CN1253952C - Method for producing multi-layer nano composite proton exchange membrane with self-humidifying function - Google Patents
Method for producing multi-layer nano composite proton exchange membrane with self-humidifying function Download PDFInfo
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- CN1253952C CN1253952C CNB200410061104XA CN200410061104A CN1253952C CN 1253952 C CN1253952 C CN 1253952C CN B200410061104X A CNB200410061104X A CN B200410061104XA CN 200410061104 A CN200410061104 A CN 200410061104A CN 1253952 C CN1253952 C CN 1253952C
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Abstract
The present invention provides a method for preparing multi-layer nanometer composite proton exchange membrane with a self-humidifying function, which is characterized in that a polytetrafluoroethylene (PTFE) porous membrane is soaked in a mixture of proton conductive resin and SiO2 or TiO2 nanometer particles firstly to form a water retaining proton conductive layer and then is soaked in a mixture of proton conductive resin and nanometer Pt or nanometer Pd particles to form a self-humidifying proton conductive layer. Used as a proton conductive membrane for a proton exchange membrane fuel battery, the composite membrane has favorable self-humidifying and water retaining capabilities.
Description
Technical field
The present invention relates in the battery operation process, have preparation method from the proton exchange membrane of humidifying capacity and water holding capacity.Be specifically related to have the preparation method of the multi-layer nano compound proton exchange membrane of self-moistening function.
Background technology
Because hydrogen fuel cell is significant to solving " energy shortage " and " environmental pollution " this two big worlds difficult problem, international energy circle generally believes that Hydrogen Energy is a kind of energy of sustainable development, 21 century is Hydrogen Energy century, and the mankind will take leave of fossil energy and enter the Hydrogen Energy economy era.Proton Exchange Membrane Fuel Cells (PEMFC) is the energy power system of new generation that has the energy revolution meaning after steam engine and internal combustion engine, in service at PEMFC, and the conductivity of proton exchange membrane and water content are almost linear.In order to make film be in the well-hydrated state, the general mode of humidification in outer humidification mode and the pile that adopts is carried out humidification to proton exchange membrane.All use the humidification auxiliary system in the PEMFC system of outer humidification and interior humidification, therefore increased quality, cost and the complexity of battery system.The proton exchange membrane that the PEMFC that explores no humidification auxiliary system particularly has from humidifying capacity is one of effective way of simplifying battery system and structure.
Some scholars adopt in the middle of proton exchange membrane or a side additional catalyst layer solve film from the humidification problem, as SangHee Hwak (Joumal of Power Sources, 2003,118,200-204) wait the people at proton exchange membrane one side plasma sputtering one deck 0.05～0.2mg/cm
2Pt, make film have self-moistening function, FuQiang Liu (Journal of Power Sources, 2003,124, black or Pt/C solves this problem at two-layer Nafion film therebetween one deck Pt 81-89) to wait the people, and the performance of compound back battery all increases significantly; The particles of inorganic material that people such as the Mao Zongqiang of Tsing-Hua University (Chinese patent CN1442913A) will have a moisture-keeping functions is coated in the both sides of proton exchange membrane, make composite membrane with self-moistening function, but these methods have increased the contact interface of film in the battery inevitably, also brought the cracking problem of inorganic particulate granulosa, improved the Ohmic resistance of battery self, and the use amount of noble metal is very big when adopting noble metal catalyst Pt, has increased battery cost widely.
The other researcher adopts the method for chemical deposition at the nano level Pt particle of the inner formation of proton exchange membrane, enters the H of film inside with catalysis
2With O
2Combination, thereby realize humidification to film, as people such as watanabe (J.Electrochem.Soc., 1996,143,3847; J.Electrochem.Soc., 1998,145,1137) with the Pt uniform particles be entrained in the proton exchange membrane, this method can realize film from humidification, but the crossover network that the Pt particle forms in film can form continuous electron channel, may cause the self-discharge phenomenon of battery and makes battery failure.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with multi-layer nano compound proton exchange membrane of self-moistening function, for Proton Exchange Membrane Fuel Cells provides a kind of proton exchange membrane with self-moistening function, thereby reduce in the battery operation process because the possibility that the ohmic polarization that the proton exchange membrane dehydration brings increases.
A kind of preparation method of the present invention with multi-layer nano compound proton exchange membrane of self-moistening function, undertaken by following steps in sequence: 1, a kind of preparation method with multi-layer nano compound proton exchange membrane of self-moistening function is characterized in that being undertaken by following steps in sequence:
1st, get clean voided polytetrafluoroethylene film and containing proton conductive resin and SiO
2Or TiO
2Fully flood in the mixture alcoholic solution of nano particle, the content of proton conductive resin is 1-5wt% in the mixture, and the content of surfactant alkylphenol-polyethenoxy 10 ethers is 0.6-4wt%, SiO
2Or TiO
2The mass ratio of nano particle and proton conductive resin is 0.01-0.2: 1;
2nd, will be impregnated with proton conductive resin and SiO
2Or TiO
2The perforated membrane of nanoparticle mixture adopts the two-wheel wheel to roll to roll and removes the unnecessary resin compound in surface, and the perforated membrane after rolling is 80 ℃～140 ℃ 40～60 seconds of heat treatment in vacuum drying chamber;
3rd, the operation of dipping and step 2 obtains water-keeping proton exchange film until the film bleach in the repeating step 1;
4th, the transparent water-keeping proton exchange film that step 3 is obtained fully floods in proton conductive resin and nanometer Pt or nanometer Pd granulate mixture alcoholic solution, the content of proton conductive resin is 4wt% in the mixture, the content of surfactant alkylphenol-polyethenoxy 10 ethers is 2wt%, and the mass ratio of nanometer Pt or nanometer Pd particle and proton conductive resin keeps 0.01-0.05: 1;
5th, will be impregnated with the water-keeping proton exchange film of proton conductive resin and nanometer Pt or nanometer Pd granulate mixture, adopt the two-wheel wheel to roll to roll and remove the unnecessary resin compound in surface, the perforated membrane after rolling is 80 ℃～140 ℃ 40～60 seconds of heat treatment in vacuum drying chamber;
6th, repeating step 4 and 5 once obtains the multi-layer nano composite membrane successively;
7th, the composite membrane that step 6 is obtained soaks in ethanol or isopropyl alcohol and removed surfactant in 5～10 minutes, deionized water in boiling soaked 8～10 minutes then, after the air dry, in vacuum drying chamber,, promptly obtain having multi-layer nano compound proton exchange membrane from humidification and water holding capacity 120～140 ℃ of 40～60 seconds of heat treatment;
Wherein the solvent of the described alcoholic solution of step 1 and step 4 adopts any in ethanol, propyl alcohol and the isopropyl alcohol.
Described PTFE film thickness is 1～40 micron, preferred 7～15 microns; 0.05～4 micron in aperture, preferred 0.05～0.2 micron; Porosity 70%～95%, preferred 80～90%.
Proton conductive resin of the present invention can be any in perfluorinated sulfonic resin, sulfonation trifluorostyrene resin, polymethyl-benzene 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.
Described clean voided polytetrafluoroethylene film can adopt voided polytetrafluoroethylene film to use 3～5 successively.The H of 5wt%
2O
2The aqueous solution and absolute ethyl alcohol clean, dry preparation in 60 ℃ drying box then.
Described clean voided polytetrafluoroethylene film is containing proton conductive resin and SiO
2Or TiO
2Dip time is 1～5 minute in the mixture alcoholic solution of nano particle.
Described transparent water-keeping proton exchange film dip time in proton conductive resin and nanometer Pt or nanometer Pd granulate mixture alcoholic solution is 1～5 minute.
Be impregnated with proton conductive resin and SiO among the present invention
2Or TiO
2The perforated membrane of nanoparticle mixture and be impregnated with proton conductive resin and the water-keeping proton exchange film of nanometer Pt or nanometer Pd granulate mixture adopts the two-wheel wheel to roll when rolling, and the gap between two wheels is greater than 1～2 micron of the thickness of film.
Described nanometer SiO
2And nano-TiO
2Grain diameter 4～20 nanometers.Nanometer SiO wherein
2The preparation method be that fully to mix mol ratio be 1: 5～10: 0.1 tetraethoxysilane and the hydrochloric acid mixed solution of absolute ethyl alcohol and 0.4M, at 40～70 ℃ of following high-speed stirred 6-24 hours; Nano-TiO
2The preparation method butyl titanate and acetate are mixed, add deionized water under the high-speed stirred and stirred 1～4 hour, add red fuming nitric acid (RFNA) then and be heated to 60～80 ℃ of lasting stirrings 1～4 hour, its butyl titanate: acetate: deionized water: the mol ratio of nitric acid is 1: 0.4: 2: 4.
The grain diameter of described nanometer Pt and nanometer Pd is 1～4 nanometer.Its preparation method can be the salt precursor solution that adds Pt or Pd in the mixed solution of proton conductive resin and water and ethanol, and the presoma salt of synthesis of nano Pt particle is H
2PtCl
6, the presoma salt of synthesis of nano Pd particle is PdCl
2, the volume ratio of water and ethanol is 4: 3 when synthetic, and the mol ratio of proton conductive resin and presoma salt is 1～10: 1, and the molar concentration of presoma salt in mixed solution is 0.005M.The method of its preparation can also be to be that 0.5M presoma salt and 4～20gNaOH add in the 200mL ethylene glycol with molar concentration, being heated to 130～150 ℃ continues to stir 30～60 minutes, obtain the Pt of ethylene glycol dispersion or the nano-metal particle of Pd, add the metal nanoparticle that concentrated sulfuric acid centrifugation goes out Pt or Pd then.
The present invention compares with background technology, the multi-layer nano compound proton exchange membrane of the present invention's preparation, owing to have homodisperse nanocatalyst particle in the both sides of film, energy catalysis penetrates into the H of film inside
2With O
2In conjunction with, have from humidifying capacity; The nanocatalyst particle only is distributed in the both sides of film, can not be compounded in the continuous electron channel of intersection that forms in the film, therefore can not cause the self-discharge phenomenon of film; Proton conductive resin and SiO
2Or TiO
2The mixture of nano particle constitutes the intermediate layer of film, has water holding capacity; The mixture of proton conductive resin and nanometer Pt or Pd particle is immersed in proton conductive resin and SiO from the humidification layer with resin state
2Or TiO
2The nanoparticle mixture water conservation layer outside, consistent with water conservation layer main body composition from the humidification layer, experience rolls, film forming and removal surfactant process, can organically combine the phenomenon that does not exist cracking and contact resistance to increase.
Description of drawings
Fig. 1 is a multi-layer nano compound proton exchange membrane structural representation of the present invention.
Fig. 2 is multi-layer nano compound proton exchange membrane preparation process figure.
Fig. 3 is the resin microphoto that is used to flood the water conservation layer, and black particle is nanometer SiO among the figure
2
Fig. 4 is the resin microphoto that is used to flood from the humidification layer, and black particle is nanometer Pd among the figure.
Fig. 5 is the discharge curve of the multi-layer nano compound proton exchange membrane of embodiment 1 preparation.
Fig. 6 is the discharge curve of the multi-layer nano compound proton exchange membrane of embodiment 2 preparations.
Number in the figure implication: 1-proton conductive resin and SiO
2Or TiO
2The water conservation proton conduction layer that the mixture of nano particle forms, the mixture of 2-proton conductive resin and nanometer Pt or nanometer Pd particle form from the humidification proton conduction layer, a-polytetrafluoroethylene (PTFE) perforated membrane substrate, b-flood proton conductive resin and SiO on the polytetrafluoroethylporous porous membrane substrate
2Or TiO
2The mixture of nano particle forms the water conservation proton conduction layer, and c-floods proton conductive resin and nanometer Pt or nanometer Pd particle on the polytetrafluoroethylporous porous membrane that the water conservation proton conduction layer is arranged mixture forms from the humidification proton conduction layer.
Embodiment
The invention will be further described below by embodiment.
1, the porous PTFE film of getting 10 micron thickness, 0.05～2 micron in aperture, porosity 80% is fixed on the polycarbonate membrane of 40 micron thickness, adopts the H of 5wt% successively
2O
2The aqueous solution and absolute ethyl alcohol clean the PTFE film, in 60 ℃ drying box dry 20 minutes then;
2, fully mixing mol ratio is 1: 5: 0.1 tetraethoxysilane and the HCl mixed solution of absolute ethyl alcohol and 0.4M, 70 ℃ of following high-speed stirred 6～24 hours, obtains the SiO of 6 nanometers
2Nano particle; Press Nafion solution (EW1100 is available from Du pont company) 120g, surfactant alkylphenol-polyethenoxy 10 ethers (OP-10) 1.3g, the SiO of 5wt%
2Nano particle 0.5g prepares mixed solution, cleaned PTFE perforated membrane was flooded 2 minutes in this mixed solution, roll to roll with the two-wheel wheel then and remove the unnecessary mixed resin solution in surface, and with resin extruded in the micropore of composite membrane, the two-wheel wheel rolls when rolling, gap between two wheels is 11 microns, the perforated membrane after rolling in vacuum drying chamber in 120 ℃ of 40 seconds of heat treatment, 10 microns of the thickness that obtains; Film after the heat treatment is at above-mentioned Nafion resin and OP-10 and SiO
2Dipping is 2 minutes in the mixed solution of nano particle, and then rolls with two-wheel wheel and to roll, and when rolling, the gap between two wheels is 12 microns, the perforated membrane after rolling in vacuum drying chamber in 80 ℃～140 ℃ 40 seconds of heat treatment, 10.1 microns of the thickness that obtains; Again with its film at above-mentioned Nafion resin and OP-10 and SiO
2Dipping is 2 minutes in the mixed solution of nano particle, rolls with the two-wheel wheel and rolls, when rolling, gap between two wheels is 12 microns, perforated membrane after rolling in vacuum drying chamber 80 ℃～140 ℃ 40 seconds of heat treatment, 10.3 microns of the thickness that obtains, this moment, film became transparent;
3, remove ionized water 80mL and ethanol 60mL fully mixes, the Nafion solution 2mL, the Pd content that add Nafion5wt% are the PdCl of 10g/L
2Solution 10mL, reflux was separated with pellicle after 20 minutes, obtained the Pd nano particle of 2 nanometers; With content is that the Nafion solution of 5wt% and surfactant OP-10 and nanometer Pd particle are according to solid-state mass ratio preparation in 8: 4: 1 mixed solution; The transparent film that step 2 is obtained flooded 2 minutes in Nafion and surfactant OP-10 and nanometer Pd particle mixed solution, adopt the two-wheel wheel to roll and roll the unnecessary mixed resin solution in removal surface, the two-wheel wheel rolls when rolling, gap between two wheels is 12 microns, 120 ℃ of 40 seconds of heat treatment, the thickness that obtains is 10.6 microns to perforated membrane after rolling in vacuum drying chamber; Film after the heat treatment flooded 2 minutes in above-mentioned Nafion and surfactant OP-10 and nanometer Pd particle mixed solution, roll to roll with two-wheel wheel and remove the unnecessary resin compound in surface, two-wheel wheel rolls when rolling, and the gap between two wheels is 12 microns, and the thickness that obtains is 11 microns;
4, the film that step 3 is obtained places isopropyl alcohol to soak and removed surfactant in 10 minutes, soaks 10 minutes in the deionized water of boiling then, promptly obtains having the multi-layer nano compound proton exchange membrane from humidification and water holding capacity.
The resulting multi-layer nano compound proton exchange membrane that has from humidification and water holding capacity is 60 ℃ in temperature, normal pressure hydrogen, and atmospheric air, active area are 25cm
2Under the condition, test the results are shown in accompanying drawing 5.
1, the porous PTFE film of getting 20 micron thickness, 0.05～3 micron in aperture, porosity 82% is fixed on the polycarbonate membrane of 40 micron thickness, adopts the H of 5wt% successively
2O
2The aqueous solution and absolute ethyl alcohol clean the PTFE film, in 60 ℃ drying box dry 20 minutes then;
2,200mL butyl titanate and the mixing of 60mL acetate are placed in the filter tunnel, with 10mL/ minute speed mixed solution is splashed in the 800mL deionized water under the high-speed stirred, continue to stir 1 hour, add the 15mL red fuming nitric acid (RFNA) then and be heated to 60 ℃ of lasting stirrings 2 hours, obtain the TiO of 7 nanometers
2Nano particle; Press sulfonated polystyrene-polyethylene/butylene-polystyrene resin aqueous isopropanol 80g, OP-10 surfactant 1.5g, the TiO of 10wt%
2Nano particle 0.7g prepares mixed solution, cleaned PTFE perforated membrane was flooded in mixed solution 2 minutes, then with two-wheel wheel roll roll remove the unnecessary mixed resin solution in surface and with resin extruded in the micropore of composite membrane, the two-wheel wheel rolls when rolling, gap between two wheels is 11 microns, perforated membrane after rolling in vacuum drying chamber in 120 ℃ of 40 seconds of heat treatment, 10 microns of the thickness that obtains; Film after the heat treatment is at above-mentioned sulfonated polystyrene-polyethylene/butylene-polystyrene resin, OP-10 and TiO
2Dipping is 2 minutes in the mixed solution of nano particle, and then rolls with two-wheel wheel and to roll, and when rolling, the gap between two wheels is 12 microns, the perforated membrane after rolling in vacuum drying chamber in 80 ℃～140 ℃ 40 seconds of heat treatment, 10.1 microns of the thickness that obtains; Again with its film at above-mentioned sulfonated polystyrene-polyethylene/butylene-polystyrene resin, OP-10 and TiO
2Dipping is 2 minutes in the mixed solution of nano particle, and then rolls with two-wheel wheel and to roll, when rolling, gap between two wheels is 12 microns, perforated membrane after rolling in vacuum drying chamber 140 ℃ of 40 seconds of heat treatment, 10.4 microns of the thickness that obtains, this moment, film became transparent;
3, get 0.5gH
2PtCl
6Add in the 200mL ethylene glycol with 10gNaOH, be heated to 150 ℃ and continue to stir 60 minutes, obtain the Pt nano particle that ethylene glycol disperses, add concentrated sulfuric acid centrifugation then and go out the Pt nano particle, its grain diameter is 2.5 nanometers.With sulfonated polystyrene-polyethylene/butylene-polystyrene resin aqueous isopropanol of 10wt% and surfactant OP-10 and nanometer Pt particle according to solid-state mass ratio preparation in 8: 4: 1 mixed solution; The transparent film that step 2 is obtained flooded 2 minutes in this mixed liquor, adopt the two-wheel wheel to roll then and roll the unnecessary resin compound in removal surface, the two-wheel wheel rolls when rolling, gap between two wheels is 12 microns, perforated membrane after rolling in vacuum drying chamber in 120 ℃ of 40 seconds of heat treatment, 10.7 microns of the thickness that obtains; Film after the heat treatment, dipping 2 minutes in sulfonated polystyrene-polyethylene/butylene-polystyrene resin aqueous isopropanol of above-mentioned 10wt% and surfactant OP-10 and nanometer Pd particle mixed solution again, and then adopt the two-wheel wheel to roll and roll the unnecessary mixed resin solution in removal surface, when rolling, gap between two wheels is 12 microns, 11.2 microns of the thickness that obtains;
4, the film that step 3 is obtained places isopropyl alcohol to soak and removed surfactant in 10 minutes, soaks 10 minutes in the deionized water of boiling then, promptly obtains having the multi-layer nano compound proton exchange membrane from humidification and water holding capacity.
The resulting multi-layer nano compound proton exchange membrane that has from humidification and water holding capacity is 60 ℃ in temperature, normal pressure hydrogen 300mL/ minute, and normal pressure oxygen 1960mL/ minute, active area are 25cm
2Under the condition, test the results are shown in accompanying drawing 6.
Claims (9)
1, a kind of preparation method with multi-layer nano compound proton exchange membrane of self-moistening function is characterized in that being undertaken by following steps in sequence:
1st, get clean voided polytetrafluoroethylene film and containing proton conductive resin and SiO
2Or TiO
2Fully flood in the mixture alcoholic solution of nano particle, the content of proton conductive resin is 1-5wt% in the mixture, and the content of surfactant alkylphenol-polyethenoxy 10 ethers is 0.6-4wt%, SiO
2Or TiO
2The mass ratio of nano particle and proton conductive resin is 0.01-0.2: 1;
2nd, will be impregnated with proton conductive resin and SiO
2Or TiO
2The perforated membrane of nanoparticle mixture adopts the two-wheel wheel to roll to roll and removes the unnecessary resin compound in surface, and the perforated membrane after rolling is 80 ℃～140 ℃ 40～60 seconds of heat treatment in vacuum drying chamber;
3rd, the operation of dipping and step 2 obtains water-keeping proton exchange film until the film bleach in the repeating step 1;
4th, the transparent water-keeping proton exchange film that step 3 is obtained fully floods in proton conductive resin and nanometer Pt or nanometer Pd granulate mixture alcoholic solution, the content of proton conductive resin is 4wt% in the mixture, the content of surfactant alkylphenol-polyethenoxy 10 ethers is 2wt%, and the mass ratio of nanometer Pt or nanometer Pd particle and proton conductive resin keeps 0.01-0.05: 1;
5th, will be impregnated with the water-keeping proton exchange film of proton conductive resin and nanometer Pt or nanometer Pd granulate mixture, adopt the two-wheel wheel to roll to roll and remove the unnecessary resin compound in surface, the perforated membrane after rolling is 80 ℃～140 ℃ 40～60 seconds of heat treatment in vacuum drying chamber;
6th, repeating step 4 and 5 once obtains the multi-layer nano composite membrane successively;
7th, the composite membrane that step 6 is obtained soaks in ethanol or isopropyl alcohol and removed surfactant in 5～10 minutes, deionized water in boiling soaked 8～10 minutes then, after the air dry, in vacuum drying chamber,, promptly obtain having multi-layer nano compound proton exchange membrane from humidification and water holding capacity 120～140 ℃ of 40～60 seconds of heat treatment;
Wherein the solvent of the described alcoholic solution of step 1 and step 4 adopts any in ethanol, propyl alcohol and the isopropyl alcohol.
2, the method for claim 1 is characterized in that described proton conductive resin is any in perfluorinated sulfonic resin, sulfonation trifluorostyrene resin, polymethyl-benzene 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.
3, the method for claim 1 is characterized in that described polytetrafluoroethylene film thickness is 1～40 micron, 0.05～4 micron in aperture; Porosity 70%～95%.
4, the method for claim 1 is characterized in that described polytetrafluoroethylene film thickness is 7～15 microns, 0.05～0.2 micron in aperture, porosity 80～90%.
5, the method for claim 1 is characterized in that described clean voided polytetrafluoroethylene film, adopts voided polytetrafluoroethylene film to use the H of 3～5.5wt% successively
2O
2The aqueous solution and absolute ethyl alcohol clean, and be dry in 60 ℃ drying box then.
6, the method for claim 1 is characterized in that clean voided polytetrafluoroethylene film is containing proton conductive resin and SiO
2Or TiO
2Dip time is 1～5 minute in the mixture alcoholic solution of nano particle.
7, the method for claim 1 is characterized in that transparent water-keeping proton exchange film dip time in proton conductive resin and nanometer Pt or nanometer Pd granulate mixture alcoholic solution is 1～5 minute.
8, the method for claim 1 is characterized in that being impregnated with proton conductive resin and SiO
2Or TiO
2The perforated membrane of nanoparticle mixture adopts the two-wheel wheel to roll when rolling, and the gap between two wheels is greater than 1～2 micron of the thickness of film.
9, the method for claim 1 is characterized in that being impregnated with the water-keeping proton exchange film of proton conductive resin and nanometer Pt or nanometer Pd granulate mixture, adopts the two-wheel wheel to roll when rolling, and the gap between two wheels is greater than 1～2 micron of the thickness of film.
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| CN103904344A (en) * | 2014-04-23 | 2014-07-02 | 北京九谷超微科技有限公司 | Proton exchange membrane and preparation method thereof |
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