tensio-active agent in the perfluor sulfoacid resin solution, it also is very difficult [Electrochimica Acta 50 that yet perfluor sulfoacid resin solution enters in the porous Teflon, 2004,571-575].
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of compound proton exchange membrane based on hydrophilic porous poly tetrafluoro ethylene matrix, be characterized in voided polytetrafluoroethylene film is carried out hydrophilic treatment, prepared compound proton exchange membrane has resin compactedness height, the proton conduction performance is good, physical strength is high, gas permeability is low, cost is low characteristics, is specially adapted to Proton Exchange Membrane Fuel Cells.
The preparation method of the compound proton exchange membrane based on hydrophilic porous poly tetrafluoro ethylene matrix provided by the invention, undertaken by following steps in sequence:
Step 1, voided polytetrafluoroethylene film is carried out hydrophilic treatment, hydrophilic porous poly tetrafluoroethylene;
Step 2, get clean hydrophilic porous poly tetrafluoroethylene and in proton conductive resin solution, flood, dipping time is 0.5～4 minute, the content of proton conductive resin is quality 1%～20% in the mixed solution, preferred 3%～10%, the content of tensio-active agent Trinton-100 (octylphenol polyethylene ethoxy ethanol) is quality 0～4%, and solvent adopts any or its mixture in ethanol, propyl alcohol and the Virahol;
Step 3, will be impregnated with the hydrophilic porous poly tetrafluoroethylene of proton conductive resin solution, and adopt the two-wheel wheel to roll to roll and remove the unnecessary resin solution in surface, the film after rolling 40～60 seconds of thermal treatment in vacuum drying oven;
Step 4, repeating step 2 become transparent to the operation of step 3 1～4 time until film;
Step 5, the film that step 4 is obtained soak 5～10 minutes removal tensio-active agents in ethanol or Virahol, in the ebullient deionized water, soaked 10 minutes then, taking-up is after seasoning, obtain hydrophilic porous tetrafluoroethylene enhanced compound proton exchange membrane 120～230 ℃ of 40～60 seconds of thermal treatment in loft drier.
Voided polytetrafluoroethylene film thickness of the present invention is 1～40 micron, preferred 8～20 microns; 0.05～4 micron in aperture, porosity 70%～95%.
It is of the present invention that voided polytetrafluoroethylene film is carried out hydrophilic treatment method is wherein any of plasma treatment, plasma graft, radiation grafting and chemical modification.
Plasma processing method is: utilize the active particle of plasma generation such as ion, electronics, free radical, excited atom and molecule that material surface is handled.Use non-polymerization gas Ar, the free radical of generation can with airborne oxygen or the water formation superoxide that reacts, further with function monomer vinylformic acid generation crosslinking polymerization, obtain hydrophilic surface; Perhaps use polymerizability gas, free radical can clash into mutually in gas phase or film surface, in conjunction with forming film polymer.
Of the present inventionly voided polytetrafluoroethylene film is carried out described Cement Composite Treated by Plasma be, use Ar gas that the voided polytetrafluoroethylene film surface is handled, the free radical that Ar produces can react with airborne oxygen or water and form superoxide and make the porous Teflon surface produce functional group's group, adopt the further cross-linking reaction polymerization of voided polytetrafluoroethylene film of function monomer vinylformic acid and functionalization again, obtain hydrophilic surface.
The plasma graft method is: plasma body initiation grafting polymeric modification, introduce long hydrophilic macromolecule chain, and bigger to hydrophilic improvement degree, and the improvement of surface properties does not decay in time.
Of the present inventionly voided polytetrafluoroethylene film is carried out plasma graft be: with Ar plasma body pre-treatment voided polytetrafluoroethylene film, use wetting ability function monomer vinylformic acid, styrene sulfonic acid sodium salt, N again, graft copolymerization takes place in the N-N,N-DIMETHYLACETAMIDE or the glycidyl methacrylate aqueous solution under the inducing of near-ultraviolet light.
Of the present inventionly voided polytetrafluoroethylene film is carried out radiation grafting be: voided polytetrafluoroethylene film is placed the polymerisable monomer of vinylbenzene, FUMARIC ACID TECH GRADE or methyl acrylic ester, with
60The Co radiation, the chemical graft polymerization takes place on the voided polytetrafluoroethylene film surface in monomer, is easy to bonding graftomer thereby make the voided polytetrafluoroethylene film surface form one deck.
Of the present inventionly voided polytetrafluoroethylene film is carried out chemical modification be, voided polytetrafluoroethylene film is handled to improve its surface hydrophilicity through chemical reagent, described chemical reagent is the ammonia solution of sodium Metal 99.5, naphthalene sodium tetrahydrofuran solution, the amalgam of alkali-metal, any in the iron pentacarbonyl solution.
Proton conductive resin of the present invention is perfluorinated sulfonic resin, sulfonation trifluorostyrene resin, polyphenylmethyl base sulfonic acid silicone resin, sulfonated polyether-ether-ketone resin, sulfonated polystyrene-polyethylene and ethylene copolymers resin, and any in sulfonated polystyrene-polyethylene/butylene-polystyrene resin.
The present invention will be impregnated with the hydrophilic porous poly tetrafluoroethylene of proton conductive resin, 120～230 ℃ of 30～60 seconds of thermal treatment, vapor away the solvent of resin, the thermal treatment temp of choosing is relevant with the proton conductive resin of choosing, and thermal treatment temp is between the second-order transition temperature of proton conductive resin and hydrophilic porous poly tetrafluoroethylene.
The present invention compares with background technology, prepared based on hydrophilic porous poly tetrafluoro ethylene matrix compound proton exchange membrane have good resin compactedness, proton conductivity is strong, the gas-permeable ability is little, mechanical property is high, steady operation for a long time in battery.
Description of drawings
Accompanying drawing 1 is the cross-section photograph of hydrophilic porous tetrafluoroethylene enhanced perfluorinated sulfonic acid proton exchange membrane among the embodiment 1;
Accompanying drawing 2 be among the embodiment 1 as a comparison, the cross-section photograph of hydrophilic treatment porous Teflon enhanced perfluorinated sulfonic acid proton exchange membrane not;
Accompanying drawing 3 is the cross-section photograph of hydrophilic porous tetrafluoroethylene enhanced sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) among the embodiment 2;
Accompanying drawing 4 for among the embodiment 2 as a comparison, the cross-section photograph of hydrophilic treatment porous Teflon enhanced sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM) not.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
Get porous Teflon (PTFE) film of 10 micron thickness, 0.05～2 micron in aperture, porosity 85%, use Ar gas that the PTFE surface is handled, the free radical that Ar gas produces can with airborne oxygen or the water formation superoxide that reacts, further, obtain hydrophilic surface with function monomer-vinylformic acid generation crosslinking polymerization.Voided polytetrafluoroethylene film after the hydrophilic treatment is placed on the perfluor proton conductive resin (Nafion of 5% (quality), EW value 1100) dipping is 10 minutes in the aqueous isopropanol, taking-up is adopted the two-wheel wheel to roll and is rolled one time then, film after rolling is put into vacuum drying oven, adjust the temperature to 160 ℃, 60 seconds of thermal treatment repeat above-mentioned dip treating process 4 times, obtain transparent composite membrane; This film soaked in Virahol removed organic impurity in 5 minutes, soaked 10 minutes at the ebullient deionized water then, take out after seasoning, obtain hydrophilic porous tetrafluoroethylene enhanced proton exchange membrane 140 ℃ of 40 seconds of thermal treatment in loft drier.
The prepared hydrophilic porous tetrafluoroethylene enhanced perfluorinated sulfonic acid proton exchange membrane cross-section photograph of the present invention as shown in Figure 1 because the raising of proton conductive resin compactedness, prepared film has excellent performance, the detailed performance parameter is listed in table 1.As a comparison, voided polytetrafluoroethylene film is not carried out hydrophilic treatment, the cross-section photograph of the compound proton exchange membrane that other process is identical with present embodiment as shown in Figure 2, this composite membrane does not have good compactedness.
Embodiment 2
Get porous Teflon (PTFE) film of 12 micron thickness, 0.05～2 micron in aperture, porosity 85%, with Ar plasma body pre-treatment PTFE film, with wetting ability function monomer vinylformic acid, styrene sulfonic acid sodium salt, N,N-dimethylacetamide and the glycidyl methacrylate aqueous solution graft copolymerization takes place again under the inducing of near-ultraviolet light.Voided polytetrafluoroethylene film after the hydrophilic treatment is placed on the sulfonated polyether-ether-ketone resin (s-PEEK of 5% (quality), EW value 900) and in the Trinton-100 ethanolic soln of 2% (quality) flooded 10 minutes, taking-up is adopted the two-wheel wheel to roll and is rolled one time then, film after rolling is put into vacuum drying oven, adjust the temperature to 230 ℃, 50 seconds of thermal treatment repeat above-mentioned dip treating process 5 times, obtain transparent composite membrane; This film soaked in Virahol removed organic impurity in 5 minutes, soaked 10 minutes at the ebullient deionized water then, taking-up after seasoning, 230 ℃ of 60 seconds of thermal treatment in loft drier, hydrophilic porous tetrafluoroethylene enhanced sulfonated poly-ether-ether-ketone (SPEEK) proton exchange membrane (PEM).Its cross-section photograph as shown in Figure 3; As a comparison, voided polytetrafluoroethylene film is not carried out hydrophilic treatment, the cross-section photograph of the compound proton exchange membrane that other process is identical with present embodiment as shown in Figure 4, this composite membrane does not have good compactedness.
The performance perameter of table 1. compound proton exchange membrane
Claims (8)
1. the preparation method based on the compound proton exchange membrane of hydrophilic porous poly tetrafluoro ethylene matrix is characterized in that, is undertaken by following steps in sequence:
Step 1, voided polytetrafluoroethylene film is carried out hydrophilic treatment, hydrophilic porous poly tetrafluoroethylene, hydrophilic treatment method is plasma treatment or plasma graft;
Step 2, get clean hydrophilic porous poly tetrafluoroethylene and in containing the mixing solutions of proton conductive resin, flood, dipping time is 10 minutes, the content of proton conductive resin is quality 1%～20% in the mixing solutions, the content of tensio-active agent octylphenol polyethylene ethoxy ethanol is quality 0～4%, and solvent is any or its mixture in ethanol, propyl alcohol and the Virahol;
Step 3, will be impregnated with the hydrophilic porous poly tetrafluoroethylene of proton conductive resin solution, and adopt the two-wheel wheel to roll to roll and remove the unnecessary resin solution in surface, the film after rolling 40～60 seconds of thermal treatment in vacuum drying oven;
Step 4, repeating step 2 become transparent to the operation of step 3 1～4 time until film;
Step 5, the film that step 4 is obtained soak 5～10 minutes removal tensio-active agents in ethanol or Virahol, then, in the ebullient deionized water, soaked 10 minutes, after taking out seasoning, obtain hydrophilic porous tetrafluoroethylene enhanced compound proton exchange membrane 120～230 ℃ of 40～60 seconds of thermal treatment in loft drier.
2. the method for claim 1 is characterized in that, described voided polytetrafluoroethylene film thickness is 1～40 micron, 0.05～4 micron in aperture, porosity 70%～95%.
3. the method for claim 1, it is characterized in that, described Cement Composite Treated by Plasma is, use Ar gas that the voided polytetrafluoroethylene film surface is handled, the free radical that Ar produces can react with airborne oxygen or water and form superoxide and make the porous Teflon surface produce functional group's group, adopt the further cross-linking reaction polymerization of voided polytetrafluoroethylene film of function monomer vinylformic acid and functionalization again, obtain hydrophilic surface.
4. the method for claim 1, it is characterized in that, described plasma graft is, with Ar plasma body pre-treatment voided polytetrafluoroethylene film, use wetting ability function monomer vinylformic acid, styrene sulfonic acid sodium salt, N again, graft copolymerization takes place in the N-N,N-DIMETHYLACETAMIDE or the glycidyl methacrylate aqueous solution under the inducing of near-ultraviolet light.
5. the method for claim 1, it is characterized in that described proton conductive resin is any in perfluorinated sulfonic resin, sulfonation trifluorostyrene resin, polyphenylmethyl base sulfonic acid silicone resin, sulfonated polyether-ether-ketone resin, sulfonated polystyrene-polyethylene and ethylene copolymers resin and the sulfonated polystyrene-polyethylene/butylene-polystyrene resin.
6. the method for claim 1 is characterized in that, the content of proton conductive resin is quality 3%～10% in the mixing solutions of described step 2.
7. the method for claim 1 is characterized in that, described voided polytetrafluoroethylene film thickness is 8～20 microns.
8. the method for claim 1 is characterized in that, is impregnated with the hydrophilic porous poly tetrafluoroethylene of proton conductive resin in the described step 3, the film after rolling in vacuum drying oven 120～230 ℃ of 40～60 seconds of thermal treatment.
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